POWERS OF TEN

10» 2 T tera
9
10 G g»ga

10
6
M mega
3
10 k kilo

10- 3 m milli
6
1(T M micro
10- 9 n nano
12
10 P pico
5
io-' f femto
10" 18
a atto
 £po~»-

CONSTANTS AND CONVERSION FACTORS

(to four significant figures)

speed of light c = 2.998 X 10 8 m/s

electron charge unit e = 1.602 X 10" 19
C
1

Coulomb force constant

" ire,
= 8.988 X 10
9
N myC•
J

477e
.2
e
= 1.440 eV •
run
4we
electron mass m = e
9.109 X 10~ 31 kg = 0.5110 MeV/c 2
proton mass Mp = 1.673 X 10" 27 kg = 938.3 MeV/c 2
M P
=
proton -electron mass ratio 1836
m ,

~ 34
Planck's constant h = 6.626 X 10 J •
s = 4.136 X 10~ 15 eV •
s

he = 1240 eV nm •

h = 1.055 X 10"
34
J •
s = 6.582 X 10-' 6 eV •
s

he = 197.3 eV nm •

-1
Avogadro's number NA = 6.022 X 10
23
mole
Boltzmann's constant kB = 1.381 X 10" 23 J/K = 8.617 X 10~ 5 eV/K
h
electron Cbmpton wavelength = 2.426 X 10
,2
m
m e
c

Bohr radius a = 5.292 X 10"" m

Rydberg energy unit E = 13.61 eV
Rydberg constant /?„ = 1.097 X 10
7
m '

fine structure constant a =

137.0
_9
Bohr magneton fiB = 9.274 X 10" 24 A •
m 2
= 5.788 X 10 eV/G
_l2
nuclear magneton fi N = 3.152 X 10 eV/G
gravitational constant G= 6.673 X 10"" N m •
2
/kg 2
electron volt eV = 1.602 X 10
19
J
atomic mass unit u = 1.661 X 10" 27 kg = 931.5 MeV/c 2
_28
cross section unit barn = 10 m 2
= (10 fm)
2

light-year lt-y = 9.461 X 10

15
m
 Digitized by the Internet Archive
in 2013

http://archive.org/details/introductiontostOObreh
INTRODUCTION
TO
THE
STRUCTURE
OF
MATTER
 INTRODUCTION
TO
THE
STRUCTURE
OF
MATTER

A Course in Modern Physics

John J. Brehm
and
William J. Mullin
University of Massachusetts
Amherst, Massachusetts

WILEY
John Wiley & Sons
New York Chichester Brisbane Toronto Singapore
Copyright © 1989, by John Wiley & Sons, Inc.

All rights reserved. Published simultaneously in Canada.

Reproduction or translation of any part of

this work beyond that permitted by Sections

107 and 108 of the 1976 United States Copyright
Act without the permission of the copyright

owner is unlawful. Requests for permission

or further information should be addressed to
the Permissions Department, John Wiley & Sons.

Library of Congress Cataloging in Publication Data:

Brehm, John J.
Introduction to the structure of matter.

Bibliography
Includes index.
1. Physics. 2. Matter — Constitution. I. Mullin,
William J. II. Title.

QC21.2.B74 1989 530 88-5768

ISBN 0-471-60531-X

Printed in the United States of America

10 987654321
 to

Mary Ellen and Sandra

with love
 PREFACE

A
first course in modern physics should be

exciting and rewarding for studentand teacher alike. Such a course offers an
opportunity to appreciate the wondrous findings of the 20th century as milestones in
the growth of a whole new science. From this perspective the student can take pleasure
in the discovery of new phenomena and the teacher can draw inspiration from the
revolutionary new ideas.

This course should be offered in a year-long format to serious students of physics no

later than their junior year. An early introduction to the 20th century is essential if the
students are to recognize soon enough the continuing flow of developments in modern
physics. The course should also be reasonably thorough so that undergraduates can
build on it as a secure foundation. Our textbook is aimed at this body of readers with
these objectives in view.
A first course in modern physics can be a daunting experience for the students, and
even for the teacher. The revolutionary nature of the material invites the students to
challenge all their classical learning and forces the teacher to encourage a continually
questioning posture. The adoption of such an attitude toward physics is difficult to
learn, and manner. This problem is compounded by the
to teach, in a constructive
fact that the subject has become too vast to be surveyed in its entirety in a single
year-long presentation. Compromises must be faced at every turn, as students and
teacher together seek a balance between the depth of the questions raised and the
breadth of the topics addressed, out of a seemingly open-ended agenda.
There may have been a time, several generations ago, when a teacher could present
all the great discoveries of modern physics in a single two-semester course. Those
prospects are no longer realistic if the level of presentation is to be sufficiently deep for
serious students. Considerable depth is desired if the students are to build a solid base
for future coursework. Such students are inclined to ask many penetrating questions.
Their goals are not properly served by a mere survey of factual information, with a
promise of detail yet to come in some future course. These arguments in favor of
depth can be accommodated through judicious planning by the teacher as to the
breadth of material included in the course.
The text writer must acknowledge this conflict between depth and breadth, and
make allowance for a variety of compromises. Our book takes the view that any
year-long course for physics students should be thorough enough to explicate the basic

VII
ww Preface

questions, and yet extensive enough to cover many areas. We also believe that, within
reason, the text should offer every topic desired by every teacher, even if the sum of all
the topics is too much for two semesters. This diversity of offerings is necessary if a
given teacher is to have access to every possible pathway through the available
material.
We recommend that four foundation stages be prepared first, and one of two main
routes be chosen afterward, with the adoption of this book as a text. The first four
quantum theory,
areas cover special relativity, introduction to quantum mechanics,
and application to atoms. These topics occupy Chapters 1-9 and should consume
more than one semester of lecture time. The teacher may then choose to go from
atoms to larger quantum systems, such as molecules and condensed matter, or to
smaller quantum systems, such as nuclei and elementary particles. The one route
spans Chapters 10-13, and the other spans Chapters 14-16. Our textbook gives ready
access to either of these alternatives.
Every topic in the book is developed to contain a core of subject matter for the
teacher's lectures and a body of supporting material for the students' readings. We
devote a substantial portion of the text to side-reading because we expect the students
to turn from the lecture to the book for a properly detailed understanding of the
subject. This plan assumes the usual ideal classroom setting, where the teacher
introduces the students to concepts and applications, and the students refine their
grasp of the material by studying on their own.
The book is aimed generally at physics majors in their junior year, although some
flexibility is built into this choice of level. In fact, a large portion of the material has
actually been taught at the University of Massachusetts to second-semester sophomores
and first-semester juniors. We assume an adequate background to be three previous
semesters of physics, a la Resnick and Halliday. We take for granted any topic found
in this preparatory body of coursework, and we occasionally reiterate certain classical
points if they bear directly on new ideas. The new material is always constructed in a
self-contained and thorough manner, consistent with the intended level. Sometimes it
is up the material from the ground and eventually "take off"
instructive to build
toward a rather high level. One of our main assumptions is that interested students
want to " take off" on occasions, with the guidance of the teacher. These instances of
excess occur here and there throughout the book and are easy to bypass if that is the
teacher's wish.
The text emphasizes discoveries and ideas, and incorporates analytical formalism
sufficient for the level of presentation. We regard our treatment of modern physics as
a prelude to a subsequent course in quantum mechanics. Hence, the text is supposed

to build a case for the quantum theory and then supply enough quantum machinery
to give the students an understanding of all the different quantum systems. The text is
not intended as a presentation of quantum formalism, however. Instead, we use only

the Schrodinger equation to convey most of the quantum mechanics in the book.
Thus, many of the essential "words" of quantum mechanics (Hamiltonian, commuta-
tion relation, spinor, matrix element, . .
.
) never actually appear, even though the
concepts lie just beneath the surface in our discussions.
The mathematical demands book are quite consistent with the level intended
of the
for the physics. We assume that all somewhat skilled in the
students at this level are
use of calculus. We also take the view that exposure to new mathematics is a worthy

secondary objective of the course and its accompanying text. Matrices are employed
on a few occasions to elucidate certain algebraic considerations. Complex numbers are
put to constant use in the solution of the Schrodinger equation and the interpretation
 Preface ix

of quantum mechanics. Differential equations are encountered throughout our de-

scription of the quantum theory. We bring forward the necessary mathematical
procedures and assume no previous familiarity in this area. Special deliberation is

exercised when the topics of interest are governed by partial differential equations.
Our main assumption about the introduction of unfamiliar mathematical techniques
is that the students are willing to move quickly into the use of differential equations in
order to grasp the interpretation of the solutions. We promote the development of
these capabilities for a good and healthy cause. The students' analytical powers are
strengthened for the future, and their understanding of the subject is enriched as a
result. Modern physics is ideal in this respect because the subject cannot be properly
supported without a certain amount of mathematical scaffolding and because the new
ideas can be fully brought to life with this support.
History is also included in order to present modern physics as a sort of adventure in
20th century science. We insert these narrative elements whenever we wish to illustrate
the growth of ideas and put separated events in proper context. Modern physics
should be viewed as an ongoing adventure, and historical background can be used as a
suitable vehicle to convey this impression.
Every major subject area has its own chapter in the book. Some of the chapters are
rather long because of the broad scope of the particular areas. This aspect of the book
should be ignored by the reader since every chapter is comfortably divided into
sections of manageable length. The sections themselves should be regarded as the
basic logical units of the text.
At least one example appears at the end of almost every section. We put all

numerical computations and some algebraic manipulations into these examples so that
we can separate illustrative material from the main flow of the text. Every topical area
is further illustrated by a wide selection of problems at the end of each chapter.
The book includes only one appendix containing our table of nuclear properties.
We deviate from the usual practice followed in other books and choose not to relegate
supporting material to a series of appendixes. Instead, we evaluate every fragment of
material on its own instructional merits. In many cases these fragments are important
for their mathematical content and are worthwhile for students to learn. Any item of
pedagogic interest is given its own place along with other pedagogic matter in the
main body of the text, and all items of less instructional value are left out of the text
altogether.
It is sometimes necessary to digress and set aside a certain derivation so that the
accompanying topic can be presented without interruption. We employ these digres-
sions sparingly and call them "details." The occasional detail is inserted at the end of
the relevant section as a sensible alternative to the use of an appendix at the end of the
book. This practice enables the reader to locate useful information out of the main
flow but still near its proper place in the text.

We have argued for a balance between depth and breadth in the teaching of
modern physics. A teacher can strike such a balance with the aid of this book by
exercising selectivity over all the available material. It is clear that every topic cannot
be covered properly in a single year. Our hope for the students is that they find this
book instructive as a presentation of the teacher's choice of topics and also enlighten-
ing as a source of further reading later in their careers.

John J. Brehm
Amherst, Massachusetts William J. Mullin
 ACKNOWLEDGMENTS

ueveral of our colleagues contributed bits of

wisdom and advice to this project. We would like to thank Ian Aitchison, Tom Arny,
Ed Chang, John Donoghue, Bob Gray, Bob Hallock, Ted Harrison, Bob Krotkov,
Francis Pichanick, Kandula Sastry, Janice Shafer, and Mort Sternheim for offering us
the benefits of their expertise.
We should also extend our appreciation to the reviewers who provided constructive
criticisms of the manuscript. All their remarks were given serious attention, and almost
all were acted on in one way or another to improve the quality of the presentation.
We were extremely fortunate to have the assistance of Nellie Bristol in the
preparation of our text. Her ability to convert a disorderly handwritten draft into a
typed manuscript was needed to carry out the project, and her customary good humor
was always greatly appreciated.
We would express our gratitude to our families too, if we could only find the words.
Their encouragement was there at the start when none of us could judge the scale of
the endeavor, and continued to be there throughout as the enormity of the work
became all too apparent.

J.J-B.

W. J. M.

xi
 CONTENTS

CHAPTER ONE
RELATIVITY /

1-1 The Luminiferous Aether 2

1-2 Principles of Relativity 6
1-3 Time Dilation and Length Contraction //

1-4 Relative-Motion Symmetry 20

1-5 The Lorentz Transformation 25

1 -6 Transformation of Velocity 32

1-7 Space-Time 38
1-8 Relativistic Momentum and Energy 44
1-9 Relativistic Dynamics 50
1-10 Collisions and Reactions 53
1-11 Four- Vectors 60

Problems 66

CHAPTER TWO
PHOTONS 73

2-1 Blackbody Radiation 75

2-2 Standing Electromagnetic Waves

2-3 The Maxwell- Boltzmann Distribution

2-4 The Quantum Hypothesis 93

2-5 The Photoelectric Effect 99

2-6 X Rays 103

2-7 The Compton Effect 107

2-8 7 Rays and Electron-Positron Pairs 114

Problems 'IS

xlii
xiv Contents

CHAPTER THREE
INTRODUCTION TO THE ATOM m
3-1 The Reality of Molecules and Atoms 122

3-2 The Electron 126

3-3 The Nuclear Model of the Atom 131

34 Rutherford Scattering 134

3-5 The Quantum Picture of the Atom 144

3-6 The Bohr Model of the One-Electron Atom 149

3-7 Characteristic X Rays 161

3-8 Atomic Processes and the Excitation of Atoms 165

3-9 The Laser 170

3-10 The Quantum of Action 175

Problems 178

CHAPTER FOUR
MATTER WAVES m
4-1 De Broglie's Hypothesis 182

4-2 Electron Diffraction 185

4-3 Particle-Wave Duality 188

4-4 Determinism and Randomness 193

4-5 The Uncertainty Principle 195

4-6 Waves and Wave Packets 205

Problems 216

CHAPTER FIVE
QUANTUM MECHANICS m
5-1 The Schrbdinger Equation 220

5-2 Probability Interpretation 226

5-3 Stationary States 231

5-4 The One-Dimensional Box 234

5-5 The Harmonic Oscillator 240

5-6 Eigenfunctions and Eigenvalues 251

5-7 Expectation Values 260

5-8 Radiative Transitions 268

5-9 Barrier Penetration 271

5-10 Two-Particle Systems in One Dimension 283

5-1 1 The Three-Dimensional Box 288

Problems 294

CHAPTER SIX
QUANTIZATION OF ANGULAR MOMENTUM soo

6-1 Central Forces 301

6-2 The Schrbdinger Equation in Spherical Coordinates 303

 Contents xv

6-3 Rotational Motion 308

6-4 Separation of Variables 313

6-5 Angular Momentum Quantum Numbers 320

6-6 Parity 325

6-7 Quantization of Energy 328

6-8 Observables in Spherical Coordinates 333

Problems 341

CHAPTER SEVEN
THE ONE-ELECTRON ATOM 344

7-1 The Radial Differential Equation 345

7-2 Solutions of the Radial Equation 348

7-3 Degeneracy 357

7-4 Probability Distributions 360

7-5 Electric Dipole Selection Rules 366

Problems 373

CHAPTER EIGHT
SPIN AND MAGNETIC INTERACTIONS 375

8-1 Atoms and Light in a Magnetic Field 376

8-2 Orbital Magnetic Moments 380

8-3 The Normal Zeeman Effect 385

8-4 The Stern- Gerlach Experiment 390

8-5 The Properties of Electron Spin 394

8-6 Magnetic Resonance 397

8-7 Spin- \ Thought Experiments 400

8-8 Addition of Orbital and Spin Angular Momenta 405

8-9 The Spin-Orbit Interaction 410

8-10 Results from Relativistic Quantum Mechanics 416

8-1 1 The Zeeman Effect 425

8-12 Hyperfine Structure 431

Problems 437

CHAPTER NINE
COMPLEX ATOMS 440

9-1 The Central-Field Model 440

9-2 The Exclusion Principle 446

9-3 The Ground States of Atoms and the Periodic Table 449

9-4 X Ray Spectra 457

9-5 Electron Antisymmetry 464

9-6 The Helium Atom 469

9-7 Alkali Atoms 476

xvi Contents

9-8 Angular Momentum Coupling 481

9-9 Spectroscopic Aspects of LS Coupling 488

Problems 498

CHAPTER TEN
MOLECULES 501

10-1 Binding by Quantum Tunneling: H/ 502

10-2 Covalent Bonding: H 2 508
10-3 Ionic Bonding: LiF 512
10-4 Van der Waals Interaction 517
10-5 Polyatomic Molecules: H 2 and CH 4 521
10-6 Botation 522
10-7 Vibration 524
10-8 Spectra 527
Problems 533

CHAPTER ELEVEH
QUANTUM STATISTICAL PHYSICS 538

11-1 Particle Indlstingulshability 539

11-2 Thermal Distribution Functions 543

11-3 High-Temperature. Low-Density Limit 554

11-4 Photon Statistics 559

11-5 Phonons 560

11-6 Low-Temperature Fermi-Dirac Systems 587

Problems 571

CHAPTER TWELVE
SOLIDS 575

12-1 The Structure of Solids 576

12-2 Bragg Scattering 584

12-3 The Free-Electron Theory of Metals 587

12-4 Energy Bands in Solids 596

12-5 The Band Theory of Metals. Insulators, and Semiconductors 606

12-6 Semiconductors 608

12-7 Semiconductor Devices 615

1 2-8 Phonon Dynamics 621

12-9 Magnetism in Solids 627

Problems 631
 Contents xvii

CHAPTER THIRTEEN
SUPERFLUIDS AND SUPERCONDUCTORS m
13-1 Experimental Characteristics of Superfluity 635

13-2 Experimental Characteristics of Superconductors 638

13-3 Superflow and the Energy Gap 640

13-4 The Bose-Einstein Condensation 643

13-5 The Two-Fluid Model of Superfluid Helium 647
13-6 Cooper Pairs and the BCS Theory 650

13-7 Theoretical Interpretation of Superconducting Experiments 654

13-8 The Josephson Effect 658

13-9 Other Superfluid Systems 664

Problems 665

CHAPTER FOURTEEN
PROPERTIES AND MODELS OF THE NUCLEUS 667

14-1 Nuclear Particles 668

14-2 Nuclear Systematics 673

14-3 Electron Scattering and the Nuclear Radius 678

14-4 Nuclear Mass and Binding Energy 682

14-5 The Semiempirical Mass Formula 689

14-6 The Fermi Gas Model 695

14-7 The Nucleon-Nucleon Interaction 699

14-8 A Simple Model of the Deuteron 705

14-9 Magic Numbers 710

14-10 The Nuclear Shell Model 714

14-11 Spins and Moments in the Shell Model 720

14-12 Charge Independence and Isospin Symmetry 728

Problems 736

CHAPTER FIFTEEN
NUCLEAR PROCESSES 740

15-1 Radioactivity 741

15-2 The Exponential Decay Law 745

15-3 a Decay 75!

15-4 Decay 759

15-5 The Weak Nuclear Interaction 767

15-6 y Decay 773

15-7 Resonance Radiation 779

15-8 Introduction to Nuclear Reactions 783

7
15-9 Nuclear Reactions and Nuclear Structure 89
xviii Contents

15-10 Nuclear Fission 796

15-11 Fusion and Thermonuclear Energy 804

Problems 811

CHAPTER SIXTEEN
ELEMENTARY PARTICLES sis

16-1 Introduction lo High-Energy Physics 816

16-2 Particles and Fields 821

1 6-3 Mesons and the Nuclear Force 826

1 64 Muons and Pions 830

16-5 Neutrinos 834

16-6 Nonconservation of Parity 837

16-7 The Weak Interaction 842

1 6-8 Strangeness 846

1 6-9 Neutral K Decay and CP Symmetry 852

16-10 Isospin 858

16-11 Baryon and Meson Resonances 864

16-12 Quarks 870

16-13 The Electromagnetic and Weak Interactions of Quarks 875

16-14 The Electroweak Interaction 881

16-15 Color and the Strong Interaction 886

16-16 Gauge Symmetries 893

16-17 Grand Unification 902

Problems 909

APPENDIX A
TABLE OF NUCLEAR PROPERTIES a-i

BIBLIOGRAPHY a-b

ANSWERS a-12

PHOTO CREDITS M6

NAME INDEX / -/

SUBJECT INDEX 1-3

 ONE
RELATIVITY

/he 20th century has been a time of extraor-

dinary achievement in physics. Every great discovery of the era has had a profound
influence on our modern view of the natural world.
This age of new ideas began with an awakening anxiety over the status of the
classical laws. Classical physics was regarded as well established, but only within a
proven domain of applicability. In fact, classical physics had apparent limitations
since the established laws were unable to account for certain puzzling phenomena.
Eventually, there was enough accumulated evidence of this sort to call for a
reexamination of existing principles.
The first decades of the 20th century saw the coming of the special theory of
relativity and the beginning of the quantum theory. These were not mere extensions of
classical physics. The new theories revised the foundations of the discipline and defined
the framework of modern physics. A revolution has resulted, affecting the course of
developments in almost every area of modern science.
Classical physics has been found to have boundaries of validity. Departures from
the classical regime may be viewed as thrusts in two main directions across these
boundaries. The first path leads us to relativity, and the second much-broader path
leads us to quantum mechanics. We are confronted with new situations in either
direction. The problems usually involve very large velocity in the first case, and very
small size in the second. We may adopt these two extremes as preliminary criteria to
identify the domains of relativistic and quantum physics.
We start with relativity because of its two fully
historical priority as the first of the
developed theories. It is instructive to look for historical background throughout our
presentation of modern physics, and it is particularly informative to go back into the
19th century in order to set the stage for relativity.

There were no serious reasons to question the soundness of classical mechanics

before 1900. J. C. Maxwell, L. E. Boltzmann, and others drew upon Newton's laws
and employed classical methods to interpret the thermal behavior of systems contain-
ing large numbers of particles. Hence, it could be said that classical statistical physics
grew up in an environment cultivated by the validity of Newtonian mechanics. These
contributions to thermal physics were among the main advances of 19th century
science.
2 Relativity

The towering achievement of the period was the unification of the laws governing
electricity and magnetism in Maxwell's electromagnetic theory. All the known proper-
ties of charges and currents and all the known behavior of electric and magnetic fields
were described by Maxwell's equations in agreement with existing experimental
evidence. The theory went further and predicted the propagation of oscillating electric
and magnetic fields through empty space. It was also possible to predict the speed of
wave propagation in terms of parameters appearing in Maxwell's equations. Labora-
tory evidence for electromagnetic waves in vacuum was subsequently demonstrated in
the experiments of H. R. Hertz. The prediction for the wave speed has been confirmed
many times in several different experiments during the past century and a half. The
current value
c = 2.99792458 X 10 8 m/s
has become known
as the speed of light, a quantity conveniently approximated as
8
3 X 10 m/s,an accuracy of three significant figures. (In fact, c has recently been
to
defined as exactly 299792458 meters per second, leaving the meter to be determined by
experiment.)
The 19th century was a productive period, when scientists could reaffirm Newton's
laws and verify Maxwell's equations as parallel bodies of doctrine. Together these
classical formulations described physics successfully over an enormous range of
applications. By 1900, however, a confrontation of principle had begun to develop
between Newton's mechanics and Maxwell's electrodynamics. The point at issue
involved the description of physical behavior in moving frames of reference. The
conflict between the two systems of classical laws was addressed and resolved by the
theory of relativity.
To appreciate the problem, we have to recall some basic notions about the use of
coordinate systems for the description of particles. In particular, we wish to examine
how these descriptions change when we pass to different frames of reference, especially
those in motion at constant relative velocity. Newtonian mechanics tells us that an
inertial frame of reference is a coordinate system in which Newton's first law holds.
Any other frame in uniform relative motion is also inertial, and so the whole
Newtonian scheme is valid in all such frames. We find, however, that electromagnetic
effects such as the phenomenon of light appear to select a privileged frame for the

validity of Maxwell's equations, and we are thereby led to a very unsatisfactory

logical conclusion.
The main issue in these arguments proves to be the behavior of the classical laws
under a transformation of the coordinates from one frame to another. The theory of
relativity examines this question with regard to the observation of the physical
quantities and the meaning of the physical laws. Principles of relativity have appeared
in physics before, associated with the names of Galileo and Newton, so that this line of

inquiry has a familiar previous theory. In modern physics we are concerned with the
principles of special relativity put forward by A. Einstein in 1905. The propagation of
electromagnetic waves and the speed of light are central concepts in the logic of this

theory. When we follow the logic we find that the theory requires us to alter our naive
attitudes about the treatment of space and time.

1-1 The Luminiferous Aether

The identification of light as an electromagnetic wave led scientists of the 19th century
topresume that light had properties in common with mechanical forms of wave motion.
The mathematical similarity between sound and light was apparent since both types
 /- / The Lumini/erous Aether

Albert Einstein

of wave were described by solutions of the wave equation. Of course, there were
distinctions to observe as well. Sound waves were known to be longitudinal oscillations
of the medium, without polarization properties, while electromagnetic waves were
understood as oscillations of electric and magnetic fields, with polarization transverse
to the direction of propagation. The similarities suggested that light, like mechanical
waves, should require a medium for support and propagation. The medium was
known as the aether, an entity that supposedly possessed some very remarkable
properties. It had to fill empty space with a universal tension in order that electromag-
netic waves could propagate in vacuum at the unique speed c. The medium also had
to beinfinitely rigid and incompressible, so that longitudinal disturbances could not
exist, and yet had to offer no obstacle whatsoever to the motion of material bodies.

Thus, the aether was conceived to be a mechanical medium for light with no
mechanical properties in the presence of matter.
Given the advantages of hindsight, we should find it difficult to appreciate the
general acceptance and appeal of such a contrivance. Physicists of the period were
accustomed to the adoption of mechanical models and were not receptive to the
possibility of wave motion without a mechanical medium. Indeed, Maxwell himself
had advocated an "aethereal medium" in his own definitive work on electromagnetic
theory. When the predicted waves were discovered after his death, the scientific
community was predisposed to accept the aether as a working hypothesis and examine
its further consequences.
We should realize that a philosophical position of some depth is rooted in these
arguments. The an aether implies mechanical wave propagation where
existence of
disturbances of the medium travel through the medium. In this context, the speed of
propagation refers to the speed of wave motion relative to the medium. Believers in the
4 Relativity

aether would therefore regard the accepted value of c as the speed of light waves with

respect to their aethereal medium. This aether would then represent an absolute frame of
reference in which all electromagnetic waves travel with the speed c. Furthermore, since

the existence of the waves and the prediction of the wave speed are consequences of
Maxwell's equations, it follows that the aether must constitute the unique frame of
reference in which Maxwell's equations are valid. Electromagnetic theory would then
have to assume an altered form in another frame in motion through the aether so that
light waves would be expected to have a different velocity of propagation with respect
to that moving frame.
The aether was obviously more than just a mechanical convenience for the
propagation of light. It also embodied a logical attitude toward the validity of certain
established physical laws. Manifestations of the aether were presumably subject to
experimental investigation. Aether believers did not presuppose that the Earth was at
rest in the absolute frame of reference and set out to devise an experiment capable of
detecting the motion of the Earth relative to the aether. The required apparatus had
to be sufficiently sensitive to measure an Earth speed presumed to be much smaller
than c. The historic experiment was performed with the aid of an interferometer,
which had been developed by A. A. Michelson for the measurement of lengths to
extraordinary precision. Michelson was joined in the aether measurement by E. W.
Morley, and the results of the famous Michelson-Morley experiment were reported in

1887.
Theinterferometer is sketched in Figure 1-1. Light of a definite wavelength is split
into two beams by a half-silvered mirror; the two beams then travel at right angles
and are reflected back by the two mirrors, and 2, shown in the figure. The beam1

returning from mirror 1 is finally reflected to the observer where it interferes with the
beam returning from mirror 2. The two beams are coherent since they originate from
a single source, and the difference in their optical paths determines how they interfere
at the position of the observer. If the paths are of equal length, the two beams have
the same transit time, arrive in phase, and produce constructive interference. This
statement suggests the following way to measure the speed of the Earth through the
aether, since it is implicit in the statement that the speed of light is the same over the
two paths.
In keeping with the aether hypothesis we let c be the velocity of light and u be the
velocity of the Earth with respect to the aether frame. The velocity of light in the
Earth or interferometer frame is therefore

c = c — u. (1-1)

It is convenient to transfer the analysis to the Earth frame and let the aether move
through the interferometer with velocity — u. Then c' represents an aether-drifted
light velocity, analogous to the velocity of a swimmer in moving water. We take the
aether drift to be from right to left in the figure, and, for simplicity, we let the two
arms of the interferometer have exactly the same length d. Equation (1-1) tells us that
the light speeds to the right and to the left are c — u and c + u, respectively.
Therefore, the transit time to mirror 1 and back is

d d 2dc

c — u c + u c — u

The inset to Figure 1-1 shows how to construct c' for the light traveling to mirror 2
 /-/ The Luminiferous Aether

Figure 1-1

Michelson interferometer with arms of equal

length. For the Michelson- Morley
experiment, the aether is presumed to be
moving through the interferometer with speed
u. The aether hypothesis implies that the light
speeds differ over the two paths, as shown.

Mirror 2

Half-silvered
mirror

© =>-
^=^
d
Light source

Observer Mirror 1

-^ Aether drift

and back. The light speed c' over this path is evidently (c
2
— «
2
)
1/2
each way.
Consequently, the transmit time to mirror 2 and back is

2d
2
(,._„«)./*

Since u/c is expected to be very small, we can use the binomial expansion to write

2 \ -1/2 2
u 1 u
1
"7 = 1 + -z +
C
and 1

c
= !
+ «- +

The two 2 /,2

transit times are then given to order (u /c ) by

2
2d
-
2rf/

c \
1 + -
ti

c
and ,
2
=
T
I

1 + --
1u

The difference in transit times causes the beams to arrive at the observer out of phase.
To the same order, the optical path difference is c{t x
— t
2 ). The number of wave-
lengths contained in this distance determines the number of fringes by which the
interference pattern departs from the situation for zero path difference. A rotation of
the apparatus by 90° introduces a change of roles between the times <, and t
2
. The
 )

Relativity

total number from the one orientation of the interferometer to the

of fringes shifted
other is consequently twice the number identified above. This maneuver is particularly
useful for the more realistic circumstance in which the interferometer arms are of
unequal length. The final result for the fringe shift upon 90° rotation of the device is

c(t, — t., d l u
(1-2)

We emphasize that these assertions are predicated upon the adoption of the aether
hypothesis and the use of Equation (1-1).
The experimenters were confident that a shift as small as ^ of a fringe could be

detected, whereas the expected result was around 8n = Michelson-

0.4. Instead, the

Morley experiment yielded a null result; no fringe shift was observed. Subsequent
versions of the experiment have reproduced this same result. To the consternation of
aether believers everywhere the conclusions were inescapable. The motion of the Earth
through the aether frame was not detectable, and the speed of light in the interferom-

eter was the same for the two perpendicular paths.

A number of revisionist theories came forward around 1900 with the proposition
that the aether existed but nature conspired to prevent its detection. The most notable
of these was a proposal offered by G. F. FitzGerald and H. A. Lorentz. According to
their idea, the interferometer arm parallel to the direction of motion through the
aether was supposed to contract by a factor (1 —
/c 2 ) ^ 2 so that
u
2
and t 2 would be
1
t
x

identical times in the above analysis. This ad hoc suggestion turned out to have its
place in future developments. However, it remained for Einstein to interpret the
problem in its proper light.

Example

The Michelson-Morley experiment used light of wavelength A = 5.9 X

~7
10 m. The interferometer ultimately achieved arm lengths with d = 1 1 m by
the use of multiple reflections along the two perpendicular pathways shown in
Figure 1-1. The speed of the Earth around the Sun was known to be about 30
km/s, and so u/c = 10
4
was used as an estimate for the Earth speed in the
aether frame. Based on these numbers, the fringe shift in Equation (1-2) was
expected to be

11 m 2
8n (10" 4 ) = 0.4,
5.9 X 10" 7 m

as remarked above.

1-2 Principles of Relativity

The concept of the aether as an absolute frame of reference was rendered meaningless
by the Michelson-Morley experiment. Einstein was not really influenced by this
result, even though he had previously entertained the desire to perform such an
 1-2 Principles of Relativity 7

experiment himself. He had already become convinced that notions of absolute rest

and absolute motion should have no observable consequences and that only relative
motion could have physical meaning. This point of view had a previous history. It was
accepted that the laws of mechanics should make no distinction between a state of rest
and a state of motion with constant velocity. The idea that uniform motion must be
relative, and hence detectable only with reference to an external point, originated with
Galileo. This venerable and self-evident relativity principle assumed a new thrust when
Einstein applied it to the propagation of light in vacuum. The question was part of
the problem of reconciling electromagnetism and mechanics to the same relativistic
viewpoint. Einstein investigated this problem during his period of employment at a
Swiss patent office in an environment isolated from the stimulus of institutional
research.
Einstein recognized a conflict between the classical theories of Newton and Maxwell.
He noted that Newtonian mechanics allowed an observer to move at speed c, since an
accelerating force could cause an object to reach any speed if applied long enough,
and he asked how electromagnetic waves traveling in the same direction, also at speed
c, might appear to the moving observer. Because the wave fronts would be accompa-

nying the observer, the oscillations of the propagating fields would not be detectable.
The electromagnetic wave motion predicted by Maxwell's equations would therefore
not exist in the observer's frame of reference. The argument employed the logic of
Newton's laws to deny a logical consequence of Maxwell's laws. This amounted to an
inconsistency or contradiction in the classical theory. Einstein also saw that his
thought experiment furnished a violation of the relativity principle regarding relative
motion. He argued that a moving observer in a closed chamber could know that the
chamber was in motion at light speed, without reference to any external point, by
noting that light could not be observed in the chamber.

Space travel at the speed of light

Impossible according to
the principle of relativity
 .

8 Relativity

Einstein's celebrated paper of 1905 demonstrates a consistent picture of mechanics

and electrodynamics based on the following two principles of relativity:

The laws of electromagnetism are valid in all frames of reference in which the laws
of mechanics hold.
The speed of light in vacuum is the same for all observers independent of their
motion or the motion of the source.

The first postulate implies that observers in relative motion at constant velocity must
agree concerning their expression of the physical laws. The second asserts that these
observers must also agree that light waves propagate at speed c with respect to every
frame of reference in which each particular observer is at rest. Einstein's theory sweeps
the aether aside and declares it to be superfluous with this assertion.
The second postulate is alien to our rudimentary common sense. Consider the
situationshown in Figure 1-2 in which a moving observer 0' carries a light source and
sees wave fronts of light propagating away at speed c. A stationary observer sees
those wave fronts moving also at speed c, even though 0' is approaching at a speed
u, which in principle could be almost as great as c. This seems paradoxical if we react

to the kind of common sense that has taught us to use Equation (1-1) as the rule for
the addition of velocities. However, we have just learned that there is experimental
evidence refuting this rule for the propagation of light. The correct method of adding
velocities must yield a different rule so that the observers and 0' in the figure can
agree that the light speed has the value c. Furthermore, a regime of speeds must exist

for things other than light, with velocities v and v' substituted for c and c' in Equation
(1-1), such that the equation is a valid approximation to the exact formula for velocity
addition. The second postulate has survived every experimental test, and so our
common sense has to be revised by giving cautious consideration to the space and time
coordinate systems used by observers in relative motion.
Let us first define what we mean by an observer in more general terms. Imagine a
coordinate frame in which clocks are placed at suitably spaced regular intervals. This
lattice of timers can be synchronized to keep identical times by the use of light signals.

A simple method for doing this is given in the example at the end of the section. Let
each lattice site be equipped with a device for recording events that occur at that

Figure 1-2

Two observers in relative motion. is at rest and 0' moves toward at constant speed u.

and 0' agree on the speed of light coming from the source carried by 0'

Observer O'
 1-2 Principles of Relativity 9

position. Such a lattice is equivalent to a reference frame populated by observers at all

the different sites, all with synchronized timers. It is obvious that a single observer who
reads the recorded data is sufficient in a lattice so equipped. The particular location of
that observer in the reference frame is immaterial. In fact, even the one observer is

redundant since it is and recorders that makes the actual

the lattice of timers
observations. From now on, when we speak of an observer we are referring to the
whole lattice frame in this kind of scheme.
Next, let us return to Figure 1-2 and identify a frame S in which observer is at

rest and a frame S' in which observer 0' is at rest. The frame S' moves uniformly

through the frame S at speed u. These two coordinate systems are shown at two
instants of time in Figure 1-3. At the first instant when S and S' coincide, a light flash
is emitted from a source at rest at the origin in S', and at the later instant, the wave

front from this flash reaches a detector at a location fixed in S. This wave propagates
spherically from its point of origin with the same light speed c in both frames,
according to the second principle of relativity. The figure indicates qualitatively thai
the detection of the wave front occurs at a distance Ax in S and at a lesser distance
Ax' in S'. In view of this the elapsed times in 5 and S' are different:

A< = —
Ax
c
in S and A/' =
Ax'

c
in S'

so that A/' is evidently less than A/. We sketch this argument here to introduce a
feature of the second postulate, which we must be prepared to accept. Observers in S

Figure 1-3

Reference frames S and S' in uniform relative motion. S' moves through 5 with speed u, and
so S moves with thesame speed in the other direction through S', A light source at the origin in

S' emits a flash at the instant when S and S' coincide, and the propagating wave front is
observed later at a location fixed in S. Emission and detection are shown in the frame S on the

left and in the frame S' on the right.

(*>- ( iy-
-o <>
Emission Emission

S'

Ax
>5>-

A.v

Detection Detection
St later At' later
10 Relativity

and in S' do not agree about time intervals or space intervals in order that they do
agree about the light speed c. We deduce the actual relations for time and space
intervals in different frames in Section 1-3.
Relative motion satisfies a reciprocal property, which we have incorporated in

Figure 1-3. We note that 5" moves to the right with speed u when 5 is the frame at
rest and that S moves to the left with the same speed u when S' is the frame at rest.

This reciprocity is necessary to prevent us from distinguishing frames and thereby

identifying an absolute frame of reference.
Time can no longer be taken for granted as an absolute variable whose ticking
frequency is common to all observers. Instead, time is a relative variable that differs
for different observers. Time is to be regarded as an attachment intrinsic to a given
frame of reference since that frame contains a lattice of synchronized clocks ticking
with a particular time interval. Another frame in relative motion has its own lattice of
clocks that tick with a different time interval to an observer in the given frame. We
have to allow for this behavior of time in our revised common sense.
The relativistic meaning of time calls for a reexamination of several familiar
notions. The idea of simultaneity is amongframe events
the first to consider. In a given
can be observed to happen at separate locations at the same time. We have just
learned, however, that the time variable is peculiar to the chosen frame, and so the
same events can be observed at different times in another frame. Thus, simultaneity is
relative, since events that are simultaneous in S' are not simultaneous in S if S' and S
are frames in relative motion. We can by means of the thought
illustrate this
experiment in Figure 1-4. A railroad car is shown moving to the right with constant
speed u in S, the frame of the Earth. Let S' denote the car frame in which the car is at
rest. The car is equipped with a light source at its midpoint and a light-sensitive
buzzer at each end of the car. The left side of the figure shows the situation in S',
where the light source and the two buzzers are at rest. First, the light flashes, and
later, the wave front reaches the ends of the car so that the buzzers go off

Figure 14
Propagation of a light flash from the midpoint of a moving railroad car. Light-triggered buzzers

act as detectors at each end of the car. In S', the rest frame of the car, the buzzers are observed
to go off simultaneously. In S, where the car is moving to the right, the left buzzer is observed
to go off before the right buzzer.

,s" ) (*>

//// ////

\/s
© S' )^- o
yv
//// s ////

////
o ^
VV
 1-3 Time Dilation and Length Contraction 1

simultaneously. The right side of the figure shows what happens in S, where the light

source and buzzers are moving to the right. The light flashes and the wave front
propagates outward from the point of origin. It is clear from the figure that the wave
front reaches the left end of the car before it reaches the right end so that the buzzers
do not go off simultaneously in S.
We have begun to describe a revised treatment of space and time as introduced by
Einstein to ensure consistency between mechanics and electromagnetism. We should
be able to see that Maxwell's theory occupies the privileged position in this picture. If

Maxwell's equations are valid in a particular reference frame, they are supposed to
hold in any other frame in uniform relative motion. Otherwise, it would not be
possible for electromagnetic theory to predict the same speed of light c for both
frames. It would therefore appear that Newton's laws must be modified in order to
complete Einstein's picture.

Example

Suppose that we have an array of clocks at rest with respect to each other and
that we wish to synchronize these clocks to read identical times. Let us consider a
linear array in which the clocks are placed along a line at locations separated by
3 m intervals. A light signal traverses a 3 m distance in 10
8
s, or 10 ns. Let the
clocks be triggered to start ticking when a wave front of light passes, and preset
the line of clocks to read sequentially 0, 10, 20, 30, . .
.
, in nanoseconds. A light
flash at the location of the ns clock activates the other clocks in sequence so
that they all keep identical times thereafter.

1-3 Time Dilation and Length Contraction

Time is a variable whose value is recorded in the observation of an event. A pair of

events spans a time interval whose duration depends on the frame of reference in
which the observations are made. In our discussion of Figure 1-3 we have considered
two such events defined by the emission and detection of a light signal. We have
acknowledged that the elapsed time between events is relative for frames in relative
motion because the speed of light is a universal quantity. We now want to show how
the universality of the speed of light can be used as a standard when we compare time
intervals in different frames. We proceed by devising "relativity laboratories" and
conducting thought experiments in which this standard is incorporated as a basic
feature.
Figure 1 -5 shows the construction of a simple laboratory consisting of a floor and a
mirrored ceiling. The structure is assumed to be moving uniformly so that two frames
of reference can be identified. The laboratory is at rest in the frame S' and is in
motion with constant speed u in the frame S. Observers in S and S' agree that floor
and ceiling are separated by the same distance d in the two frames. (They agree on
this because there is no relative motion in the vertical direction and so there is no way
to distinguish heights, or vertical coordinates, from one frame to the other.) The
thought experiment employs a light source and a detector located at the same position
on the floor of the laboratory. The source emits a light signal, which the mirror reflects
back to the detector as shown in the figure. In S', the signal travels straight up and
straight down, a distance 2d, in a time interval A^'. In S, the signal travels out to the
moving mirror and back to the moving detector, a distance 2c* > 2d, in a time interval
12 Relativity

Figure 1-5

Relativity-of-time laboratory at rest in S'and

moving S with speed u. In S', the light
in

path has length 2d and transit time At'. In

S, the light path has length 2/ and transit
time At. The time interval in S is greater
than the time interval in S' by the factor
(1 — u /c 2 ) '
J
. In this experiment At' is a
proper time interval.

t
d
source
i
.Or
-\3T
detector

t' = ® k_j At
mS'

t = ^)At
mS
x = M u At

A/. We use the universality of the speed of light to express the time intervals as

2d 2(
At' = —c
in S' and At = —
c
in S.

It is obvious from these relations and from the figure that At is greater than At'. If we
examine the light path in 5 we see that

= d2 4 | -A

Elimination of / and d from these equations yields the relation

-A,] -l-M -A,

+i
When we solve this expression for At in terms of At', we obtain the final formula:

At'
At = " (1-3)
/l - u
2
/c 2

This very important result describes the phenomenon of time dilation.

 1-3 Time Dilation and Length Contraction 13

Figure 1-6

Fixed synchronized clocks showing more elapsed time than the clock in motion. The measuring
rod from A to B is at rest along with the synchronized clocks in S. Its length D is a proper
length determined by the spatial interval in S between points A and B.

0-
"0 D
Measuring rod

The device in the experiment is a kind of clock. The fact that the clock is at rest in
S' distinguishes that frame from S, which may be any other frame where the device is

moving. We have timed the interval between two events, again using the emission and
detection of a light signal. The frame S' is distinguished as the only one in which these
events occur at the same spatial location. The time interval between two such events at
the same point in space is a unique quantity called the proper time interval between the
events. According to Equation (1-3), the elapsed time A/ between the same events in
any other frame is dilated, or enlarged, by the factor (1 — u
2
/c 2 )~ x/1
compared to the
proper time interval A/'.
The identification of a proper time is often the key to the resolution of many
puzzling applications of time dilation. Consider clocks in relative motion as a first

example. We can expect such timekeeping devices to record different times in the
manner illustrated in Figure 1-6. The array of clocks between points A and B in the
frame S are synchronized, and another clock in motion from A to B indicates a
smaller time interval for the journey than that recorded by each of the clocks in the
fixed array. In terms of Equation (1-3), the moving clock reads A/' while the
synchronized array reads A/ for the elapsed time. The moving clock keeps proper
time; the ticks of that clock are events at a fixed location in the moving frame and are
being observed at a sequence of locations in the fixed frame S. The relation between
A/ and A/' depends on the ratio u/c. Time dilation has real effects that are not
readily observed unless the speed u is sufficiently close to c. The phenomenon is

therefore surprising to us because the regime of such large velocities is beyond our
limited experience.
Observers in relative motion must also disagree over the measured length for a
spatial interval when the length is along the direction of motion. To see how their
measurements differ, let us construct another kind of relativity laboratory, building
again on the propagation of light signals. As before, we want a design in which light is
emitted and returned to the same point in the laboratory. Figure 1-7 shows a
construction consisting of two facing walls in which the one wall is mirrored while the
other contains a light source and a detector at the same location. The device is in
motion at constant speed u in the frame S and is at rest in the frame S'. The
wall-to-wall distance depends on the frame and is denoted by L' in S' and by L in S.
We can measure these lengths by timing the passage of a light signal from the source
14 Relativity

Figure 1-7

Rclativity-of-length laboratory at rest in 5"

and moving in S with speed u. The lengths of
the laboratory in the two frames are denoted
by L' and L, respectively. The transit time of

a light signal from the source back to the

detector is observed in both frames. The
time intervals At and At' are related by the
time-dilation formula, and the length L is

shorter than the length L' by the factor

(1 — w /c )'' . In this experiment L' is a
proper length.

Mirror

Source

Detector V inS'

L inS

inS'

0<
At'C-*-

inS
t = 0'

M i
C^

At e*-

u M L L + u At

back to the detector after its reflection at the mirror. In S', the light flashes at /' =
and the reflected signal arrives at the detector at t' = At' after traveling the distance
L' each way. The transit time is

2L'
At' = -
in S'.
c

Note that At' is a proper time interval because the emission and detection of the
signal are events at the same location in S'. In S, the light signal propagates as shown
in the figure. The mirror moves to the right with speed u while the signal travels with
speed c and overtakes the mirror. If the flash goes off at / = in S, then at / = A/,
 1-3 Time Dilation and Length Contraction 15

the signal reaches the mirror, which has moved to the location L + uAt and at {
,

t = At the reflected signal arrives at the detector, which has moved during the
intervening time to the location «A(. Since the light travels the distance L + u At x
in

the time At l
, we have
I + uAi,
= At l

and so

L
At = .

x
c — u

The reflected light travels from L + uAt l

back to «A( in the time At — A/,;
therefore, we set

I + i/Ai,- u At.
A/ - A/,
c

so that

At - At = l

c + u

These results imply

L L
At = + = —2Lc in S.
c + u c — u c" — u~

We also know that A< and At' are related by Equation (1-3), because we have
identified At' as a proper time interval. The resulting equality is written as

2Lc At' 2L'

c
2
~u 2
yl-.-'/r- yjc
2
- «-•

The final formula then follows by solving for L to get

L = Z/yi- (1-4)
7 .

This very important result describes the phenomenon of length contraction.

The laboratory in Figure 1-7 has length L' in the frame S' where the device is at
rest. The rest frame is a distinguished frame and so the length L' is a unique quantity,

called the proper length. Equation (1-4) says that the length L of the same object in any
frame S in which the object is moving is shortened relative to the proper length by the
— 2 x/2
contraction factor (1 u /c 2 ) . Length contraction, like time dilation, is a real
effect that becomes observable for sufficiently large values of u.

Some of these manipulations are reminiscent of aspects of the Michelson-Morley

analysis. In fact, the conclusion in Equation (1-4) reproduces the ad hoc proposal
made by FitzGerald and Lorentz to explain the null result of the Michelson-Morley
experiment. The phenomenon is often called Lorentz contraction for this reason. Note,
however, that the result is a consequence of Einstein's theory and makes no use of
16 Relativity

Lorentz's assumption that objects contract along their direction of motion because of
the mechanical properties of materials. Instead, Einstein's view holds the observable
contraction to be an intrinsic property of space and time coordinate systems.
The relativity of space intervals can be deduced in another way. Let us return to
Figure 1-6 and assume that an observer travels with the moving clock between the
indicated points A and B. The observer measures the elapsed time A/' on that clock
and then uses the speed u to compute

D' = ubt'

as the distance from A to B. This result represents the length of the array of clocks in
S, observed in the framemoving clock as the array passes by (traveling to the
S' of the
left). The corresponding distance in S from A to B is given by the length D of the

measuring rod shown in the figure. An observer in S reports that the moving clock
travels the distance D (to the right) in time A< so that

D= ubt.

We can use Equation (1-3) and immediately relate the lengths D and D'\

2
u

This conclusion agrees with Equation (1-4), even though the two results may not
appear to be quite the same. It is important to realize that the distance D is the length
of a rod in the rod's rest frame and is The observer on the
therefore a proper length.
moving clock measures and obtains D', the appropriately contracted
this distance
length. Figure 1-8 shows the situation in the frame S' where the moving clock,
mounted by the primed observer, is at rest. In this frame the rod moves to the left with
speed u, and so the length D' is seen by the primed observer as the contraction of the
proper length D.
Some bewilderment over these formulas is inevitable. When circumstances involve
two (or more) relatively moving frames, it is natural to wonder where the primes
should go in the use of Equations (1-3), (1-4), and (1-5). The recommendation would
be to identify wherever possible the proper time or proper length in the appropriate
frame. The time or space interval in any other frame is then dilated or contracted
according to the formulas.

Figure 1-8

Observation of the length of a moving rod.

The proper length is D; the observer in .S"

measures the contracted length D'.

inS' [T_
 1-3 Time Dilation and Length Contraction 17

Example

An experimenter transports a clock on an eastbound transcontinental flight.

The instrument has been synchronized with a clock on the West Coast and is

compared with another clock on the East Coast after the journey. The West
Coast and East Coast clocks remain synchronized throughout. The picture is the
same as the one shown in Figure 1-6. Let the speed of the plane be u = 300 m/s
and let the transcontinental distance be D = 6000 km. A ground-based observer
records the flight time to be

D 6 X 10
6
m
At= — =
2
= 2 X 10
4
s.
u 3 X 10 m/s

The traveling experimenter records a shorter proper time interval given by

At' = A<y 1 — u
2
/c
2
. The traveling clock therefore runs slower by the amount

1 u- At i u
At - At' = A/ 1-11- = At 1
-
?'
2

(We use the binomial expansion and note that the first nonvanishing term is
~6
enough since u/c = 10 .) The time difference between clocks at the end of the
journey is

4
2 X 10 s ,
At - At' = (l0-
6
r = 10~ 8 s.
2

Time dilation has a very small effect here because jet travel is so slow compared
to the speed of light. The traveler observes the transcontinental distance to be
D' = u At' . This corresponds to the Lorentz-contracted version of the proper
length D, where D and D' are related as in Equation (1-5). The difference
between D and D' is

u(A«-A«') =
At

«y(-J =7(7)
I

="
u\ 2
D I u\* 6
—
X 10
6
m
"(10- 6 r =
,
3x 10~ 6 m,

a minuscule distance of only 3 micrometers.

Example

The situation is quite different in high-energy physics where relativistic effects

are among the essential properties of the elementary particles. Indeed, it is here
that we routinely find convincing evidence to support our belief in relativity.
Let us consider the muon as an example of an unstable elementary particle.
The muon has a 2 jus average lifetime and decays into lighter particles. Muons
are produced in the interactions of other very-high-energy particles as they enter
the Earth's atmosphere. Many fast muons are able to reach the surface of the
Earth before decay, even though they must travel a considerable 10 km distance
through the atmosphere to do so. Time dilation is in evidence here as the 10 km
18 Relativity

distance and the 2 /is time interval do not refer to the same space-time frame.
The 2 [is lifetime represents a proper time interval in the muon's rest frame. A
fast muon, traveling at 99.9% of the speed of light, would see only about 600 m
of atmosphere pass by before decay:

D' = u A/' = 0.999(3 X 10

8
m/s)(2 X 10~ 6 s) = 6 X 10
2
m.

~ /l
For u/c = 0.999 the time dilation factor is (1 — u
2
/c '
)
'
= 22. Hence, an
observer on Earth sees these muons live 22 times longer -and travel 22 times
farther. From Equation (1-5) we have

D'
D= .
= 22(0.6 km) = 13 km.
/l - u
2
/c 2

Thus, the Earth observer sees the muon's lifetime dilated, and the muon in turn
sees the distance through the atmosphere contracted.

Example

The relativity of simultaneity is the key to the following famous puzzle, which
we present with numbers first and then with general expressions. Let us use what
we have learned in order to make a 5 m pole fit into a 4 m barn. The obvious
procedure would be to run with the pole at speed u = \c into the barn (which
we assume to be open at both ends), as described in Figure 1-9. The observer
in the figure sees that the 5 m length of the pole is contracted by the factor

y 1 — u and hence can say that the pole just fits in the 4 m length of the
2
/c = 2
i

barn. Of is more to the puzzle than this. The observer 0' sees the
course, there
barn approaching the pole, observes that the 4 m length of the barn is
contracted by the same factor '\, and therefore says that the barn is only 3.2 m
long, too short to contain the entire length of the 5 m pole. We have an obvious
disagreement here between two observers and this would appear to be a
contradiction in relativistic physics. In fact, the disagreement is real and is to be
expected. To appreciate this we must realize that we are describing the obser-
vation of two events. Event B is the arrival of the right end of the pole at the
right end of the barn, and event C is the arrival of the left end of the pole at the
left end of the barn. Observer sees these events as simultaneous, but observer
0' cannot agree since the simultaneity of the two events is relative. Thus, the
lining of the pole in the barn is also relative, and observers in relative motion
are bound to disagree over it. Let us examine their disagreement in general
terms, letting S be the barn frame and S" be the pole frame. For reference, we
identify event A, the arrival of the right end of the pole at the left end of the
barn. Let this event occur at the origin in both frames, when / = in S and

when t' = in .S". Call the proper length of the pole L' (the length of the pole
in ,S"), and call the proper length of the barn <f
()
(the length of the barn in S).
The sequence of events A, B, and C is shown in the figure. In S, the length of
the pole is

L = L'
\l
1 - - 2
 1-3 Time Dilation and Length Contraction 19

Figure 1-9

Pole-in- the-barn puzzle. The pole has proper length L' ,

and the barn has proper length
if < L' . Pole and barn are in relative motion at speed u, chosen such that the Lorentz-contracted
length of the pole equals the proper length of the barn. In the rest frame of the barn, events B
and C are simultaneous. In the rest frame of the pole, event B precedes event C.

Observer 0'

Jl^
k* Observer O

inS inS'

11

A A
t =
u
1
f-Q
-L = ( e
-«o -L'o

u
B
''
l
f
l

t -'^
C
u
B
< -t'
B~ "

BC "

o e

*~ u
C

fC -&
< u
'

We choose u such that L = tf , so the pole "fits" in the barn in S. Then, when
t = t
BC = tf /u, the events B and C are observed in S as simultaneous. In 5", the
length of the barn is

r = /n \ i
-

(Remember, we are not to be confused about the placement of primes in the

equations as long as we identify the proper length and then Lorentz contract it.)
In 5', event B occurs when t' = t'B = £'/u, and event C occurs later when
t' = t' = L' /u. Note that, since L = tf by construction, we have
c Q

r= L\ i = L' \l
20 Relativity

The times in the two frames are re ated:

2 2
u / u
t
B = -u
= -v 1-7
u V -'«V
,_
7
and
1 ^BC
u u \ - 2
U /<T
2
^1 _ „2/ f '-'

Thus, there is a time gap in S', by which the events 5 and C fail to be
simultaneous.

14 Relative-Motion Symmetry

Relativity denies the concept of absolute motion and treats relative motion symmetri-
cally. We
have noted the reciprocal symmetry of frames in uniform relative motion in
Figure 1-3. We have also used the symmetry implicitly in Figure 1-5 to claim that

observers in such frames agree on lengths transverse to the direction of motion. This
reciprocity has certain confusing aspects that we now want to consider.
Suppose that two frames S and S" are in relative motion with velocity u. If we can
draw conclusions about S' moving at speed u in one direction through S, we must be
able to draw similar conclusions about S moving at speed u in the opposite direction
through .S". Let us visualize this in terms of a rocket ship traveling past a platform in
deep space as in Figure 1-10. Call the rocket frame S' and the platform frame S, and
assume two frames are synchronized when the
for convenience that clocks in the
origins of the frames coincide. We already know from Figure 1-6 that a moving rocket
clock at the origin in S' runs slower than a fixed array of platform clocks in S.
However, we can equally well say that the platform is moving past the rocket in the
other direction since only their relative motion is physically significant. Relative-
motion symmetry then requires a moving platform clock at the origin in S to run
slower than a fixed array of rocket clocks in 5". A picture of the symmetrical situation
is included in Figure 1-10.
It would appear that we have the possibility of a contradiction in the application of
this symmetry. In fact, no difficulties can arise, but we must be careful to examine
possible problems with questions that are properly posed. Note that each point of view
in Figure 1-10 employs a single clock keeping proper time in a "moving" frame,
compared with an array of synchronized clocks in a " fixed" frame. Note especially
that the proper time of interest refers to the ticks of the single moving clock as events
at the same position in that clock's frame.
The moving clocks have to be examined differently if we want to relate readings
between a single rocket clock and a single platform clock. We might wish to compare
a clock (call it C") at the origin in S' with a clock (call it C) at the origin in 5 by
letting the rocket pass the platform and then return. This procedure allows C" and C
to separate and then come back together for confrontation at the same location. We
must realize, however, that the clock C" parts company with the frame S' as soon as it
stops moving uniformly, as it must in order to reverse direction and return. Thus, is C
at rest in S" a new frame of reference moving through S, when it comes back to meet
,

C. Of course, the clock C remains at rest in S throughout. This method of comparing

clocks evidently requires the use of three reference frames.
 14 Relative-Motion Symmetry 21

Figure 1-10

Rocket ship and space platform in uniform relative motion. A rocket clock, at rest in S\ runs
slower than an array of platform clocks in S. A platform clock, at rest in S, runs slower than an
array of rocket clocks in S'.

Ny Ny

Let us apply the symmetry in a different way by letting an observer with one clock
look through a telescope at another receding clock and compare readings. The clocks
maintain uniform relative motion, and so the two frames S and S' suffice in this case.
We recognize first of all that the act of reading the time through a telescope is

accomplished by receiving the light emitted previously from the receding clock. In S,
let C" be moving away and sending its light to the location of C, as described in
Figure 1-11. Light that reaches the origin in .S' at time / = /, is light from C, emitted
earlier in S at time / = t . Since the light travels the indicated distance ut in the time
interval /,
— t , we set

ut.

so that

1 + u/c
22 Relativity

Figure 1-11

Reading a receding clock C" and comparing

with a clock C in hand. Light received at time
t
]
in 5 is light from C", emitted at time t' in

S'. The reading on C" is related to the reading

on C by t'() = r<,, where r determines the red
shift.

t' =
& S'

( =
&

f = t'

t = t o© in,,

t = t, (C

The reading on C" is a proper time, denoted by t'

Q . We therefore obtain

1 - K/f
«o .2 'o
1 + «/f

Thus, when C is read through a telescope and compared with C, it is found that the
time recorded on C is behind the time recorded on C by the factor

(1-6)
c + u

If we reverse the situation so that an observer in S' reads C and compares the reading
with C", we reach the symmetrical conclusion in which the receding clock is observed
to hand by the same ratio r given in Equation (1-6).
run behind the clock in

The Doppler effect for light offers an interesting practical realization of these ideas.
The effect for sound is familiar, and it is instructive to recall the results so that we can
appreciate the distinctions.
Sound waves
are observed to undergo a shift in frequency when the source of sound
is motion through the medium, either approaching or receding from the observer. A
in
different shift is obtained if the observer is moving and the source is stationary in the
medium. The shifts for sound waves are not symmetrical because the medium
provides a frame of reference in which source motion and observer motion can be
distinguished. Formulas for the various cases may be found in any introductory
textbook. We can combine all the possibilities in a single expression by writing the
 1-4 Relative-Motion Symmetry 23

observed sound frequency / as

w+ u,
/
= -fo- il-!)
W — M,

In this equation, / is the frequency of the stationary source, w is the speed of sound
in the medium, and u s and u are the speeds of the source and the observer, also with
respect to the medium. The signs of these last two quantities are such that u s is
positive when the source moves toward the observer, and u is positive when the

observer moves toward the source. (As a check, let source and observer move in the
same direction with the same speed so that u = — u s The result from Equation (1-7) .

is f=f , as we might expect.)

Light waves experience a different Doppler effect because light
is a unique form of

wave motion. There

no medium, and so there is no distinction over source motion
is

and observer motion; instead, source and observer are governed by relative-motion
symmetry. Moreover, time intervals for the source and time intervals for the observer
differ in relative motion according to the time-dilation formula. There are several
ways Doppler result for light. Let us analyze the effect in the manner
to derive the
customarily used for sound but adapted suitably to apply to light.
We distinguish light and sound from the outset by adopting different notation. Let
us call the source frequency and the observed frequency v, and consider the case
i>

where the source moves toward the observer with speed u, as shown in Figure 1-12. Of
course, only the sense of the relative motion (approaching rather than receding) is

physically significant. Let S' be the source frame and S be the observer frame, and
consider the situation in the figure where two wave fronts are observed at instants a
full cycle apart. In S', the time interval T' between the emission of these wave fronts

Figure 1-12

Doppler effect for light where the source

approaches the observer with speed u. Two
consecutive wavefronts of like phase are
observed in order to identify the Doppler-
shifted wavelength A. The observed frequency
v is blue shifted relative to the source
frequency v according to the formula v =

inS
u ^
t = ©
Observer

t = T

L
x = uT cT
24 Relativity

is the period
1

T= -
v,

In S, the corresponding time interval is denoted by T. Since T' is a proper time

interval, Equation (1-3) applies:

T
T= -7=
2 /„2

At t = 7" the observer notes the current position of the wave front, previously emitted
at t = 0, and measures its distance from the wave front of identical phase coming
from the moving source at the same instant. This measurement determines the
observed wavelength

A = cT- uT
as indicated in the figure. The observed frequency is therefore given by

A (c-u)T'

When we fold the time-dilation equation for T into this, we obtain the desired relation
between v and vn :

c + u

\c — u) 1 V
I 1 " —
c
= V
V c — u
"o-

The result is the Doppler formula for relative motion in the approaching sense. The
receding case is described simply by changing the sign of u. Note how the factor r,

defined in Equation (1-6), makes its appearance in the two situations. The quantity r

determines a red shift since, in the case of a receding source, the observer detects a
lesser red-shifted frequency given by

Receding = rV0' I 1 "8)

In astrophysics, the red shift for a receding emitter is expressed by the parameter
z = \/r — 1. The formula obtained above from Figure 1-12 applies to the case of an
approaching source, where the observed frequency is given by

approaching '
V ^/

In this circumstance, the observer detects a blue-shifted frequency.

The result for light in Equations (1-6) and (1-9) is obviously rather different from
the result for sound in Equation (1-7). This is expected since the processes differ in
several respects as noted above. In fact, the observation of red-shifted light is quite
similar in concept to the act of reading the time on a receding clock and comparing
with a clock in hand, the exercise that has led us to Equation (1-6) in the first place.
Of course, we must be reminded again how small u/c is in practical circumstances. A
sensitive measurement is necessary to verify Equation (1-9) is correct for
that
Doppler-shifted light. It is interesting to compare the Doppler shifts for light and
 1-5 The Lorentz Transformation 25

sound by expanding the relevant formulas in powers of the ratio between the speed of
relative motion and the wave speed. It happens that the light formula in Equation
(1-9) is exactly the same as the sound formula in Equation (1-7) to first order in this
ratio. The differences between the two expressions only begin to appear when the

equations are examined in second order.

The Doppler shift is a very useful tool in astronomy. We can use the effect to learn
how fast celestial objects such as stars or nebulas are moving toward or away from us.
These bodies emit wavelengths characteristic of their constituent matter, and the
observation of the Doppler-shifted wavelengths leads to a determination of their radial
velocities with respect to the Earth. We can even use the effect to deduce the
rotational speed of a star like the Sun. The edge of such a body emits blue-shifted
light as it rotates toward us while the opposite edge emits red-shifted light as it rotates

away. Characteristic wavelengths from the source are therefore observed to be

broadened, by a blue shift on the one side and a red shift on the other.

Example

Let us return to the rocket ship and space platform in Figure 1-10, and suppose
that "space twins" are born at the instant of coincidence between the rocket
origin in S' and the platform origin in S. The "twins" are Chester, whose
location is at the S' origin on the rocket, and Esther, whose position is at the S
origin on the platform. Let the relative speed between frames be u = |c, so that

the time-dilation factor is (1 — u /c )~ ' = |. Suppose that when Esther is 5

years old, Chester's rocket turns around abruptly and comes back to the
platform at the same speed |c. We have already noted that the frame S' carries
on without Chester, who has now taken residence at the origin in a new frame
S" (not shown in the figure). This frame moves in from right to left through the
frame S. Reunion takes place after the passage of 10 years in S, Esther's frame;
therefore, Esther has reached "age" 10 at this time. Chester's clock, in S' on the
way out and in S" on the way back, runs slower by a factor of f so that Chester ,

has reached "age" 8 when he returns to confront his "twin." The famous twin
paradox asks why we cannot reverse the situation symmetrically to Chester's
point of view and argue instead that it is Esther who goes off on her platform
and then comes back as the younger of the two. In response, we can say that
relative-motion symmetry applies between 5 and S', and between S and S", but
does not apply over the whole excursion. Chester's entire motion is not symmet-
rical to Esther's, and so the age difference, whereby Esther stays at home and

"ages" more, is a real asymmetrical effect. Chester knows, without reference to

any point outside his rocket, that it is he who goes off and comes back because
he experiences a lurching force when he reverses direction. The resulting
acceleration temporarily breaks the symmetry by dividing the relative motion
between its receding and approaching phases. We return to look at some more of
the details of this problem later on.

1-5 The Lorentz Transformation

The dilation of proper times of proper lengths are the first main
and the contraction
results of relativity. Now thatwe know how these proper intervals are altered as we
pass to other frames, it is appropriate that we generalize and ask next how arbitrary
26 Relativity

descriptions of space and time transform when we move from any one frame of
reference to another. Again, we are guided by the principles of relativity and
particularly by the universal property of the speed of light.
We are concerned with the space-time description of events. The word event has
already been put in use to denote a happening associated with a location in space and
an instant in time. Occurrences at the same spatial location are distinct events if they
happen at different times. In more abstract language, an event defines a point in
space-time. Observers in relative motion make different assignments of space-time
coordinates for such a point. Thus, a given event has space-time coordinates
(x, y, z, t) in S and (*', y\ z' , t') in S', where S and .S" are frames in relative motion.
Our problem is to deduce the transformation rule by which the coordinates in one
frame are determined, given the set of coordinates in the other frame.
Let us restrict our attention to frames in relative motion along the direction of a
common axis. Two such reference systems S and S' are shown in Figure 1-13, where

S' moves through S at speed u along the x and

Each frame contains a lattice x' axes.

of synchronized clocks, reading As usual, we choose to start the

/ in 5 and t' in S'.

clocks at = and t' = when the two frames coincide. Then, at a later time / in S,
/

the primed origin at x' = is located at the point x = ut. The event shown in the

figure has coordinates (x, y, z, I) in and (x\ y', z', t') in .S". For reasons that we
.S'

have already discussed, the spatial coordinates transverse to the relative motion are
the same in the two frames, so that y' = y and z' = z in this case. Hence, the
relations at issue are those between the variables (x, t) and (x', t').
In pre-Einstein relativity, the time coordinates / and t' are presumed to be the
same for an event, in keeping with the notion of absolute time. Let us adopt t' = t
temporarily and pursue the consequences before we consider the true relativistic
picture. We can use the fact that x = ut when x' = to establish the equality

Figure 1-13

Reference systems S and S' in relative motion. An event occurs at (x, y, z, t) in S and
(*', y', z', t') in S'. In this view, S' is moving through S.

y'

t' =
x'
e = o

© Event
 1-5 The Lorentz Transformation 27

x' = x — ut. The collection of relations among the space-time coordinates may then
be written as
=x—
x' ut,

/ = y,
*' = *,

t' = t. (1-10)

This particular system for relating the space-time descriptions of a given event is

called the Galilean transformation.

The transformation formulas is part of the Galilean-Newtonian principle of
set of

relativity,which says that if the laws of mechanics hold in S, they hold also in S\
where S and S' are related by Equations (1-10). To see this, let the event of interest
denote the instantaneous position of a particle, and consider the velocity of the particle
as seen in the two frames. If we introduce the vector u = uxas the constant velocity of
S' in S and differentiate Equations (1-10) with respect to the time, we get the vector
result

d
v' = —dv'
- = — (r - ut) = v - u. (1-11)
dt' dt

Note that explicit use is made of the notion of absolute time.

A second differentiation yields a' = a; therefore, the acceleration of the particle
measured same as that measured in S. The particle accelerates when a
in S' is the
force is applied. The components of this force are (Fx F F, in S and Fx F Fz ) in ,
, ) ( ,, >,

S' We recognize that the components are not altered by the transformation because
.

the orientation of the axes is retained and the time variable is unchanged. We can
express this equality of components by writing F' = F and conclude that, if F = ma
governs the motion in S for a particle of mass m, then F' = ma' holds likewise in S'.
Thus, Newton's law has the same form in any two frames connected by the Galilean
transformation of coordinates.
Note that Equation (1-11) immediately becomes Equation (1-1) when the event of
interestis chosen to be a point on a wave front of light. We can therefore regard

Equation (1-1) as a by-product of Galilean relativity. Since we have already dis-

avowed this equation as inconsistent with the observed behavior of light, we can argue
that the Galilean transformation is likewise inconsistent with the proper description of
electromagnetic phenomena. In fact, it is possible to show that the transformation of
coordinates defined by Equations (1-10) does not preserve the form of Maxwell's
equations. Thus, the improper behavior of the speed of light is only one of the
manifestations of the failure of Galilean relativity. Of course, it is Einstein's theory
that provides the correct principles of relativity and produces the desired set of
transformation formulas. The laws of mechanics have to be modified to accommodate
those principles.
We have known all along that the absolute-time prescription t' = t cannot be
allowed in Equations (1-10). Instead, we expect that /', like x'', should depend on x
and t. It is clear that the variables (x,l) and (x',t') must be related by linear
equations since the corresponding intervals are related in Equations (1-3) and (1-4) as
simple proportionalities. To proceed, let us again refer to the event in Figure 1-13 and
use the fact that x = at when x' = 0. This time we assume that x' is proportional to
x — ut and set

x' = y(x-ut), (1-12)

 ,

28 Relativity

Figure 1-14

Another view of the frames S and S' in which

S is moving through S'.

y'

t=
f = ~x'

(?) Event

where the proportionality constant y is to be determined. We should realize in

advance that y depends on u, the speed of S' moving through S. Next, let us reverse
our point of view and take 5 to be moving through S' in the other direction, as in
Figure 1-14. Since the unprimed origin at x = corresponds to the point x' = —ut',
the coordinates of the indicated event must have the property that x is proportional to
x' + ut'. We use the same proportionality constant as in Equation (1-12) and write

x — y(x' + ut') (1-13)

because the relative speed between frames is u from either point of view and because
y depends only on u.

We can now connect the viewpoints in the two figures and determine y by
considering the propagation of a light signal. Let a light flash be emitted at the
coincidence of origins in the two frames when / = and t' = 0, and let the given
event at the later time represent a point on the propagating wave front. For simplicity,
we choose y' =y= and z' = z = so that the event occurs at a location on the x
and x' axes. The coordinates must satisfy x = ct in S and x' = ct' in S' because of the
universality of the speed of light. When these data are inserted in Equations (1-12)
and (1-13), the expressions become

ct' = y(ct — ut) and ct = y{ct' + ut').

Two relations between t and t' result:

u\ I
u
t' = y 1 - t and / = y 1 + - I
 .

1-5 The Lorentz Transformation 29

We can combine these to get an identity,

t = y(l + -I

and immediately solve for the unknown constant of proportionality:

y ' (1-14)
l/l
- u
2
/c 2

The resulting quantity is recognized as the familiar time-dilation factor appearing in

Equation (1-3) and in other formulas thereafter. Next, let us return to Equation (1-13)
and insert Equation (1-12) to get

x = y (x — ut ) + yut'

We can solve this equality for t' and obtain

2
1-Y
t = yt -\ x.
Y«

Equation (1-14) tells us that (1 - y 2 )/yu = —yu/c 2 and , so the final relation takes
the form

t' = y{t- ^x). (1-15)

These results fulfill our objective, as Equations (1-12) and (1-15) serve to determine
the transformed variables (*', /') in S' from the given variables (x, t) in S.

The rules for finding the coordinates of an event in S', given those in S, are
cpllected as follows:

x' = y(x - ut),

y = y,
:'
^3
II

X (1-16)
-A'- 7
t'

This famous set of formulas is known as the Lorentz transformation. Credit is given to
Lorentz because of his discovery, before Einstein, of the curious mathematical
property that the form of Maxwell's equations remains unchanged when the space
and time variables are substituted according to Equations (1-16) and when the fields

in the equations are also transformed by a suitable set of rules. Lorentz's contribution
isthat of a believer in the aether hypothesis and should therefore be regarded as a
mathematical observation without physical foundation. Einstein's theory gives status
to the contributionby providing the proper theoretical setting in which the transfor-
mation emerges logically from the principles of relativity. Einstein's famous paper of
1905 demonstrates over again Lorentz's observation that the transformation rules
leave the form of Maxwell's equations unchanged. Thus, the Lorentz transformation
30 Relativity

supplies the general mathematical language to use for the description of space and
time and for the formulation of dynamical principles.
The speed of light has a central role in all these proceedings. We can see that the
light speed represents a speed limit inasmuch as y in Equation (1-14) becomes infinite
in the limit u —> c. Hence, frames of reference may have relative motion at any speed
u, even u approaching c, as long as u remains smaller than c. Of course, our
experience makes us more familiar with the nonrelativistic regime where u is much
less than c. When we examine the Lorentz transformation in the nonrelativistic limit,
we find y —» 1 and t' -* t. Therefore, absolute time and the Galilean transformation
become valid approximations to Equations (1-16) in this regime.
The Lorentz transformation can be inverted so that we can pass from the frame S'
to the frame Equation (1-13) is evidently one member of such an inverse set of
S.

relations. The whole set may be obtained from Equations (1-16) simply by exchanging
primed for unprimed coordinates and changing the sign of ;/:

x = y(x' + id'),

y = /,
z = z',

t = y(t'+ j,x'Y (1-17)

Note that we can associate Equations (1-16) with Figure 1-13 and Equations (1-17)
with Figure 1-14. Of course, relative-motion symmetry assures us that both sets of
relations are Lorentz transformations with entirely symmetrical meanings. Frames of
reference are called Lorentz frames if their space and time coordinates possess these
transformation properties.
The Lorentz transformation is a general scheme of relations between any two
Lorentz frames. Let us gain familiarity with some of the transformation strategies by
confirming the relativistic effects that we have already investigated regarding the
relativity of time and space intervals and the relativity of simultaneity.

To examine time dilation, shown in Figure 1-5 so that we

we return to the situation
can identify two events occurring at the same space point x' in >S" and then transform
the events to S. Denote the coordinates of the events in each frame as

( x x
, /, ) in S and ( x' , t\) in S'

for event 1 , and

(x 2 , t
2 ) in S and (x' , t
2 ) in S'

for event 2. The time interval between events is At = t

2
— t
i
m S and A/' = t'
2
— t[

in S'. When we apply Equations (1-17) to the two events, we obtain for the time
coordinates in S

t
2
= y\t'2 + —x'

and
u
l
\
= y\ t'\ + —x'o
 1-5 The Lorenlz Transformation 31

The time interval in S is found by subtracting to get

A/ = yA/\ (1-18)

Since A<' is a proper time interval in this situation, the result describes time dilation as
in Equation (1-3).
To examine length contraction, measurement illustrated in
let us consider the
Figure 1-8. We want to determine the length of the moving rod
in S' by locating the
endpoints of the rod in that frame, where the two spatial locations are to be found at
the same time t' Associate an event with the simultaneous arrival of each end of the
.

rod as shown in the figure, letting the coordinates in S' be

(x[,t' )
and (x'2 ,t' )

for the arrival of the left and right ends, respectively. We can determine the
corresponding spatial coordinates for the two ends in S by applying Equations (1-17)
to each event:

x2 = y(x'2 + ut'Q )

and

*i = y( x {
+ ut'o)-

When we subtract, and use D= x2 — x x

and D' = x'2 — x\ to define the lengths in

the figure, we get

D
D= yD', or /)'=—, (1-19)
Y

in agreement with Equation (1-5). As in the earlier derivation, D is the proper length
of the rod and D' is its contracted length.
To examine the relativity of simultaneity, we
refer back to the thought experiment
in Figure where the soundings of two buzzers at opposite ends of the moving
1-4,
railroad car represent two spatially separated events, occurring simultaneously in S'
but not in S. Let these events be denoted in S' by the coordinates

(x[,t' )
and (x'2 ,t' )

for the buzzers on the left and right, respectively. Note that both events have the same
time coordinate in S'. When we apply Equations (1-17) to each event, we find the
time when each buzzer goes off in S:

u
{ , ,

and

/ "
t\ = y\ <<>
,

+ —> x
,

Finally, we subtract, and let \t = t., — t

]
and L' = x'2 — x[ to obtain

M = y^L'. c
(1-20)
32 Relativity

This result formalizes the qualitative description given to accompany Figure 1-4. The
distance L' is the length of the railroad car in S'. Since the car is at rest in S', L' is the
proper length of the car. In S, where the car is moving, the left buzzer is observed to
go off before the right buzzer with intervening time given by Equation (1-20).

Example

Here is a final illustration of the Lorentz transformation based on the issue of

simultaneity. Two hunters are separated by a 9 m distance and fire their
shotguns 10 ns apart. A passing game warden observes that the shots are
simultaneous. The speed of the warden in the frame of the hunters can be
deduced from this information. Regard the gunshots as two events, and intro-
duce Lorentz frames S and S' in relative motion such that the hunters are at rest
in 5 and the warden is at rest in S'. Let the first shot occur when t = t' = 0, and

assume for convenience that S and S' are coincident at this instant. The two
shots are events, with coordinates

(0,0) in S and (0,0) in S'

for the first shot, and

(*,,£,) in 5 and ( x],0) in S'

for the second shot. The given data are x, = 9 m and /, = 10

8
s. Note that
both events occur at /' = in 6". Equations (1-16) may then be consulted to
interpret the simultaneity hypothesis as

= Y /

Therefore, S' must be moving through S with speed u given by

8
(3 X 10 m/s)(l(T 8 s) 1

9m 3'

and so the game warden's speed in the hunter's frame is c/3 = 10

8
m/s. Note
that the warden can observe the firing of the second shot before the first by

traveling at a speed greater than c/3.

1-6 Transformation of Velocity

The motion of a particle is described by the time dependence of the particle's position
vector r(/). The velocity vector is then obtained by differentiating:

dx
y(t
dt

These familiar statements pertain to the description of motion in a particular

 1-6 Transformation of Velocity 33

Figure 1-15

Particles in motion with velocity v. The

velocities refer to the frame S, while S' moves
through S with speed u.

reference frame S, where the coordinates of the moving particle are (x, y, z, I). In
another Lorentz frame S' in motion relative to .S", the coordinates of the particle
transform into (x', y', z' , and so the description in that frame is in terms of the
t'),

transformed vectors r'(t') and v'(t'). The interesting feature is the transformation of
the time as we pass to the new frame. We have to take this into account when we
determine how v transforms into v'.

The motion of the particle is taken to be arbitrary in the following derivations.

Figure 1-15 shows some sample cases along with two frames S and S' related to each
other by the Lorentz transformation developed in Section 1-5. Let us consider first the
case of straight-line motion in the x direction, where the particle velocity is denoted by
v in the frame S, as shown in the figure. In 5", we have

dx'

dt"

the limit of Ax '/At' for small space and time intervals. Let these intervals refer to the
space and time coordinates of events 1 and 2 defined by two successive locations of the
particle along its path. Then, from Equations (1-16), we obtain

A*' y(x 2 - ut
2 )
- y(.v, "I i

7
It - YM, - ~7*!
t
2
~ ~^x 2 \

Ax - u At At
u Ax
A/
7 Ji
2
34 Relativity

The result follows when the limit of vanishing time intervals is taken:

w-
-
(1-21)
1 -

One-dimensional velocities transform their speeds from v to v' according to this rather
complicated formula.
Two elementary checks may be made on
the result. Suppose that the particle has
constant speed and that S' moving along with the particle; we then have u = v so
is

that v' = 0, as expected. Suppose instead that the particle is at rest in S; in this case
v = and so !»'= — «, also as expected. A more critical check on Equation (1-21) is
made by applying the formula to the speed of light. If we set v = c we find

c.
1 - uc/c'

Thus, the light speed transforms into itself, in keeping with the property of universal-
ity.

Figure 1-15 also shows the more general case in which v, the particle's velocity

vector in S, has three nonzero components. The transformed components of the

velocity v' in S' are

"x ~
-
1
~7
v
,.' >
°y~ uvx \

,(.

Vz
f _
(1-22)
Y|l --£

We can infer the first of these formulas directly from the derivation of Equation
(1-21). The second and third involve identical manipulations, so let us consider
only v' :
y

A/ __ y't
- y\ y-i
- 7.
:

u u
bt' t'- /
-
\
1[
y\t 2
72
x2 -y M.t^x,

/
u k \ . I u A.v

The result given in Equations (1-22) is obtained when the limit defining dy'/dt' is

taken. Note that v' and v are not the same, even though y' = y, because of the
invalidity of absolute time.
 1-6 Transformation of Velocity 35

The inverse transformation of velocity proceeds as in the treatment of coordinates,

by exchanging primed for unprimed components and by making the replacement
u — > —u. When we perform these substitutions, we get

v' + ;/

Vx ~
1 + 2
C

v'y
°y~
>(

(1-23)
uv, *

Y 1
+

The formulas given in Equations (1-22) and (1-23) constitute the correct relativistic
rules for adding velocities. These results take the place of Equation (1-11) and of
course reduce to that equation in the nonrelativistic limit, when both u and v are very
small compared to c.

The aberration of starlight can be discussed in these terms. We know that if we

observe a " fixed" star with a terrestrial telescope we have to tip the orientation of the
lenses because of the motion of the Earth relative to the star. The situation is

illustrated in Figure 1-16, inwhich S is the star frame and S' is the Earth frame. A
light ray emitted from the star at an angle 8 in S is received in S" at a greater angle
8', according to the following analysis. The components of the velocity of light in 5

are

vx = — cs'mS and v = —ccosd.

The corresponding components in S' are obtained by means of Equations (1-22):

c sin 6 + u c cos
v. = indJ
"*" v'
"y
=
u u
i
-sin 6 y 1 + -sin i

<

With a little algebra we can verify that v'x

2
+ v'
y
2
= c~. The desired direction angle 6'
is given by computing the quantity

v[ c sin + u
tan#' = — = y-

oi

1
/
u
tan 6' = -7= tanfl+ . (1-24)
VI - u
2
/c 2
\ c COS0 I

It is clear from this expression that 8' is larger than 8. Therefore, we see that we must
36 Relativity

Figure 1-16

Abberation of light from a fixed star observed

with a moving telescope. A light ray from the
star makes an angle in the star frame and
is received in the Earth frame at a larger
angle 6'. The classical method of adding
velocity vectors is shown below, in the frame
of the telescope. The relativistic prediction

differs from the classical result by the fac-

tor y.

ccos e

tip the telescope forward relative to the direction defined by 6, as indicated in the
figure. The classical treatment of the aberration of starlight employs nonrelativistic
velocity addition. This analysis is also sketched in the figure, in an inset taken from the
telescope's point of view. We note that the same answer results except for the presence
of the y factor in Equation (1-24). Consequently, there is no difference between the
classical and relativistic predictions to order u/c.
 1-6 Transformation of Velocity 37

Example

Relativistic velocity addition is nicely illustrated by considering the passing of

two rocket ships, as shown in Figure 1-17. Let the rockets have the same 20 m
proper length, and assume that in the Earth frame S the speed of each rocket is

u = \c. The problem is to find the speed of rocket 2 relative to rocket 1 and then
to find the time elapsed on rocket l's clock while rocket 2 passes. The figure
shows the motion of the rockets in two Lorentz frames; on the left the passing is
seen in the Earth frame S, and on the right the passing is seen in S', the rest
frame of rocket 1. The speed u' of rocket 2 in S' is obtained by inserting v = —u
and v' = — u' in Equation (1-21):

lu 2(f0 40
c.
2
1 + u /c' 1 + 16/25 11

The contraction factor associated with this relative velocity is y 1

— L
ti

Let the length of rocket 1 in S' be denoted by / '; this specifies the rocket's

proper length so / '

()
= 20 m. The length (' of rocket 2 in the frame S' is given
by length contraction:

r = ^\ -u"/c 2 =(20m)(^)= *»m.

Figure 1-17

Two rocket ships passing each other. The proper length of each rocket is /„'. In S, the Earth
frame, both rockets have speed and contracted length ( Passing takes place in S between
u .

times t = and t — /, = f/u. In S\ the rest frame of rocket 1, oncoming rocket 2 has
speed u' = 2u/{\ + «-' /c~) and contracted length /'. Passing in S' takes place from l' = to

t > = t[ = (^ + /')/»'•

t=
f =

-<3
1 l_S'
-( V
o

t= U =77 f = (
1 "

^-<3
*o- e ' f
- o
38 Relativity

The passing time in S' is noted in the figure:

4 + <" 20 +
<;
= m/c = 25 m/c,
hi
n

using meter/c as a convenient unit of time. These results complete the problem.
Let us confirm the answer for t[ by analyzing the motion in S, as shown on the
left side of the figure. In this frame each rocket has the contracted length

t = / Vl - u
2
/c 2 = (20 m)(f) = 12 m,

and so the passing time in S is

( 12m
t, = - 15 m/c,

as indicated in the figure. This represents a proper time interval because it gives
the time elapsed between two events at the same point x = in S. Therefore,
the corresponding time inteival in S' is dilated relative to /,:

/; =(l5mA)(f) = 25mA,
- 2 ;

/I u /c

in confirmation of our previous result

1-7 Space-Time

Relativity dissolves the boundaries of definition between space and time, and mixes
these variables together in the passage between Lorentz frames. We see this most
clearly in the Lorentz transformation, where one observer's time for some event is

related to another observer's time and position for the same event. We have already
adopted a notion of space-time as the setting in which events happen. Now we want
to extend the idea so that we can visualize several Lorentz frames at once, and let the
space and time coordinates mix accordingly.
Let us first introduce some new notation by setting

(S = - and y (1-25)
c 1

As S and S', as in Figures

usual, u refers to the relative speed between two frames
1-13and 1-14. We then observe that the equations of the Lorentz transformation
become more symmetrical when we take ct instead of t for the time variable.
Equations (1-16) may be rewritten to incorporate these features:

x' = y(x - fict),

y' = y,
Z' = 2,

ct' = y(d- fix). (1-26)

 7-7 Space -Time 39

The resulting set of formulas employs coordinates (.v, y, z,ct) that have the same
dimensions of length and display an obvious interchangeability in the variables .v and
ct.

The appealing symmetry of the equations takes on considerably more substance

when we recognize the important property of Lorentz invariance . For an event at
(x, y, z, ct), let a "distance" s be introduced by defining the quantity

2
s
2
= x +y + 2
z
2
-c 2 t
2
. (1-27)

A primed version of this is also defined by the coordinates (*', y', z', ct') for the same
event in another frame. We can use Equations (1-26) to relate s' and s:

^=x ' 2
+y' 2 + Z
' 2
- c
2
t'
2
= y (x
2
- Pctf+y 2 + z
2
- y (ct
2
- (3xf
= y
2
(l-p 2
)x
2
+y 2 + z
2
-y 2
(l-(] 2 )c 2 t
2

= x2 + y2 + z
2
- c
2
t
2

The remarkable result is that s is not changed in the transformation to the new
Lorentz frame. Therefore, s has the same value in all Lorentz frames and is said to be
a Lorentz-invanant quantity.

The conclusion that s'

2
= s
2
is a statement of Lorentz invariance. Equation (1-27)
reminds us of the expression for the square of the distance r between the origin and a
spatial point (x, y, z),

r
2
= x
2
+ y2 + z
2
.

This distance does not change when we perform rotations of the three-dimensional
coordinate system. Similarly, we can regard j as a "distance" in four-dimensional
space-time between the origin and an event (x, y, z, ct). Lorentz invariance then says
that this "distance" remains unchanged when we carry out Lorentz transformations
on the space-time frame. The negative sign is crucial for the time contribution in
Equation (1-27) since Lorentz invariance would not follow without it. In a given
frame space and time have distinct meanings, and the minus sign for the time
highlights that distinction. The sign tells us that Euclidean geometry does not hold in
our four-dimensional space-time. The interpretation of s as a distance must therefore
be made advisedly since s is not a positive quantity in all cases. We may extend the
meaning of Equation (1-27) by considering two events and defining the space-time
interval As between the corresponding points in space-time:

2 2 2 2 2
(A*) = (A*) + (Ay) + (Az) - c
2
(A0 - (1-28)

This expression is Lorentz invariant and may be either positive or negative. Space-time

can present a complicated picture owing to the mixing of coordinates in the passage
from frame to frame. It is very useful to know that such features of the general picture
as the space time interval remain unchanged during the mixing process.
A full visualization of space-time requires a four-dimensional picture. Let us
forego this complication by concentrating on problems for which there is only one
spatial dimension. Consider the straight-line motion of a particle whose path, x versus
t, lies in the plane of the variables (x, ct), as in Figure 1-18. The locus of points on the
40 Relativity

Figure 1-18

World-line for a particle in straight-line

motion. The motion from x =

starts when
/ =and has constant velocity v until t = /,.
Three possibilities are shown thereafter,
corresponding to different accelerations of the
particle. The dashed line at 45° refers to
motion at light speed from the same starting
point.

t=

rt,

path is called the world-line of the particle. The figure shows the motion beginning at
x = when = and proceeding at
t constant speed v until t = t
l
. Thereafter, the
world-line may continue as a straight line, if the particle does not accelerate, or may
curve downward or upward if the particle speeds up (a > 0) or slows down (a < 0).
Note that the slope at any point along the world-line is

del c

'

dx dx/dt

where dx/dt is the instantaneous velocity of the particle. This slope must always
exceed unity for a moving particle and may approach unity from above as the
particle motion approaches light speed.

We can use such diagrams in the (x, ct) plane to visualize various kinds of events in
their space-time setting. It is especially useful to see how the interpretation of the
diagrams can be extended by defining different pairs of axes corresponding to
different Lorentz frames. We let the axes denoted by (x, ct) pertain to the particular
choice of frame S, and we consider the transformation to another frame S' by means
of Equations (1-26) so that we can introduce new axes in space-time labeled by
(x\ ct'). The orientation of the new primed axes in the plane of x and ct is established
as follows. Equations (1-26) tell us that along the ct' axis we have

so that ct = — ,
 1-7 Space- Time II

and along the x' axis we have

ct' = so that ct = fix.

The lines ct =and ct = /8* are drawn in Figure 1-19 and labeled as rf' and x'
x/fi
Note that these axes are not perpendicular but skewed. Each axis is
axes, respectively.
rotated inward toward the 45° line by the same angle a, where tan a = u/c = ft. The
axes approach the 45° line from either side in the limit u —* c and (5 -> 1, as the speed
of the frame S' approaches light speed in its uniform motion through S. A given event
at (x, ct) in S and at (*', ct') in 5" can be plotted with respect to either set of axes.
Because the primed axes are skewed, the projection of primed coordinates parallel to
these axes differs from the usual method of dropping perpendiculars onto the axes. We
should not be surprised to encounter such non-Cartesian properties since we have
already noted the non-Euclidean nature of space-time. The space-time interval
between the origin and the event indicated in the figure is given by

We may also consider a third frame S", which, like S', moves through S at the same
speed u but does so in the opposite direction. The coordinates (x", ct") in S" are
found by formulas identical to Equations (1-26) except for the replacement u — — u.
>

Figure 1-19 Figure 1-20

Space- time diagram showing three pairs of Events in a space-time diagram with axes for
axes for three different Lorentz frames. The two Lorentz frames S and S'. Events 1 and
transformed axes are skewed, inward for S' occur at the same spatial location in S'.

moving through S along the positive x axis, Events 2 and are separated by the
and outward for S" moving through S along propagation of a light signal. Events 3 and
the negative x axis. In the space-time are simultaneous in S'.
diagram, the x' axis is along the line ct = fix,

and the ct' axis is along the line ct = x/fi.

Slopes are determined by the angle a, where
= X = ct
tan a fi.
' X' =
ci(- ct'

ct" ct ct
Event

u -^ *i
42 Relativity

Accordingly, the axes in the space-time diagram are rotated by the same angle a in
the outward direction, as shown in the figure.

Example

Let us apply these space-time perspectives to look at several kinds of events.

Event is introduced for reference at the space-time origin, and other events
are located as in Figure 1-20. Events 1 and occur at the same point in S', the
spatial origin at x' = 0. The time A/' between these events in S' is therefore a
proper time interval. In S, the corresponding time interval is A/, as indicated in
the figure. We can use the invariance of the space-time interval to write

2 2 2
(uAt) - (cA<) = -(cht')

and solve for A/ to recover Equation (1-3), the time-dilation formula. Note how
the non-Euclidean geometry may tend to deceive us here; despite appearances
in the figure, A< is larger than A/'. Events 2 and are separated by the
propagation of light. Note that event 2 satisfies x = ct and x' = ct', and so a
light flash emitted at can propagate outward and be detected later at a
location on the x and x' axes as event 2. Events 3 and are observed in S' to be
simultaneous since both occur at t' = 0. Note that event 3 follows event in S

by the indicated time interval /,. The relation between these events is the same
as that in the example of the hunters and the game warden in Section 1-5.

Example

As a finale, let us return to the twin paradox and reconsider the motion of the
space twins Chester and Esther at the end of Section 1-4. Recall that Chester has
gone on a rocket trip away from Esther on at speed u = jc and, after 5 years
Esther's clock, abruptly turns same speed. We
around and comes back at the

know that the problem involves three Lorentz frames, Esther's frame 5 and
Chester's frames S' on the way out and S" on the way back. Figure 1-21 shows
the axes for these three frames in a space-time diagram, where 5 is chosen as
the frame at rest. We use years and light-years for the unwritten units of time
and distance in the diagram and in the following discussion. (Recall that a
light-year is the distance traveled by light in 1 year.) When / = /' = /" = 0, the

frames S and S' coincide and the spatial origin

in space, in S" is located at
x = 6 in S. The moving frames approach each other so that S' and S" coincide
when their origins reach x = 3 at / = 5 in S. This instant corresponds to
Chester's turning point, when the clocks in S' and S" read t' = t" = 4.

World-lines for Chester and Esther are also shown in the figure. Esther remains
at x = for 10 years in S, while Chester stays at x' = for 4 years out in S'

and then changes his address to x" = for 4 years back in S". Chester's clock
reads /" = 8 upon reunion with Esther. We have reached this conclusion from
Esther's point of view by staying in the single Lorentz frame S and observing
that Chester's time runs slower. Thus, we have recognized that her time is

dilated by the factor \ relative to the proper time in his frame, whether in S'
going out or in S" coming back. The puzzling aspect of the twin paradox arises
 1-7 Space -Time 43

when we adopt and try to confirm Esther's

Chester's point of view instead
advanced time. Relative motion
symmetry implies that Chester's time in S' is
dilated relative to Esther's proper time by the same factor |. Hence, Chester
observes that his outward transit time A/' = 4 corresponds to only At = 3.2 on
Esther's clock. Exactly the same relation holds between At" and At for
Chester's return. It would appear that Esther's time is coming up short in
Chester's calculation. In fact, Chester knows that the passage of Esther's time
gives t = 10, and not t = 6.4 (twice 3.2), because he sees that a certain aspect of
the problem has been left out of the bookkeeping. We can see what the missing
feature is by looking at the space-time diagram, especially at the point on

Figure 1-21

Lorentz frames and space- time diagram for

the twin paradox. The axes are (x, ct) in S,
(x', ct') in S', and (x", ct") in S". Coordinates
on the axes are given in light-years. Esther

stays at x = in S, while Chester goes off at

x'= in S' and comes back at x" — in S".

Upon reunion, Esther's clock reads I = 10,

while Chester's inbound clock reads t" = 8.

Chester's time intervals, A/' = 4 on the way

out and A/" = 4 on the way back, are
dilations of proper intervals in Esther's time of
duration At = 3.2 at each end of the journey.
The changeover from S' to S" accounts for
the gap At = 3.6 in Chester's view of Esther's
time.

fi'i
£l
t"=
t' = x' x"
t= 6 t-v
44 Relativity

Chester's world-line where he reverses his rocket and changes over from S' to
S". Two drawn through the space-time location of this event, one
lines are

parallel to the x' axis and another parallel to the x" axis. Along these two lines
events occur in S' and in S" that are simultaneous with Chester's turn-around
event. On Esther's clock, the times for these events occur 3.2 units from the
beginning and 3.2 units from the end of the trip, as indicated in the figure. Thus,
the diagram reveals a simultaneity gap of duration At = 3.6, which Chester must
include in his bookkeeping to account for all of Esther's time. Of course, the
calculation is much easier in S where Chester's turning point is simultaneous
with the midpoint of Esther's world-line. We have appealed to the relativity of
simultaneity to resolve the paradox, and we have found the space-time diagram
to be an indispensable aid in visualizing the argument.

1-8 Relativists Momentum and Energy

The properties of space-time follow directly from Einstein's second postulate of

relativity regarding the universality of the speed of light. Little need has arisen yet to
invoke the other postulate, which stipulates that the physical laws maintain their form
from one Lorentz frame to another. We now want to use this first postulate more
prominently as a constructive influence in the development of the principles of
relativistic dynamics.
We are concerned with the motion of a particle of mass m and velocity v in a
specific frame of reference. Newtonian dynamics is valid as long as the velocity
much smaller
remains than the speed of light. Then we know that we can define
momentum and kinetic energy for the particle as

p = m\ and K= \mv (nonrelativistic). (1-29)

These quantities appear in conservation laws determined by the dynamics. Examples

are the conservation of the total momentum in a free system of particles and the
conservation of the total kinetic energy in an elastic collision between particles. Our
objective is to extend the principles of dynamics by removing the restriction to small
values of v/c and generalizing the quantities given in Equations (1-29). The newly
formulated dynamical laws must continue to provide for the conservation of momen-
tum and energy. In fact, the first postulate of relativity requires that if the conserva-
tion laws hold in one Lorentz frame they must also hold
any other Lorentz frame as in

well. The problem is to deduce the proper relativistic expressions for momentum and
energy so that the corresponding conserved quantities are respected by the Lorentz
transformation. We know that these expressions must also reduce in the nonrelativistic
limit to the familiar forms in Equations (1-29).
The most direct way of presenting this problem is simply to divulge the answer
immediately and then demonstrate the properties of the solution. In this spirit we
assert without further ado that the relativistic momentum p and the relativistic energy
E are given for a particle of mass m by the formulas

OTV
P= ,

- 2
(1-30)
/l v /c 2
 1-8 Relatmstic Momentum and Energy 45

and

mc"
E= 9 ,
(1-31)
,
/l - v
2
/c 2

The momentum obviously goes over into its nonrelativistic form for v <s: c. The
energy E is a new kinematical quantity whose meaning is to be examined in due
course.
The underlying strategy should be spelled out clearly so that these assertions can be
grasped. We expect observations of momentum and energy to yield altered values
when the observations are made in a different Lorentz frame. Our strategy focuses on
the proper behavior of these kinematical quantities under transformation to any such
new frame. We know that Equations (1-26) describe the passage from one space-time
frame S, where the coordinates are (x, y, z, ct), to another space-time frame S',

where the coordinates are (x', y', z', ct'). Let us set up a correspondence of properties
between the momentum and energy variables and the space and time coordinates by
first assembling the kinematical quantities into the fourfold set (p x , p , p., E/c). (We
use E/c instead of E for the fourth variable so that all four quantities in the set have
the same units of momentum. This convention parallels our use of ct instead of / in

Equations (1-26).) We then assume that these four variables in the frame S transform
into a new set (p'x p', p': E'/c)
,
, when we pass to the new frame S' , and require that

the transformation rules have exactly the same form as those used to relate (x, y, z,ct)
and (x', y', z', ct'). The proposed relations are just like Equations (1-26):

p: = p„
E' IE
— = y I--J8/.
\

I, (1-32)

where and y are again given by Equations (1-25). These relations specify the
/?

behavior of relativistic momentum and energy under Lorentz transformation. Note in

particular that p and E are mixed in the passage to the new frame just as x and /
t

are.
The argument behind Equations (1-32) should be restated for emphasis. We want
to guarantee the transfer of conserved quantities from one Lorentz frame to another
and ensure specifically that, if p and E obey conservation laws in S, then p' and E'
automatically obey the same conservation laws in by arguing
-S". We accomplish this

that p and E and E' according

should transform into p' to the same rules that govern
the transformation of coordinates from S to S'. Thus, the strategy starts with the
formulas for momentum and energy in Equations (1-30) and (1-31) and requires that
these quantities transform like space and time. Our remaining task is to demonstrate
that the strategy works.
The demonstration employs Equations (1-22) for the transformation of velocity
along with the equations given above. Let us begin by recognizing the resemblance
between the Lorentz transformation parameter y and the ^-dependent root factor in
46 Relativity

the expressions for p and E. We define

Y,.=
'

(1-33)
i 2

as a shorthand device and note that y depends on the relative speed u between frames
5 and S' while yv depends on the velocity v of the particle in the frame S. Thus, y is a
constant parameter since u constant, while yB is a dynamical variable that varies
is

with time in situations where the speed of the particle is changing. Equations (1-30)
and (1-31) take the form

p = yv m\ E= 2
and y„mc

when yu is introduced. In S', the particle velocity is v', and so a corresponding

variable yu is defined by analogy with Equation (1-33). The components of v and v'
.

are related in Equations (1-22). We can use these formulas to establish a remarkable
algebraic relation among the y's:

YB ' = YY.|l (1-34)

--J]-
This result contains all the complicated algebra needed to demonstrate the transfor-
mation properties of p and E. We confirm the first of Equations (1-32) by making the
following calculation:

y
/

\
a - P-]
c
E \

= yyM v -
I
x ") = y,,-™—
1
vx

—
: ——
—
uvx /c
u
>
= y^ mv ' = P'
x -

We have used, in turn, Equations (1-30) and (1-31), (1-33), (1-34), (1-22), and finally
(1-30) again in its primed form. The last of Equations (1-32) follows in similar
fashion:

y(E - ficpx )
= yy„m(c 2 — uvx )
= y^mc 1 = £".

Here, we use the same series of formulas concluding with the primed version of
Equation (1-31). These two derivations along with analogous ones for p' and p'.
furnish the desired proof that p and E in Equations (1-30) and (1-31) indeed
transform under Lorentz transformation according to Equations (1-32).
Our discussion has focused on transformation properties, and so the presentation
may seem somewhat abstract. We should realize that relativity is a treatment of
frames of reference where rules for the transformation between frames are essential
considerations. We have acknowledged this by introducing relativistic momentum and
energy in context with the Lorentz transformation. Now that these abstract conceptual
features have been presented, we can proceed to the physical interpretation of the new
dynamical quantities.
It is obvious that p and E should depend on the velocity of the particle. We can

eliminate the explicit dependence on v and relate p and E directly to each other by
squaring and comparing expressions. The result is a very important equality known as
the relativistic relation between energy and momentum:

E2 = c
22
p + m 2c\ (1-35)
 1-8 Relativistic Momentum and Energy 47

We have yet to identify the meaning of the relativistic energy E. Let us note first that
E has a definite nonvanishing value, even when the particle is at rest. If we set p =
in Equation (1-35), we obtain

E rest
= mc\ (1-36)

the minimum energy possible for a free particle. This quantity is determined by the
mass of the particle and is called the rest energy. If we let v be nonzero but very small
2
compared to c, we can approximate yv by expanding in powers of (v/c) :

2 \ —1/2 2
V \ ' V

'
+ '"-
2^

Insertion of this expansion in Equation (1-31) results in an approximation for the

relativistic energy:

E= mc + -,mv
2
(nonrelativistic)

to order (v
2
/c 2 ). We recognize the two contributions to be the rest energy and the
Newtonian kinetic energy. This calculation is useful only for small v/c. The result can
be generalized for any value of v by defining the relativistic kinetic energy as

-1 . (1-37)

A graph is shown in Figure 1-22. The effect of the speed limit is seen
of this expression
clearly in the definition and in the figure. The kinetic energy of the particle is not a
real-valued quantity and is therefore undefined for v > c. The nonrelativistic version
of K is an adequate approximation to Equation (1-37) for !»<c but departs from the
exact expression and eventually violates the speed limit as v grows without bound. The
interpretation of the relativistic energy may be summarized by writing

E= mc 2 + K. (1-38)

This formula is valid for any v < c and consists of two separate pieces, the one
associated with the mass of the particle and the other associated with its motion.
Equations (1-30) and (1-31) suggest the identification of a mass" in the
"relativistic
combination of factors yu m. This quantity grows as v increases and becomes infinite as
v -» c. The factor m by itself is sometimes called the "rest mass" to distinguish it from
the ^-dependent relativistic mass. Figure 1-22 indicates how a practical application
may be made of this nomenclature. We know that the kinetic energy of a particle can
be increased by applying a force and doing work. The work done on the particle
causes a gain in the particle's relativistic mass along with the expected increase in
velocity. The figure shows that we cannot accelerate the particle to indefinitely large
velocity since there is a speed limit at v = c. Close to the limit, the increase in
relativisticmass becomes the dominant effect as further increase in velocity becomes
more and more restricted. It is obvious from the figure that an infinite amount of work
is required to accelerate the particle all the way to light speed. We have already noted

that the relativistic mass approaches infinity in this limit, while the rest mass remains
fixed throughout the acceleration process. Now that we have acknowledged the
48 Relativity

Figure 1-22 Figure 1-23

Relativistic kinetic energy versus particle Conversion of mass to energy. The nucleus A
velocity. K is not defined beyond the speed changes into the less massive nucleus B, and
limit where v = c. The nonrelativistic y rays carry away the energy arising from the
expression A" NR = -,mv
l
violates the speed difference in mass. The elementary particle
limit and holds only for v <s. c. decay t" —> y + y illustrates the complete
conversion of mass into y-ray energy.
K

distinctive behavior of "relativistic mass," let us forego the terminology hereafter and
always refer implicitly to "rest mass" whenever we speak of mass from now on.
The formula E = mc 2 appears frequently in popular science writing. In context,
the usage refers generally to a nuclear process in which a small portion of the mass of
an atomic nucleus is converted into a large amount of energy. Prospects for obtaining
energy from mass have their origin in one of Einstein's thought experiments. His
hypothetical process involves a mass at rest spontaneously changing into a lighter
mass, also at rest, with the simultaneous emission in opposite directions of two
high-energy electromagnetic waves, called y rays. The described process

A B + y + y

is shown schematically in Figure 1-23, where A and B denote two species of atomic
nuclei. The sum of the energies carried away by the two y rays is evidently given by

A£ = kMc 2
,

where A M is the nuclear mass difference MA — M B . A more current realization of

Einstein's thought experiment is found in the indicated process of 7r° decay,

77"° —* y + y,

in which one of the elementary particles, the it meson, is observed to change into y
rays and convert all its mass into y-ray energy.

Mass is an intrinsic attribute of a particle. A nonvanishing value for the mass is a

requisite property for any classical particle, as entities with no mass have no place as
particles in classical physics. Relativity makes room for massless particles inasmuch as
the expressions for relativistic momentum and energy make sense in the limit of zero
mass. Equations (1-35) and (1-36) tell us that

E= cp and £ rest = o (1-39)

 ,

1-8 Relativistic Momentum and Energy 49

in this case. Equations (1-30) and (1-31) make sense as indeterminate forms in the
limit m —* 0, provided the simultaneous limit v —> c is also taken. Thus, massless
particles may exist provided they travel at the speed of light. Such particles cannot be
found any frame and must have speed v = c in all Lorentz frames. The
at rest in
limiting behavior of energy and momentum E — and p —» may be observed for a >

massless particle provided the small values occur together in the appropriate frame
obeying Equations (1-39).
The first of these two equations may be somewhat familiar. We know from
Maxwell's theory that electromagnetic waves carry energy and momentum according
to the properties of the Poynting vector. The energy and momentum of the radiation
satisfy a relation identical to the equation E= cp. The possible massless-particle
aspects of the radiation remain to be explored in Chapter 2.

Example

The momentum and energy of a particle are determined by the relativistic

formulas, and not by Equations (1-29), whenever the kinetic energy of the
particle is comparable with its rest energy. To illustrate, let us consider beams of
accelerated electrons and protons and take the approximate values 0.5 MeV and
1 GeV for the respective rest energies. (Recall that the electron volt eV is a unit
of energy equal to that acquired by a single electronic charge accelerated in a
potential difference of 1 volt.) It is clear that a 1 MeV beam kinetic energy is

relativistic for the electron but not for the proton and that a 10 GeV beam is

relativistic in both cases. We can assess any of these situations by turning to

Equation (1-37) and solving for the ratio v/c in terms of the ratio K/mc . The
result of this exercise is given in Problem 25 at the end of the chapter:

v
- =
/(c(k + 2)
, where k = — A'
- .

c k + 1 mc

We note that the formula becomes

v
- = v2k when k •« 1

in agreement with the result obtained from the nonrelativistic expression A

= L,mv~.
At 1 MeV we have

v
k = 2 and - = \l - for electrons,
c V 9

/hile

v / 1

and - = \ = 0.045 for protons,

1000 c V 500

At 10 GeV the electron case gives

v / 100020000
k = 10000 and - = \ = 0.999999995,
c V 100020001
 .

50 Relativity

while the proton case gives

V / 120
k = 10 and \\
= 0.996.
c V 121

Since the electron is ultrarelativistic at this energy, it is more practical to

compute v/c from an expansion o f the formula in powers of 1/k. The result is

also to be found in Problem 25:

V 1 1

- = 1
- to order —7
c 2^ K

The computation gives

v 1
H
" 2k 2 ' = 0.5 x 10 forx = 10
4
,

in agreement with the answer given above.

1-9 Relativistic Dynamics

Classical dynamics begins with concepts of force and mass in the context of Newton's
laws of motion and then proceeds to the conservation laws of energy and momentum.
The empirical approach is taken to establish the equations

F = ma and F = —
dp
dt
(classical)

as principles that govern the behavior of particles. This scheme is internally consistent
and amply confirmed by experiment, as long as the particles have velocity much
smaller than c.

Our treatment of relativistic dynamics begins with a different premise based on the
conservation of momentum as a first principle. The conservation of relativistic energy
follows logically from the same starting point. We have introduced these ideas in
Section 1-8 and we are now prepared to take up the concept of force, again pursuing
the empirical approach to the dynamical equations. We turn to this question next,
after we have made the following observation about the two conservation laws.
Let us consider a process in which an initial system of colliding particles reacts to
form a final system of emerging particles. The particles in the final state of the
reaction do not have to be the same We suppose that an
as those in the initial state.
observer S determines the total momentum and total energy, before and after the
in

reaction, and records the results as (P bl fort., ^before) anc (Pa fter> ^after)- Differences in
.
^

momentum and energy can be defined as

A" "after "before

.Hid

A'k £ after ^before 1

 1-9 fielativistic Dynamics 51

The transformation rules in Equations (1-32) can then be used to deduce the
corresponding differences determined by an observer in another Lorentz frame S' in
motion relative to S. The relations are

A£
ap; = y
/
ap, - p— \
,

ap/ = ±py ,

ap; = ap,
AP' / AP \
=y /?AP I
(1-40)

Next, we suppose that the observer in 5 confirms momentum conservation by finding

^before to De tne same as ^after so tnat AP = 0. We also assume that the observer in S'
agrees, finding momentum to be conserved in AP' = 0. Equations (1-40)the form
then imply that AP = in S and that AP' = in S'. Thus, both observers agree that
the total relativistic energy is conserved because they have already agreed that the
total momentum is conserved. This linkage of agreements is secured by the Lorentz
transformation. The agreement itself is the first premise of relativistic dynamics,
coming before the introduction of forces.
We express the force law for a relativistic particle by writing

m\
¥= —
dp
= -
d
.

-
(1-41)
dt dt /l D 2/ f 2

It is understood that we must establish the operational validity of such a law by

turning to experiment, just as in the case of Newton's equation F = ma. The most
useful candidate for investigation is the electromagnetic force on a charged particle.
The dynamics of a charge e, moving in electric and magnetic fields E and B, is

governed by

F = f(E + vXB), (1-42)

the well-known Lorentz force from classical electrodynamics. It is an empirical fact

that Equations (1-41) and (1-42) together provide a description of charged-particle
motion in agreement with experiment for any velocity v. Equation (1-41) is consider-
ably more complicated than the simple expression F = ma. Often, it is possible to
obviate some of the complications by relying on conservation laws wherever possible.
The concept of work links the force in Equation (1-41) with the relativistic energy.
We can examine this we do
connection by constructing the work-energy theorem, just as
in Newtonian mechanics. For simplicity, let us confine our derivation to the case of
motion in one dimension. The work done by the force as the particle moves along the
x axis between points x and x 2 is expressed in terms of the familiar integral over x.
x

We convert this to an integral over v in the following sequence of steps:

[dp dp
W= J
r*2
Fdx = I —vdt = jvdp =
r /•'..

J
v — dv,
 .

52 Relativity

where y, and v 2 are the velocities of the particle at x, and x 2 - We then use

2
dp d
(
dy\ I v

in which we have inserted the relation

:
dyv d 1 v/c
~& -
' ~dv /i v */ c 2 '
(1 -v 2 /c 2 Y

These maneuvers transform the formula into an integrable expression:

II
r mo

(i-, 2 A 22\V
>

)
/
TTjdv
v
2 /
/c
:
= £,-£,.

We may then use Equation (1-38) to rewrite the result as

W= K 2
- A', (1-43)

Thus, the work done by the force on the particle is equal to the change in the

particle's relativistic kinetic energy, a conclusion parallel to that found in the

Newtonian version of the theorem.
Next, let us apply the dynamical equations in three-dimensional vector form to
demonstrate how the relativistic momentum of a charged particle can be measured.
The application is the familiar one in which the moving charge is injected into a
uniform magnetic field, as sketched in Figure 1-24. The motion is governed by the
force

F = e\ X B. (1-44)

Figure 1-24

Relativistic charged particle in a uniform

magnetic field.

1
 .

1-10 Collisions and Reactions 53

As usual, this force does no work since F and v are perpendicular vectors:

2
W= '

( F • dr = (~F •\dt = 0.

It then follows from Equation (1-43) that the kinetic energy is constant, and so the
speed of the particle is also constant. Therefore, yv is a constant parameter in
Equation (1-41), and the equation of motion takes the simpler form

dv
fvXB = yv m — dt
(1-45)

This expression tells us that the acceleration a = dx/dt is perpendicular to v and B. If

v is initially perpendicular to B when the particle is injected into the field, the three
vectors a, v, and B remain mutually perpendicular throughout the motion. We
recognize that a particle orbit with these properties must be planar and circular, as
indicated in the figure. The familiar centripetal acceleration results, with magnitude
a = v~/R, where R is the radius of the circular orbit. We insert all this information
into Equation (1-45) to get

2
v
evB = y, m — ,

and we rearrange to obtain the final formula:

eBR = yv mv = p.

This expression for the relativistic momentum is identical in form to the nonrelativistic
result. The measurement of p then follows directly from measurements of B and R.

1-10 Collisions and Reactions

Modern physics is concerned with the structure of matter and the interactions of the
constituents of matter. These basic properties of nature can be investigated by probing
systems of particles in collision processes. Thus, we are able to "see" the structure of
the atom and by exposing the systems to beams of suitable particles with
the nucleus
appropriate incident energies. Studies of matter on an even smaller scale are accom-
plished in collisions at relativistic momenta. The larger collision energies make
possible the disintegration of the nucleus and the production of new elementary
particles. These investigations at high energy are analyzed according to the principles
of relativistic kinematics. The analytical procedures are in essence exercises in the
application of momentum conservation and energy conservation. It is important to
realize that we do not have to understand the specific nature of the forces between
particles in order to implement these conservation laws.
To begin our survey of relativistic kinematics, let us reconsider the conversion
between mass and energy and emphasize that mass does not have to be conserved. We
are guided by the principle of conservation of the total energy, where we construe the
energy to include all possible manifestations. Consider the collision shown in Figure
1-25 in which the two colliding particles are assumed to have the same mass m and
speed v. The particles come together from opposite directions and interact in a
completely inelastic collision to form a single mass M. We refer to the process in these
54 Relativity

Figure 1-25 Figure 1-26

Inelastic collision in m + m — M.
which > Inelastic collision in a conservative classical
Conservation of momentum and energy imply model. The initial kinetic energy is converted
that mass is not conserved. into potential energy stored in the compressed
spring.

.0_Q_Q_Q_Q_Q.

m jOJJflfl(
m

terms since all the kinetic energy of the initial system disappears in the collision. The
finalmass M is produced at rest because the conserved total momentum is zero. We
determine this mass by invoking conservation of the total energy in either of the two
forms

mc 2
Mc 2 = 2
l/l - v
^/c=
2 2
(1-46)

or

Mc 2 = 2mc 2 + 2K,

where K is the kinetic energy of each initial particle. It is obvious that the final mass
M exceeds the total initial mass 2m as the initial kinetic energy is entirely converted
into the increase in mass.
Let us imagine a classical model for such an inelastic collision in which the masses
stick together and yet only conservative forces are involved in the balancing of all the
energy. We may use the massless ratchets-and-spring device in Figure 1-26 for this
purpose, and assume that the colliding particles lock onto each other with negligible
friction and compress the spring between them. The spring absorbs, and stores as
potential energy, the total kinetic energy brought into the collision by the initial
particles. Our relativistic treatment simply identifies the final aggregate as a new
system having its own mass M, whose rest energy includes the effect of the potential

energy modeled by the compressed spring. If we remove the spring from the classical
model, we conclude that all the initial kinetic energy is dissipated in friction and shows
up as heat in the final system. Again, the relativistic treatment regards this quantity of
heat as part of the final rest energy Mc'. Thus, even thermal energy can be associated
with an identifiable mass from the viewpoint of relativity.

Next, let us reverse the completely inelastic process and consider the breakup of M
into two unequal masses, as shown in Figure This phenomenon is realized
1-27.

physically in the spontaneous fission of a nucleus into two fragments and in the
two-body decay of an unstable nucleus or elementary particle. Since M is at rest,
momentum conservation demands that m and m 2 have
x
opposite momenta of the
same magnitude p, as indicated. Conservation of energy then requires that

£, + E2 = Mc 2
 1-10 Collisions and Reactions 55

-2*,2
c
c c „2 4
+ m\r + \ic
i i
+ 2,4
m\c
w 2
= Mc
p p

2
with the use of Equation (1-35). It is not difficult to solve this relation for p , the only
unknown quantity, and obtain

2
[M 2 -{m +m f\[M -{m -m 2 f\
x 2
2
x

P = (1-47)
\M'-

Thus, the momentum of each particle in the final state of the two-body breakup
process is uniquely determined by the values of the participating masses M, m,, and
m2 . Conservation of energy may also be written in terms of the kinetic energies of m,
and m 2 :

m x
c
2
+ K + m 2c 2 +
x
K 2
= Mc 2 .

The difference in rest energy between initial and final states is called the Qvalue for
the given process. In this instance, the ()-value has the form

Q = (M - m, - m 2 )c 2 = K + K2 x
. (1-48)

Note that the kinetic energy in the final state is obtained from the excess mass in the
initial state.

Let us now introduce Lorentz frames in our discussion of the breakup process. For
simplicity, we take the masses of the two final particles to be equal and consider the
two-body decay M— > m + m described in Figure 1-28. The upper part of the figure
shows the decay of M at rest in the Lorentz frame 5". Note that this view of the process
is the reverse of the collision in Figure 1-25, and so Equation (1-46) gives the correct

Figure 1-27 Figure 1-28

Two- body decay M— » m, + m , with M at Two-body decay — m + m for M > M at rest

rest. and for M

in flight. The decay in flight has

© the simplifying feature that one of the final

particles
by a transformation
which S'
is

is
left at rest.

the rest frame of

These decays are related
of Lorentz frames in
M and S is the
£2 frame of the decay in flight.

®
S'
^K5 &^
56 Relativity

relation between the indicated speed vand the masses of the particles. The Lorentz
transformation comes into the picturewhen we also consider the decay of in flight M
and introduce another Lorentz frame S in which is a moving particle. This version M
of the process is illustrated in the lower part of Figure 1-28 for the special situation
where one of the final particles happens to be produced at rest. Our problem is to
determine the velocity v of the other final particle in the frame known
S, given the
velocity v in the frame S'. Special circumstances characterize this problem; the initial
mass is at rest in S', and one of the final masses has speed v in S' and is at rest in S.
These conditions tell us that S' must be moving through S wifh speed u = v and that
M must be moving in S with the same speed, as shown in the figure.
We analyze the problem by using the Lorentz transformation to relate momenta
and energies between the frames S' and S. The transformation from S' to S is
performed with formulas inverse to those in Equations (1-32):

/ E'

E E'
- =
y[
I

— +£/,;• (1-49)

Let i's apply the first of these relations to the final particle moving to the right in the
figure. In S' we have

P'x
= yv mv an d £' = Y, W(:
">

and so

~ Yv mv ~"Vv mc
=
Px M ~*~
2y,r'»»'.

Note that we have used u = v to replace y by y v and /? by v/c. We know, however,

that the momentum in .V is given in terms of the speed v by

px = y-M>-

These two expressions for p imply an equality between the factors 2y,r^ and
x
y-y.
t
The
desired solution for v emerges from this equality after a few algebraic steps:

2v
r,= (1 -
50)
rr^7^-
+ v/c
1

We should recognize the result. Equation (1-50) expresses the relativistic addition of
velocities according to the first formula in Equations (1-23).
Our point in this discussion of Figure 1-28 is to emphasize the fact that the two

indicated decays, at rest and in flight, are one and the same phenomenon viewed from
two different Lorentz frames. It is evidently sufficient to understand the decay at rest
since the decay in flight can then be analyzed by applying the Lorentz transformation.
Many interesting phenomena are observed in relativistic collisions as a consequence
of the conversion between mass and energy. The conservation laws allow processes in
which particles collide and produce altogether different systems of particles in the final

state. These reactions must conserve the total momentum and the total energy, so that
 1-10 Collisions and Reactions 57

the equations

P before = Paf.er and £ before = £ aft , r ( 1

-5 1 }

govern the production of new particles. There also exist other conservation laws that
pertain to other attributes of the interacting particles. An assessment of all possible
conservation laws in a particular reaction constitutes a certain view of the interactions
responsible for the process, where the observations are made at a great distance from
the scene of the reaction. The subscripts before and after in Equations (1-51) are meant
to convey this sense of the observation procedure.

The observations generally involve a two-body collision between an incident beam

particle and a stationary target particle. An accelerator is usually the source of the
incident beam. The laboratory (lab) frame designates the Lorentz frame in which the
target particle is at rest. The Lorentz transformation can be used to describe the same
process in the center of mass (CM ) frame, defined as the Lorentz frame in which the
colliding particles have zero total momentum. We should recognize the similarity
between this special frame of reference and the rest frame of the decaying particle in
Figure 1-28. It is convenient to formulate the physics of an observed process in the
CM frame and then transform to the lab frame for comparison with the measured
data. The transformation from CM to lab is therefore an especially important
application of the Lorentz transformation.
Beams of particles can also be made to collide with each other and produce new
particles in the head-on collision. The colliding beams provide the experimenter with
an opportunity to observe reactions directly in the CM frame. The advantages of
colliding-beam experiments are illustrated in the example below.
Let us look at the details of the lab «-> CM transformation and adopt notation
according to Figure 1-29. The lab frame is S, where the target particle is at rest M
and the beam particle m has speed v. The CM frame is S', where m and approach M
each other with speeds v' and u, respectively. We recognize immediately that u must
also be the speed of S'moving through S. Our goal is to establish relations among the
three given speeds. Let us digress for a moment and recall the following two formulas
taken from the Newtonian view of the transformation between S and S':

v' = v — u and rrw' = Mu (nonrelativistic).

Figure 1-29

Two-body collision in the lab frame and in

the CM frame.

CM frame S'

Lab frame S
58 Relativity

The first equation is a statement of velocity addition in Galilean relativity, and the
second is a statement of nonrelativistic momentum conservation in the CM frame. We
can eliminate v' between these two equations and obtain the desired relation between
u and v.

m
u = v (nonrelativistic). 1-52)
m + M (

To conclude the digression, let us recall that the center of mass of the Newtonian
system is a well-defined point, located between m and M, whose speed remains
unchanged before, during, and after the collision. The relativistic transformation
between S and S' calls for more complicated equations. We express velocity addition
and momentum conservation by writing

v — u mv' Mu
v' = and

It is obvious that the elimination of v' is more laborious in this case. The result is left

to be derived in Problem 36 at the end of the chapter:

mv

m + M\j\ - v
2
/c 2

Of course, the final formula goes over into Equation (1-52) for v «c c.

We have only sketched this route to Equation (1-53) because we now want to show
the simpler recommended way to obtain the speed u. Let us return to Figure 1-29 and
identify the total momentum and total energy for the two-body system in the lab

frame S:

mv mc
Ptcai - "7= =T7T and £«- = = +Mc2 (1 - 54)
\jl - d/c yi
T7T
- »7c
-

The Lorentz transformation generates the corresponding quantities in the frame CM

S'.However, the total momentum in S' is known to be zero by definition of the CM
frame. We use this information as a constraint on the transformed momentum:

^ta. = YUotal " 7^«otal

=0-

A very general expression for the ratio u/c results:

^ total

The formula takes the form

2
u mv /l/l - i' /c-

c mc'/p - v
l
/c l + Mc'
 I 10 Collisions and Reactions 59

when Equations (1-54) are used, and the desired Equation (1-53) follows directly from
this result. We note in passing that the relativistic relation between S and S' does not

refer to any point called the "center of mass." Instead, S' is characterized by the
momentum condition P ^ = 0. It would t tal
be more fitting to call S' the "center of
momentum" frame for this reason.

Example

Formulas in relativistic kinematics become simpler when the colliding particles

have equal mass. To illustrate, consider proton -proton collisions and let each
particle have the same mass in Equation (1-53): M

l + yi - v
2
/c 2

This relation gives u, the speed of the CM frame through the lab. We can turn
the equation inside out and solve for v, the speed of the beam particle in the lab:

2a

+ ir/r

The result is easily understood by noting that the two protons must have the
same speed given by u in S', the CM frame. The expression for the speed v of

the beam proton then follows directly from velocity addition. We have found it

instructive to refer to P^ t (ai

in the preceding paragraph, so let us now evaluate its

partner
'
i? t jta ,
, the total energy in the CM frame. The second of Equations (1-49)
gives the relation between the total energies in the two frames:

£ o«a. = y(Ku*
t
+ ^p ; t tal )
= y£ ; t tal ,

where

Mc 2
EL, = 2 = 2yMc 2
yl - Myc-2

in this equal-mass situation. We solve for the Lorentz-transformation parameter

F'total
L-

2Mc 2

and combine this equation with our expression for £ tota |

to find the interesting
result

E; 2 a] = 2Mc% otal .

Let us apply our formula to an illustration involving colliding proton beams,

each with 10 GeV kinetic energy. For convenience, we let the proton be assigned
an approximate 1 GeV rest energy. The resulting total energy for the CM
two-proton system is

£,'otai
= 2(10 GeV + 1 GeV) = 22 GeV.
60 Relativity

The related value of the total lab energy is quite large because of the quadratic
relation between the two quantities:

2
£/!, (22 GeV)
£«.,
'total
= t-^7 = = 242 GeV.
2 Mr- 2 GeV

The beam proton must therefore have a correspondingly large kinetic energy in
the lab frame, where the target proton is at rest:

K=£ totaI
- 2Mc 2 = 240 GeV.

This calculation tells us that a 10 GeV-on-10 GeV colliding-proton facility is the

equivalent of a 240 GeV proton accelerator with a fixed proton target, in the
sense that the total energy in the center of mass system is the same in the two
laboratories. A large portion of the incident beam energy on the stationary
target is evidently consumed in transporting the "center of mass" of the
two-proton system through the collision process. This allocation of energy to
center of mass motion makes that amount of energy unavailable for reactions in
which new particles can be created. Colliding beams operate ideally in the CM
frame where none of the energy is impounded in this way.

1-11 Four-Vectors:}:

Relativity invites us to think in terms of four dimensions where the fourth dimension
refers to the time. We already know and time is
that a geometrical conception of space
useful for the presentation of events and world-lines. We now want to incorporate
relativistic momentum and energy and expand the presentation into a more fully

developed geometrical picture. The utility and elegance of such a four-dimensional

description become more apparent as the effects of the Lorentz transformation
materialize in the picture. This treatment of relativity by the methods of four-dimen-
sional geometry is the contribution of H. Minkowski. The four dimensions define a
geometrical framework for relativity known as Minkowski space. We introduce these
elegant methods at the end of the chapter so that we can enrich our outlook over the
concepts of Einstein's theory.
A particular choice of Lorentz frame S corresponds to a certain set of space and
time axes in the four-dimensional space. We specify the space-time coordinates of a
given event with respect to these axes and assemble the coordinates in the form
( x, y, z, id ). The variables define the space-time (or position) four-vector that locates the
event in .S' with respect to the origin in Minkowski space. Note that the fourth
dimension is taken to be an imaginary- valued coordinate; this feature of the definition

serves to distinguish time from space in the chosen Lorentz frame.

It is convenient to represent the position four-vector for the event in 5 by
introducing the column matrix

y
(1-56)

ict

$The methods and results of this section are needed again only in isolated parts of Chapters 2
and 16.
 /-// Four- Vectors 61

A different Lorentz frame S' corresponds to another set of space and time axes in
Minkowski space. The given event is located in S' by means of a primed four-vector,
with coordinates (x\ y', z', id') and column matrix

(1-57)

id'

Thus, we use o to specify some event in one frame S, and we use a' to specify the same
event in another frame S'.
The Lorentz transformation relates the components of o and o' according to
Equations (1-26). We can rewrite these relations in more compact notation with the
aid of the matrix equality

x Y iyfi x

/ 10 V

10 (1-58)

id' iyfi y id

(It is important to appreciate the equivalence between Equations (1-26) and Equation
(1-58). Similar techniques of matrix multiplication are put to use freely throughout
this section.) We take advantage of the simplifying matrix notation to cast Equation
(1-58) into its final concise form,

= 2>o (1-59)

in which =£? denotes the indicated four-by-four matrix parametrized by the constants
ftand y. This square matrix depends only on the speed u of S' moving through S. It
therefore contains all the information needed to relate position four-vectors for any
given event as observed in the two Lorentz frames 5 and S' The highly streamlined .

formula replaces a cumbersome set of relations and thereby facilitates our interpreta-
tion of Minkowski-space geometry.
We are immediately brought back to familiar ground when we evaluate the
T 1
product of matrices o o (where o denotes the transpose of the matrix o):

X
y
i
nl = ^+y + z- 1-60)

id

and, in similar fashion.

x'
2
+/ 2
+ z' :V 2 . 1-61

These calculations reproduce the squared space-time intervals s 2 and s separating

2
the origin and the event in the frames S and S'. Recall that s has been defined in
Equation (1-27). We have learned that this quantity does not change under Lorentz
transformation; therefore, we can reexpress the Lorentz invariance of the space-time
interval in terms of Minkowski-space four-vectors by writing

(1-62)
62 Relativity

The main reason for the imaginary number i in the time coordinate of o is now
apparent. We need the i to secure the vital minus sign in the c
2
t
2
contribution to
T
o o.

This sign then ensures Lorentz invariance in the form expressed by Equation (1-62).
Our strategy may be summarized and evaluated as follows. We have two space-time
frames S and Minkowski space, and we are given a specific event for
S' in

observation. The in S and in 6" by the four-vectors o and o',

event
is located

respectively. Passage from S to S' is described by a Lorentz -transformation matrix ££ that

transforms o into o' The Lorentz-invariance condition in Equation (1-62) tells us
'.

that the "length" of the original four-vector is preserved in this operation. It follows
that the Lorentz transformation can be interpreted as a rotation of the axes in
Minkowski space, since rotation preserves length. The Lorentz transformation of
interest refers to motion of S' through S along the x direction, and so the correspond-
ing rotation involves the x and ict axes in the four-dimensional space. This remark-
able correspondence between frames in relative motion and rotations in space-time
can now be used to good advantage.
Thegeometrical interpretation of Lorentz invariance translates directly into a
characterizing property of the transformation matrix ££ Let us return to Equation '.

(1-59) and take the transpose of both sides:

.'T = o
T££'>

Equation (1-62) then becomes

r T T
c <e sec

when Equation (1-59) is also used. The product of matrices y T££ evidently has the
same effect as the four-by-four unit matrix on any four-vector o. The matrix equation

<e
Tse= i (i-63)

follows from this observation. We can verify the equality by explicit matrix multipli-
cation:

Y ) -iyfi Y
1 1

') (i
1 1

lyfi 3 y _-iyfi Y

Vo-zn
1

J - 1
Y (1 a

Since y
2
(\
)
—
= 1, the unit matrix is obtained and Equation (1-63) is confirmed.
fi
2

Minkowski space is constructed on the notion of a position four-vector. Let us

broaden the concept and take any collection of four physical quantities to be a
four-vector, provided those four quantities transform just like the components of the
position four-vector in the passage to another Lorentz frame. To be specific, the
column matrix of quantities

b
y

bz

ib.
 /-// Four- Vectors 63

is defined to be a four-vector in the frame S if there is a corresponding set of

quantities I' in another frame S' that satisfies the transformation rule

6'=<e&, (1-64)

where ¥
is the same transformation matrix used in Equation (1-59) to pass from S to

*S". Thus, 6 is a four-vector if 6 transforms like c. Not every three-dimensional vector

b can be promoted to four-vector status. A case in point is the velocity of a particle

v = dr/dt; the transformation properties of v in Equations (1-22) do not conform to
the necessary rule.
The best example of a four-dimensional entity that transforms like o is the
momentum-energy (or momentum) four-vector. If we take p and E from Equations (1-30)
and (1-31) and assemble the column matrix

A
Py
/ (1-65)
Pz
iE/c

we then know from our discussion in Section 1-8 that ft meets the necessary
transformation criterion. The components of ft give the momentum and energy of a
particle as observed in the frame S. These quantities transform to the frame S'
according to Equations (1-32). The transformation rule has the form of the matrix
equation

ftt=Seft, (1-66)

as required for a four-vector. In fact, we have anticipated this desired behavior in our
discussion of the properties of relativistic momentum and energy. Note that the
imaginary factor i is needed in the fourth component of
ft
to make the transformation
of the momentum four-vector come out correctly.
We can now begin to appreciate the power and elegance of four-vectors. Let us
start by showing that the Lorentz-invariance condition in Equation (1-62) holds ior ft
as it does for a:

T T
ft' ft'=ft ft. (1-67)

7
This statement is easily proved by multiplying through Equation (1-63) with ft
on
the left and ft
on the right, and by using Equation (1-66). The resulting equality
becomes

p? + p:
2
+ p:
2
— E' 2
r = p* + p; + p- -
E2
—•
c

or

2
E'
1
„
i
E 1

P' = P 2 ,

when the components of the momentum four-vectors are inserted in the calculation.
Observe again how the presence of the factor i in the fourth component of
ft
affects
the identification of a Lorentz-invariant property. Equation (1-35) tells us that the
64 Relativity

T
invariant quantity ft ft
is determined by the mass of the particle:

/'/' =// 2,2

= -mrc (1-68)

Thus, Lorentz invariance holds for masses as it does for space-time intervals,
requiring in this instance that all observers agree on the mass of a given particle.
Equation (1-63) can be regarded as the source of all possible Lorentz-invariance
properties. If we
choose 6 to represent any four-vector, and we multiply this basic
equation fore and aft by & T and & and use Equation (1-64), we obtain

t"t' = t't (1-69)

as a more general statement of Lorentz invariance. Let us apply the general

expression to the reaction problem described in Figure 1 -30. We take to be the total
momentum four-vector for the system of particles in the lab frame S, and we let 0'
be the analogous four-vector in the CM frame S'. The equality of four-vectors

before after

expresses conservation of momentum and energy in S, while the analogous equality

cs>>
,y
— opt
before ^after

makes a similar statement in 6". Of course, we cannot say that 0' and are equal.
These four-vectors refer to different frames and must be related, component by
component, via the Lorentz transformation

0" =<£0.

Figure 1-30

Collision process leading to several final particles m 4- M— » m + m2 +

]
• • •
+m n
. The reaction
is shown, before and after the collision, in the lab frame S and in the CM frame S'.

Before After \

0—^ -«— ® ,
©—
•
•

CM fra me S'

Lab frame S

©- > (M ©-*
Before After
 /-// Four-Vectors 65

Because of Lorentz invariance, however, the statement

(1-70)

can be made as a valid equality. This simple formula opens the way for an endless
variety of applications.

Example

Every elementary particle has its own antiparticle, where the two species have
the same mass but opposite charge. The proton and antiproton are related to
each other in this way. Antiprotons can be produced in reactions initiated by the
collisions of a beam of protons incident on protons in a stationary target. The
specific process that involves the least number of final particles is

p + p^p + p+p + p.

Note that the creation of the antiproton p requires the simultaneous production
ofan extra proton in the final state in order to conserve the total charge and the
total number of nuclear particles. This reaction cannot proceed unless the beam
proton has enough kinetic energy to produce the excess mass in the final system.

Our problem is to determine the minimum beam kinetic energy, or threshold, for
the process. The situation at threshold is such that, in the CM frame, the four
final particles are produced at rest, and so just enough energy is available to
account for the four final rest energies. In the lab frame, the four equal-mass
particles travel together, in the same direction as the beam, and carry equal
shares of the total momentum. If the beam energy is increased above threshold,
it becomes possible for the final masses to separate from each other, as in the

example shown in Figure 1-30. At threshold, the total momentum four-vector in

the CMframe after the reaction is

&' = (I

i\Mc

where M is the proton mass. In the lab frame, the total momentum four-vector
before the collision is

i{E + Mc 2 )/c

where p and E pertain to the beam proton. When we use the Lorentz-invari-
ance relation in Equation (1-70), we obtain the equality

(E + Mc 2 Y
2,2
= -16A/-V
66 Relativity

Since p and E satisfy

E2 = c
22
p + M c\ 2

the equality becomes

1EM + 2M 2c 2 = l6M 2c 2 =* £ == IMc 2 .

We want to know the beam kinetic energy, and so we ntroduce

i

= K + Mc 2
and get

j K = 6Mc 2

for the final answer. If we call the proton rest energy 1 GeV, wc : see that the
beam kinetic energy for protons in the lab must be at least 6 GeV for the
production of antiprotons.

Problems
1. Consider the Micholson-Morley experiment in Figure 1-1 for the realistic situation in

which the arms of the interferometer have unequal lengths d {

and d, Assume that the
.

light speeds are aether drifted and obtain a formula for the difference in transit time for
the light to travel to and from each mirror. Repeat the derivation with the apparatus
rotated by 90°. Obtain an expression for the number of fringes by which the interference
pattern shifts owing to this rotation.

2. A runner moves with speed u = i~ c

t
along a 100 m track. Determine the time on the
runner's watch to run the course. What is the length of the track in the runner's frame?

3. A meter stick approaches an observe! horizontally with speed f^c. What is the length of

the stick in the observer's frame? Suppose instead that the meter stick is oriented at an

angle 6' = cos \D in the frame moving with the stick. Calculate the length of the stick

and its angle of orientation in the frame of the observer.

Barney wishes to drive his racing car the length of a straight track at high constant speed
u. His serviceman Clyde has observed from the pit stop that the car consumes fuel at the
rate dn/dt (in droplets of fuel injected in the carburetor per second). Clyde has filled the

tank with exactly enough fuel for Barney to drive the course. What rate does Barney
measure for his fuel consumption? Does he observe his car to reach exactly the end of the
track, to run short, or to have fuel left over at the end?
 Problems H7

Electrons from the main beam at the Stanford Linear Accelerator Center can reach speeds
as large as 0.9999999997c Let these electrons enter a detector 1 m long, and calculate the
length of the detector in the rest frame of one of the particles.

A rocket ship has proper length 30 m and travels at ~c past an installation equipped to
emit and receive radar signals. The emitter sends out a signal at the instant the rear of the
rocket goes by, and the signal is reflected from the nose of the rocket back to the receiver.

Determine the transit time of the signal out and back, as measured at the radar station.

The Doppler shifts for sound and for light may be compared in terms of their power series
expansions. For sound, distinguish as two separate formulas the one for source motion
alone by taking u n = 0, and the one for observer motion alone by taking us = 0. Expand
1
the expressions to second order, that is, to order (u/w) for sound and to order (u/c) for

light, to show that the differences between the two cases do not show up until the second
order.

Unlike the case for sound waves, there is a Doppler shift for light when the source moves
at speed u transverse to the orientation of the observer. Prove that the formula for the

observed frequency in this situation is

= "ov 1 ~ "
2
A 2

9. An observer is located between two stationary light sources emitting at the same frequency
i> . How fast must the observer move toward one of the sources so that the observed

frequencies differ by a factor of 2?

10. The radiation received from quasars contains wavelengths characteristic of the common
elements, except that the wavelengths are obseived to be red shifted. If the shift is entirely

attributed to the Doppler effect, the amount of the shift AA relative to the emitted

wavelength X (1
can be used to determine the recessional speed v of the quasar. Derive a
formula for the ratio v/c in terms of AA/A . Since 1986, several quasars have been found
with red shifts greater than 4. Calculate the value of v/c corresponding to AA/A = 4.

11. The indicated frames S and S' coincide when t = t' = 0. In S, event A occurs at the
origin when = / 0, and event B occurs later at jr ,
= 9 m when I = t
]
= 10 s. In S',
events A and B are simultaneous, occurring at the origin and at x[, respectively, when
t' = 0. Determine the speed of the frame S' moving through the frame S. How far apart

are the simultaneous events in S'?

/ = f'=

®- ®-
-V'

t= r.

-©-
68 Relativity

12. Two hunters are located 4 m apart. Each of them fires his shotgun, the one preceding the
other by 20 ns. A passing game warden claims that the shots are fired simultaneously. Is

this possible? If it is, how fast must the game warden be moving?
13. A laboratory has proper length L' = 10 m and moves through S with speed u = § c.
Another Lorentz frame S' moves with the device. Three events are observed as indicated.
Event A is the emission of a light signal at (x = 0, I = 0) in S and (V = 0, /' = 0) in S'.
Event B occurs when the signal reaches a mirror at the right end of the laboratory. Event
C occurs when the signal returns to a detector at the left end of the laboratory. Determine
the space and time coordinates (x, 1) in S and (x', l') in S' for events B and C.

s
H u
S'

s
u
<L
S'

14. The runner in the figure is being filmed by a camera operator who moves with speed v
= j
',;<
,
parallel to a 100 m track. The figure shows the situation at / = in S, the Earth
frame, when runner and camera operator are 10 m apart. The runner's watch in S' reads
t' = at this instant, where 5' is the runner's frame. Calculate the relative speed with
which the runner overtakes the camera operator. Determine the time on the runner's
watch required for overtaking. Does this occur before the runner has completed the
course?

10

15. A skateboard has speed u = \c in S, the Earth frame; its proper length is 1 m. A bug
crawls in the same direction along the board with velocity v' = fc, relative to the board.
In .S", the rest frame of the board, find the time for the bug to crawl from one end of the

board to the other. In S, find the speed v of the bug and the time for the bug to crawl the

length of the board. The bug carries a watch; find the time on the watch for the bug to

crawl the length of the board.

16. When hockey star Guy L'Einstein takes his relativistic slap shot, his body is moving along
the ice at speed u u while his wrist is thrust forward at speed u[ relative to his body and his

hockey puck is pushed ahead at speed v" relative to his wrist. Each of these speeds has the

same value, «„ = u\ = v" = \c. The speeds in S, the ice frame, are shown as u , u t
, and
v in the figure. Determine the speed v of the puck in S. Let his slapshot have stroke length
d = \ m in S, as illustrated, and calculate the time required to get the shot off in S.

Determine the corresponding time interval observed on Guy's wristwatch.

 Problems 69

^v >- v

d= 1 m

17. Refer to Problem 12 and identify the gunshots as events in a space- time diagram. Use the
diagram to prove that the game warden's claim is impossible.

18. Refer to Figure 1-9 for the details of the pole-in-the barn puzzle, and plot all the various
distances and times on a space-time diagram, using (x, ct) and (*', ct') axes. Indicate the
events A, B, and C on the diagram. Calculate the Lorentz- invariant space-time intervals

between events A and B to relate the times t

Br and t'
H and between events A and C to

relate the times t

B(: and t'
c .

19. Refer to Problem 13 and plot the events A, B, and C on a space-time diagram. Draw the

world-line of the propagating light signal.

20. The elastic scattering of two equal masses is shown in two Lorentz frames S and S\ before
and after a collision.The total momentum is zero before and after in S', where all speeds
have the same value v'. The frame S' moves through the frame S with speed u in such a
way that, in S, one of the particles has no x component of velocity before and after the
collision. Determine the indicated velocities u, a,, v2x , and v
2y
in terms of v' under these
conditions.

Before After

21. Continue Problem 20 and demonstrate as follows that the total relativistic momentum is

conserved in 5. First, show explicitly that Ptolai ,

= 0, where

mu, x

total i

'1 - v.j/c~ i/l - v^/c

1

before the collision. Then, argue from the symmetry of the figure that PUttal y
is conserved.

Finally, argue that Ptma ,

,
is also conserved, again from the symmetrical construction of

the special situation shown in the figure.

70 Relativity

22. Prove the validity of the relation

-1 ^ 2 =
for velocities v and v' related by velocity addition, where y = (1 — u
2
/c ) , y,,

(1 - v
2
/c 2 y^ 2
, and Y„< = (1 - v'
2
/c 2 y^ 2
.

23. The Lorentz transformation equations for relativistic momentum and energy are ex-
amined in the text. The demonstration of their validity is not giyen for the components of
the momentum transverse to the x direction. Prove that p' =p holds, and argue that
p' = p. follows by an identical derivation.
24. The angle </> in the figure is defined by sin <£ = v/c, where v is the speed of a particle of

mass m. Identify all the straight lengths in the figure in terms of the appropriate
kinematical quantities.

25. A particle has speed v and relativistic kinetic energy K. Prove that

v /k(k + 2)

C K + 1

where k = K/mc 1 . For k 3> 1, expand the result in powers of 1/k and show that

v
-
c
= 1 - —
2k-
1

7 +

to order 1/k .

26. The value of v/c for a 1

J proton is very very close to unity. Find how close by making an
explicit calculation of 1 — v/c.

27. Draw graphs of the relativistic momentum and energy

mv mc~
p — .
=- and E=
- 2
_
2
'l - v
2
/c
2
^1 v /c

as functions of the speed v. Make the substitution m —* ijx and let v exceed c to obtain a
modified version of p and E. How does the relativistic relation between these quantities
differ from the unmodified case? Draw graphs of p and E, in their modified form, and
observe their behavior as v —» oo. (These manipulations describe faster-than-light par-
ticles, called lachyons. Such a particle cannot be found at rest in any Lorentz frame;
therefore, the mass parameter m is not interpretable in terms of a rest energy and is not

required to be real valued.) Where are the world-lines of tachyons supposed to lie in a
space- time diagram?
 Problems 71

28. Prove the work-energy theorem for particle motion in three dimensions. To be specific,

use the relativistic force law F = dp/dl, consider the work done by the force between
locations 1 and 2 along the path of the particle

2
W= /
J
F •
*,
\

and show W= —that E., £,

29. A particle of mass M at rest disintegrates into two fragments of equal mass m. Determine
the velocity of each fragment in terms of M and m.

30. A particle of mass M at rest decays into two unequal masses m and m 2 Show
x
. that the
square of the momentum of each of the final particles is given by

2
[M 2 - (m l
+ m2 ) [m \
2
- {m - m 2 f\ l

P =
AM 1

31. Continue Problem 30 and derive formulas for the relativistic kinetic energies of the final

particles. Show that the results can be expressed as

M- m, + m., M—m , + m.
A' = -0
^ and K = 2
- n
K
2M 2M
,
' '

where Q denotes the Q-value for the decay.

32. Consider an elastic collision of equal-mass particles with one particle initially at rest. The
conservation laws imply that the final momenta are perpendicular in the nonrelativistic
case. Is this true for a relativistic collision? Answer the question by deriving the relativistic

formula

c p, •
p, = A", K,

relating the final momenta and kinetic energies.

33. In S, a particle of mass = f c strikes a target particle of mass 5 m at rest.

m and speed v
Let the frame S' be the center of mass frame, and determine the speed u with which S'
moves through S. Find the speeds v' and u' of the two masses m and 5m in S'.

34. The lower part of Figure 1-28 shows a particular example of the decay M —* m + m in

flight. Use the conservation laws to obtain v in terms of v, where the speeds are identified

in the figure.

35. Consider a reaction caused by m ]

colliding with m_, , where m , is initially at rest. The
collision is completely inelastic as the two masses stick together to form a single object of
mass M. Derive a formula for M in terms of m x ,
m.,, and the incident kinetic energy Kv
36. Figure 1 -29 shows a two-body collision of unequal masses m and M in the lab frame and
in the CM frame. The indicated speeds v, v'', and u are constrained by the velocity
addition formula and by the condition on the momenta that defines the CM frame. Use
these two relations to eliminate v' so that u is determined in terms of v.

37. In S, a particle of mass m has the momentum four-vector

iE/c
72 Relativity

Let S' be the rest frame of the particle so that the corresponding momentum four-vector

ft' is obtained from f by the Lorentz transformation ft'

=
££f. Determine the transforma-
tion matrix ££* required to obtain the form necessary for ft Construct ££ by deducing the
' .

parameters /? and y in terms of m, p, and E.

38. A proton-proton collision can create a 77" meson as an additional particle in the final

state, if there is sufficient energy. The observed reaction is

p+p->p+p + 77°.

Derive an expression, in terms of the masses, for the minimum kinetic energy -K thrcshold for

beam protons incident on protons at rest in this reaction. Calculate the numerical value of

^threshold' usm g 938.3 MeV and 135.0 MeV for the rest energies of the proton and the
meson.
 TWO
PHOTONS

/he beginnings of quantum physics occupy a

period of history that spans a quarter of a century. Our survey of these important
developments is spread across the following three chapters. The topics in this survey
describe the evolution of a new treatment of radiation and matter in which certain
basic notions of classical physics are questioned and discarded. A series of discoveries
points the way toward a new theory and, at the end of the evolutionary period,
quantum mechanics finally emerges as the governing body of principles.
The quantum theory is a revision of physics that supersedes classical mechanics and
has a classical limit in the regime where Newton's laws are valid. The main inspiration
for the new theory is the observed phenomenon of quantization, in which physical
quantities are found to exist in discrete states rather than continuous distributions. Our
plan is to introduce quantization and quantum behavior in the form of accumulated
evidence. We proceed along historical lines in these three chapters as we prepare for
the more formal material in the chapters to come.
We should note that quantization in nature was certainly not unknown in the 19th
century. It was believed that an examination of bulk matter on a sufficiently small
scale would reveal a discrete composition, supposedly made up of molecules and atoms.
This microscopic particle model was invoked by Maxwell, Boltzmann, and others in
the formulation of the kinetic theory of gases. Molecules and atoms were similarly
anticipated in the early laws of chemistry through the findings of J. Dalton and A.
Avogadro. The quantization of electric charge was also known in this same period.
Faraday's experiments on the conduction of electricity in solutions gave evidence for
charged ions with charges equal to multiples of a basic indivisible unit. This unit was
eventually identified with the charge of the electron, a fundamental constituent of all
atoms. Thus, the quantization of matter and the quantization of charge were recognized in
context with certain discoveries and were accepted as concepts before the end of the
19th century.
These properties of nature should be set apart from the quantum revolution since
they did not point directly to the need for a new fundamental theory. The real
revolution began when physical motion was found to have quantized behavior in
radiation and in matter. Once it became apparent that the energy of certain systems

73
74 Photons

Max Planck

could exist only in discrete states, it was clear that a serious break with classical
physics was at hand.
Quantum physics came to life in the year 1900. The occasion was marked in
history by a famous pronouncement put forward by M. K. E. L. Planck to explain the
observed properties of the radiation emitted by incandescent objects. This common-
place phenomenon posed an unsolved problem that had lodged at the forefront of
theoretical physics for several decades. Principles of thermodynamics and electromag-
netism had been applied to the problem, but classical methods had failed to give a
sensible explanation of the experimental results. Finally, Planck grasped in despera-
tion for a solution based on the new idea of quantization.
The quantum hypothesis of Planck and the subsequent interpretation of the idea
by Einstein gave electromagnetic radiation discrete properties somewhat similar to
those of a particle. These quantized components of light became known as photons. It
was surprising that such discrete characteristics should be in evidence since light was
firmly established as a wave phenomenon. The quantum theory made provision for
radiation to have both wave and particle aspects in a complementary form of
coexistence. The theory was extended when matter was also found to have wave
characteristics as well as particle properties. These formative notions continued to
evolve, completely at variance with classical ideas, until 1925 when the formal
apparatus of the quantum theory finally came into being.
The evolutionary phase of quantum mechanics is called the period of the "old
quantum theory." We devote the following two chapters to the main feature of this
theory, the quantization of energy in radiation and in atoms. The last of our three
introductory chapters then concludes these developments with a preliminary picture of
the wave description of matter.
 21 Blackbody Radiation 75

2-1 Blackbody Radiation

An ordinary property of every object is its ability to emit and absorb electromagnetic
radiation. The phenomenon is called it involves an inter-
thermal radiation because
change between radiation energy in the electromagnetic fields around the object and
thermal energy owing to the motion of particles within the object. The interchange is
assumed to be an equilibrium process occurring at a certain temperature. Some of the
features of this complex problem appeal to common sense. The familiar observation
that an incandescent solid glows "red-hot" when heated, and "white-hot" when
heated more, suggests a correlation between the temperature of the solid and the
frequency of the emitted radiation. In fact, the object emits and absorbs radiation of
all frequencies, and so a particular range of emitted frequencies tends to prevail for a

particular temperature. Hence, the problem of interest for a body at a given

temperature concerns the distribution of the radiated electromagnetic energy as a
function of the emitted frequency. This distribution is called the frequency spectrum of
the radiating object.
Let us define the various relevant quantities so that we can describe the phenome-
non. The radiant emittance (or radiancy, or emissive power) M( T ) refers to the total
energy radiated by the object at Kelvin temperature T per unit time per unit area.
This quantity is a temperature-dependent function, given in units W/nv. A continu-
ous frequency spectrum is also defined since the emittance has contributions in every
frequency interval dp. We express this distribution of frequencies by writing

/•CO

M(T)= [ M {T)dv.
v
(2-i;
•'o

The integrand M^T) identifies the spectral radiant emittance, or total energy radiated
per unit time per unit area per unit frequency interval. Our notation stresses the
dependence of this spectral quantity on the two variables, v as well as T.

The emission of radiation is simultaneous with the incidence of radiation for an

object at equilibrium. Incident energy may be either reflected or absorbed, and so two
separate incident quantities are specified at frequency v and temperature T, the
spectral reflectance p,,(T) and the spectral absorptance a^T). These fractions of
the energy incident per unit time per unit area per unit frequency interval must satisfy
the equality

p,(T) + a,(T)= 1. (2-2)

We are concerned with the equilibrium situation where the rates of emission and
absorption are equal by definition. A perfect absorber reflects no incident radiation
and therefore satisfies a (T) =
lt
1. This ideal radiator is a perfect emitter and is called
a blackbody. Figure 2-1 shows a model of a blackbody constructed in the form of an
evacuated cavity with walls at temperature T and with a hole in one of the walls. The
hole is very small so that rays entering the cavity have essentially no chance to be
reflected back out. The spherical shape shown in the figure is not a necessary feature
of the model.A blackbody is a useful idealization, which we can employ as a standard
by introducing the associated spectral emittance M*(T) as a standardizing function.
We can use this fundamental fictitious quantity to define the spectral emissivity

M„(T)
«,(r) = Tsbv; (2-3)
M {T) f
b
76 Photons

Figure 2-1

Model of a blackbody radiator. All radiation

incident on the hole in the wall of the cavity
is effectively absorbed. The flux rate of energy
radiated at temperature T is given by the
blackbody emittance M (T).
b
The spectrum
spans all frequencies and has a universal shape
for each temperature.

this ratio then provides a measure of the radiating efficiency for a real object whose
spectral emittance is M (T).V

The following facts should be added as background for the blackbody problem. In
1859 G. R. Kirchhoff proved that the ratio M (T)/a ,(T)
p l
should be a universal
function of v and T, the same for all radiators. He used thermodynamic arguments to
show that a failure of this universal property was equivalent to the existence of a
perpetual motion machine that violated the second law of thermodynamics. The
universal function in Kirchhoff's theorem was identified to be the spectral emittance
of a blackbody M„(T). These arguments presented a challenge for the physics
community to deduce the form unknown
function. In 1879 J. Stefan conjec-
of the
tured, on empirical grounds, that the emittance of an object should be proportional to
the fourth power of its temperature. In 1884 Boltzmann proved the conjecture
theoretically, but only in the case of a blackbody. Their conclusion, the Stefan-Boltz-
mann law, was expressed as

/•OO

M '(T) = / Mt(T)dv = oT\ (2-4)

•'n

with a = 5.67 X 10
8
W/m 2
K 4
Stefan-Boltzmann constant.
for the value of the
The burden of Kirchhoff's challenge on experimenters to develop a
fell initially

suitable laboratory blackbody and then measure the radiation over a broad range of
frequencies at fixed temperature. In time the shape of the blackbody spectrum became
established. Curves like those in Figure 2-2 were obtained for various temperatures,
where each curve displayed a single maximum occurring at a particular frequency vm .

The observed variation of the spectrum with T was such that the peak of the
distribution shifted to higher frequency as the temperature was increased. In 1893 W.
Wien deduced from thermodynamics that vm and T should obey a linear relation. He
also proposed a form for the frequency distribution M^(T) in agreement with the
limited available data. Meanwhile, pioneering improvements were being made on the
experimental front as O. Lummer and E. Pringsheim proceeded to broaden the range
of frequencies in the measured distributions. By 1900 it was clear from these data that
Wien's proposed formula was not adequate as a fit to the whole known spectrum.
Thus, Kirchhoff's challenge continued to stand through the end of the century.
This brief summary sets the stage for Planck's contribution. The great importance
of his idea warrants a detailed analysis of the entire blackbody problem. We
 21 Blackbody Radiation 77

Figure 2-2 Figure 2-3

Blackbody frequency spectra for temperatures Blackbody wavelength spectra for

T, < T,. The distribution of emitted temperatures 7", < T,. The maximum occurs
frequencies has a maximum at vm for at \m for temperature T, where the product
temperature Tx
and at Pm for temperature X„,T is given by Wien's constant.
T2 . According to Wien's law, vm is MAT)
proportional to T.

M V
(T)

concentrate on the ideal blackbody radiator and suppress the superscript on A/*( T ),

as we have already done in Figure 2-2. Our system is the cavity model in Figure 2-1
whose shape, we have noted, can be arbitrary. The derivation of the spectrum requires
several steps, the most important of which is the use of Planck's quantum hypothesis.
Any desired property of the resulting blackbody solution may also be deduced,
including particularly the Stefan-Boltzmann T A
law in Equation (2-4).
One of the deductions that we can draw from Planck's result is Wien's law for the
position of the peak in the blackbody spectrum. This result is more often expressed in
terms of the wavelength as the variable rather than the frequency, so let us show how
these two types of distribution are related. Equation (2-1) may be consulted for this
purpose and written in two ways:

/•OO ,-00

M(T) =
J
/ M„(T)di> = /
•'0
M {T)d\.
x (2-5)

The second integral defines M (T), the wavelength

K distribution of the emittance. We can
transform the integration over v into an integration over A according to the familiar
rule

/•oo
ro UV
dv
Jo
I M {T)dv=
v
M (T)—dX.
d\
v
•'oo

Note how the range of integration is reversed to accommodate the inverse relation
between v and X. When we compare with the A integration in Equation (2-5) we get

dv c c
M (T)= -M (T) -^
X r
= -^MXT) where v = — (2-6)

We note that the A dependence of M

X (T) is not the same as the v dependence of
M (T), although both types
V spectrum display peaking behavior. Figure 2-3 shows
of
how the wavelength spectrum maximizes at A
m for a particular temperature T, and
especially how A m shifts to lower wavelength as T is increased. For wavelength
78 Photons

distributions of blackbody radiation, Wien's law takes the form

\m T= 2.898 X 1(T 3 K m
•
(Wien's constant). (2-7)

It should be emphasized that there is no reason for the peak positions vm and X m in
the respective distributions to be connected by the relation c = v\.
Blackbody radiation is realized physically in many practical applications. The
radiation from the Sun is a particularly conspicuous candidate for treatment by
the blackbody model. Measurements of the solar spectrum reveal that 99% of the
radiation falls in the wavelength range 270-4960 nm. The quantity of interest is the
solar constant S, defined as the total solar energy received at the Earth per unit time
per unit area at normal incidence, corrected for the effects of the Earth's atmosphere.
A recent determination of this quantity quotes the value 5 = 1351 W/m 2
. The
wavelength distribution of the incident radiation is called the solar spectral irradiance.
This function of A peaks around X m = 470 nm, and so Wien's law gives T = 6166 K
for the Sun's surface temperature. The quoted solar constant may also be used in
conjunction with the Stefan-Boltzmann law to produce the slightly different result
T= 5762 K. A blackbody distribution at this temperature can be made to fit the solar
spectral irradiance and reproduce the quoted value of 5 for the integrated area under
the curve.
Blackbody radiation also leaves its traces in more subtle areas. Experiments
conducted in the 1960s by A. A. Penzias and R. W. Wilson have demonstrated the
existence of isotropic background radiation that presumably permeates the universe.
This electromagnetic background can be fit by a blackbody distribution with a

Solar spectral irradiance versus wavelength. The area under the curve gives the value of the
solar constant S = 1351 W/m'. Data are taken from the survey of M. P. Thekaekara et al.,

Appl. Opt. 8:1713-1732 (1969).

2000

1500 -

1000-

500
 21 Blackbody Radiation 79

parametrizing temperature close to T = 3 K. The phenomenon constitutes substantial

evidence for the Big Bang theory of the universe, inasmuch as the radiation energy
apparently represents the residue in the current epoch of the primordial energy
produced in the Big Bang.
Let us return to the analysis of the Planck law and take two preliminary steps that
serve to isolate the crucial feature of the problem. We begin by shifting the focus of
the investigation away from the energy flux rate out of the cavity and onto the energy

density contained inside the cavity. The relation between the corresponding spectral
quantities is

C
M {T)=
V
~u v (T), (2-8)

where u v (T) denotes the electromagnetic energy in the cavity per unit volume per
unit frequency interval. We then recognize that the radiation in the cavity takes the

form of standing electromagnetic waves. These occur in every interval dp as discrete modes
whose number per unit frequency interval depends on the frequency. We can
therefore determine the spectral energy density at frequency v if we count the number
of modes and multiply by the average energy for each mode. This construction is

expressed as

«„(r) = y<E>, (2-9)

where V is the volume of the cavity, N v

is the number of electromagnetic modes at
frequency v per unit frequency interval, and (c) is the average energy per mode. The
problem thus reduces to the determination of the two factors N v
and (e). Each of
these quantities involves a rather complicated derivation, requiring separate sections
for a careful treatment. We learn where the heart of the problem lies by separating N v

and (e), as we find that the quantum hypothesis makes its appearance through the
Independent factor (e).

Example

Consider the application of Wien's law to the following rather different blackbody
situations. If we take the surface temperature of the Sun to be 5800 K and
consult Equation (2-7), we find that the peak of the solar spectrum should occur
at

2.898 X 10~ 3 K m
Xm = = 500 nm,
5800 K
a wavelength near the center of the visible range. On the other hand, the
universal 3 K background radiation gives

2.898 X 10
3
K m •

Xm = = 0.97 mm,
3 K
a wavelength in the microwave region.
80 Photons

Figure 24
Averaging over rays with velocity components
to the right.

^z
Area
2wr 2 sin ede

Example

The energy flux rate M(T) and the energy density u(T) are related for cavity
radiation by a proportionality factor c/4, as in Equation (2-8). We can deduce
this result as the product of two contributions with the aid of Figure 2-4. The
relation calls for a factor of \ because, for all the electromagnetic radiation in
the cavity, only half of the standing-wave energy corresponds to rays with
velocitycomponents to the right where the hole is located in the figure. (Recall
that a standing wave is an equal-parts admixture of traveling waves having
opposite directions of propagation.) These rays carry energy through the hole
with an average velocity to the right given by the z component of the velocity of
light, c z = c cos 6, averaged over the right hemisphere. If we let the sphere in the
figure have arbitrary radius r and average over the hemispherical area we
obtain

2
/ (c cos #)277T sin Odd cj xdx

<o =
(" /2 2mr 2 sm0 dO 2'
C dx '

in which we have used the substitution x = cos 6. The desired relation is then
found by assembling factors:

C
M=\(cz )u= -u.

The corresponding frequency distributions are related in similar fashion, in

agreement with Equation (2-8). We should note that the derivation does not
require the cavity to have a spherical shape.

2-2 Standing Electromagnetic Waves

An blackbody absorbs and emits equal amounts of radiation in steady equi-

ideal
librium. Our
cavity model of a blackbody treats the interior of the cavity as a storage
volume for the incoming and outgoing radiation. We assume perfectly conducting
 2-2 Standing Electromagnetic Waves 81

walls for the enclosure so that the fields are completely enclosed and the energy is

stored in the form of standing electromagnetic waves. We realize at once that the
geometrical and physical properties of the cavity select only those particular con-
figurations of wave fields that "fit" the enclosure. Each of these allowed configura-
tions, or modes, has own characteristic frequency of oscillation. Our first objective
its is

to determine the number of modes Nv dv that occur in the frequency range between v

and v + dv. The ^-dependent quantity N

v
has been identified in Equation (2-9). To
minimize the mathematical complications, we take advantage of the assertion that the
shape of the cavity does not matter, and we choose a cubical enclosure for this phase
of the problem. Figure 2-5 shows the geometry of our chosen cube of dimension L by
L by I.
Let us prepare ourselves for the mathematics of standing waves in a three-dimen-
sional region by recalling the one-dimensional problem of a vibrating string with fixed
ends. In this case the oscillating variable is the transverse displacement y, a function
of position x along the string as well as time t. Figure 2-6 illustrates the lowest modes
of vibration for a string with ends fixed at x = and x = L. The nth standing wave
has n — 1 additional points of zero vibration, called nodes, at equally spaced locations
along the string. Each of these modes can be described by a standing-wave function of

the form

2ttx
y{x,t) =jv sin—- — sin 2Trft (2-10)
A

with amplitude y , wavelength A, and frequency /. The function satisfies the wave

Figure 2-6

Standing waves on a vibrating string with

fixed ends. The wavelength of the nth mode
is A„ = 2L/n.

Figure 2-5

Cubical cavity with perfectly conducting walls

as an enclosure for standing electromagnetic
waves.
n= 2
\= L

n - 3
. -2
82 Photons

equation

dy 1 dy
Y~2 = -l^' (2- 11 )
ox v at

where v is the speed of wave propagation in the string medium. It is easy to verify that
the parameters obey v =/X by inserting Equation (2-10) into Equation (2-11). Recall
that the standing-wave character of y(x, t) is attributable to the multiplicative
construction of the expression. This product of oscillating functions of x and /

describes oscillations that remain in place and do not travel along the length of the
string. The explicit form of Equation (2-10) exhibits the required node at x = and
also incorporates the other node at x = L if A satisfies the condition

lirL
sin— — = 0.

The wavelengths are therefore limited to the set of values

2L
A„=— n
,
(2-12)

and so the allowed frequencies are correspondingly restricted:

= (2-13)
l-=i il"-

Hence, the modes of the string are indexed by an integer and assume the form

mrx nirvt
y*(*>t) =J>osin— sin-^— (2-14)

when Equations (2-12) and (2-13) are inserted into Equation (2-10).
We describe standing electromagnetic waves in a cavity by similar methods, with
allowances made for the three-dimensional nature of the wave configurations and for

the vector character of the electromagnetic field. The oscillating quantity of interest is

the electric field E(x, y, z, t ). (The accompanying magnetic field is known in terms of
E and does not have to be discussed explicitly.) Each component of E is a wave that
satisfies the wave equation in three dimensions with speed of propagation c:

d 2Ex 2
Ex E
2 2
d E d i d x
— -I
—x A — = -= t- and similarly for E v and E.. (2-15)
2 2 2 2 2
dx dy dz c dt '
"

A boundary condition holds at each wall of the enclosure since the components of E
tangential to the wall are required to be continuous as a consequence of Maxwell's
equations. Our cubical enclosure is bounded by a perfectly conducting medium in

which the E field vanishes. Therefore, the tangential components of E inside the cavity
must vanish at each wall to meet the requirements of continuity. If we refer to Figure
 2-2 Standing Electromagnetic Waves 83

2-5, we see that this implies the following specifications:

E =
x
at y = and L and , at z = and L ,

E =
y
at at = and L, and at z = and L,

E2 = at x = Oand L, and at y = and L. (2-16)

For standing waves we again want multiplicative expressions like Equation (2-10), but
adapted for three-dimensional configurations and three-component fields. The waves
describe oscillations in place in all three spatial variables and obey boundary
conditions as specified if the components of the field are

n 7Tx n.jry
E = Ex
fos
x

sin — — sin n 3
TTZ
sin 2mvt,

E' = v
.£ n „sin
'
n

n^x
ILL
x
mx
cos
n
— — sin n^irz sin 2ttv(.
2
iry

E. = E0z sm—— sin-^

2
— cos—n^mz
n. "ny
sin 2mvt. (2-17)

Note that three separate integers are needed here in place of the one employed in
Equation (2-14). It is not difficult to demonstrate that these functions behave correctly
at the walls and satisfy the wave equation in all three components. The latter point
should be examined closely since it leads to a restrictive condition on the frequency v.
If the first of Equations (2-17) is inserted in the wave equation for E x the result is ,

n,7T - 77 d rinir
\ / tf \ (

T) +
T
2
+
T"
e- -
-(2™r'£,

This equality tells us that the allowed frequencies are given by a formula like

Equation (2-13),

v = + nl + n\ ,
(2-18)
21

except that the role of the single integer in that result is now played by the three
integers «,, n 2 , and n 3
.

The modes that " fit" the cubical enclosure are not as easy to picture as the modes
on a string. Equations (2-17) and (2-18) prescribe the allowed fields and frequencies
according to the values assigned for the set of three independent integers («,, n .,, «,).

We associate each selected triplet of integers, such as (0, 1, 1) or (1, 2, 3) or . .

.
, with a
unique frequency, such as {c/2L)\J2 or (c/2L)vl4 or ..., and a unique spatial
configuration of standing electromagnetic wave fields oscillating in the cavity. The
most illuminating way employ these integers in a bookkeeping scheme is to
to
introduce a three-dimensional space whose axes are defined by the integer variables
(n,, n 2 , n 3 ).
Figure 2-7 shows how the various triplets of integers are plotted as points
in a lattice so that each lattice site specifies an allowed mode and its corresponding
frequency.
84 Photons

Figure 2-7

(n,, n.,, n ., ) space. Each lattice site refers to an

oscillating configuration of fields in the cavity.
The number of sites in the frequency interval
dv at frequency v is equal to the volume of
the corresponding spherical shell in the first

octant. The shell has radius 2Lv/c and

thickness (2L/c) dv.

Octant of a
spherical shell

The figure can be used to count the number of modes A",, dv in a given frequency

interval dv. Let us choose a frequency v and interval dv and visualize the calculation
with the aid of the indicated spherical shell in the three-dimensional (n,, n 2 « 3 ) space.
,

Equation (2-18) gives

- 21
2
In + n\ + «3 =

for the radius of the shell, and {2L/c)dv for its thickness. A unit cube in this space
contains one lattice and all the sites lie in the first octant, where each of the n 's is a
site,

positive integer. Therefore, we can count the number of oscillating field configurations
by calculating the volume of the octant shell that contains the corresponding lattice
points. We take V= I? for the volume of the cavity and get

2 2
2L 2L
-
47r| v\
\
dv = —^~ Vdv
4-ttv

for the volume of the shell. The desired number of modes Ar„ dv is actually twice this
result, because every spatial configuration of fields has two independent polarization
states. We therefore obtain

.Y (2-19)

as the final expression for the number of modes at frequency v per unit frequency
interval.
 2-2 Standing Electromagnetic Waves 85

This construction gives the correct formula for one of the factors that make up the
spectral energy density u p {T) in Equation (2-9). Classical methods can also be used to
deduce a result for the other unknown factor (e), the average energy per mode in the

cavity. We are concerned with this second result only in passing since it leads us to a
prediction for u v (T) that cannot be correct. Our motive in presenting the classical
form of (e) is to prepare the way for Planck's quantum hypothesis.
We want to know the average energy for a population of many radiation modes,
each with its own energy. The enclosed fields are in equilibrium with the walls of the
cavity at temperature T, and so the radiation exchanges energy with the many
material particles bound to the walls. Statistical physics teaches us how to average
over such large numbers of particles in order to deduce bulk properties for the system
and average values for certain particle variables. The kinetic theory of gases is an
example of this averaging procedure. Each of the three dimensions of linear particle
motion in a gas at temperature T is assigned an average kinetic energy ^k B T, where
kB is Boltzmann's constant. We can apply this conclusion to an oscillating particle
bound to the walls of the radiating cavity if we allow the oscillator to have potential
energy as well as kinetic energy. We know that the averages of these two contributions
to the energy are equal for any oscillating particle in simple harmonic motion.
Therefore, T
we obtain k B as the average total energy for each degree of freedom of a
linear oscillator in a collection of such particles at temperature T. This result is an
application of the classical principle of equipartitwn of energy. We then return to our
system of enclosed radiation in equilibrium with bound oscillators and simply transfer
the result for the average energy from one part of the system to the other. If we equate
the average energy per degree of freedom of a bound particle to the average energy
per mode of radiation, we obtain

<e> = kB T (2-20)

as the desired factor remaining in the formula for u v (T).

When Equations (2-19) and (2-20) are assembled in Equation (2-9), the conclusion
is

u v {T) = —r 8 77 v 2

c
kB T (2-21)

as the classical prediction for the spectral energy density of a cavity radiator. Equation
(2-8) then gives

2
lirp
M (T)=—^k B T
v
c
(2-22)

for the corresponding spectral emittance. The failure of these predictions can be
ascertained from the graph of M (T)
lf
in Figure 2-8. We see that the result resembles
the experimental spectrum in Figure 2-2 only at low frequency. We also see that the
increase at high frequency causes a catastrophic divergence of the integrated emit-
tance as defined in Equation (2-1).
The principle of equipartition of energy was applied to radiation by J. W. Strutt
Rayleigh around the turn of the century. Rayleigh's name has been attached to the
unsatisfactory result in Equation (2-21) for this reason. The high-frequency catastrophe
was a disastrous conclusion for the blackbody problem. This issue proved to be a
critical breaking point for classical physics.
86 Photons

Figure 2-8

Rayleigh's form for the frequency spectrum of

the blackbody emittance.

MAT)

2-3 The Maxwell- Boltzmann Distribution

Planck's solution to the blackbody problem is based on an average energy (e) that

differs radically from k B T. We can appreciate this feature of the problem more fully if
we first understand how such average values are determined for systems containing a
large number of elements in thermal equilibrium. It is instructive to digress from
blackbody radiation for a while and devote an entire section to this question. The
digression follows a straightforward line of statistical arguments to a rather general
conclusion. Our purpose in the end is to apply the resulting statistical formalism to a
collection of electromagnetic modes, even though the arguments are developed for a
collection of particles.
Statistical physics deals with systems whose variables are far too numerous to treat
individually and whose properties are therefore defined in terms of averages. This
approach takes advantage of the large number of variables to analyze the unobserved
behavior of the constituents of a system and extract the observed thermodynamic
features of the system as a whole. The average energy of a particle in a many-body
system one such dynamical quantity of particular interest.
is

We are concerned with a large collection of identical particles, individually labeled

so that each can be said to have its own well-defined energy. Of course, we recognize
at once that these energies change repeatedly because of collisions among the particles.
The average particle energy depends on the temperature T, while the system has a
certain distribution of particle energies for a given value of T. Our main objective is

to learn how a given total energy E is distributed over N identical constituents in

thermodynamic equilibrium. We visualize the distribution in terms of a large collec-
tion of cells of definite energy to particles in the system can be assigned. We
which the
refer to these energy cellsby means of a discrete integer index, and we let the
increments of energy be as refined as we like. Thus, if the th cell is reserved for ?

particles with energy e (

, the goal is to determine the number of particles n in that i
cell

for a large system of particles in thermal equilibrium at temperature T. The

population of the various energy cells gives an indication of the likelihood, or
probability, for some given particle energy to occur in the system. The desired result is

a formula, derived independently by Maxwell and Boltzmann around 1860, ex-

pressing 72, as a function of e, with T appearing as a parameter.
Our first notion to develop is the concept of a state describing the entire system.
Classical physics allows us to introduce distinguishing labels so that we can follow
each of the N identical particles and assign an energy cell for every particle. This
 2-3 The Maxwell- Bolizmann Distribution 87

Figure 2-9

Three identical particles distributed over two

cells. Microstates of the system are the eight
distinct particle assignments to each cell

noting, for example, that

a a
and
be cb

denote the same microstate. Macrostates of

the system are the four different cell

populations disregarding the labels of the

individual particles. The number of ways to
realize each macrostate is given by N\/n^.n 2 \,
where N= n i
+ n2 = 3.

IV icros tates Macrostates

abc n2 = 3
1 way
nx =

be ac ab n2 - 2
, 3 ways
a b c n.\ - l

a b c n2 = 1
3 ways
be ac ab n, = 2

n2 =
-, 1 way
abc ni = 6

complete specification of the system is called a microstate. Such a detailed description is

unnecessarily complete since distinct microstates should be regarded as physically

equivalent if their cell population numbers are the same without regard for the labels
that distinguish the particles from cell to cell. We therefore adopt another less specific
scheme in which we simply list the numbers of particles that occupy each energy cell,

assigning n x
particles with energy £,, n 2 particles with energy e 2 , and so on. This
revised method employs the original variables n :
and c, to generate a list of
occupation numbers (n {
, n 2 ,. . . , n r ) for the distribution of N particles into r cells.

Such a list defines a macrostate of the system.

We see immediately that many different microstates can often be identified with a
single macrostate. This multiplicity of ways to assemble a given macrostate is a
measure of the likelihood of achieving the corresponding configuration of particles.
Thus, a certain macrostate has a highly probable distribution of cell occupations, and
defines a correspondingly likely state of the system, if a sufficiently large number of
microstates contributes to the distribution.
A very simple example is illustrated in Figure 2-9 to differentiate these two kinds of
states. The microstates for N= 3 and r = 2 are shown as the eight distinct ways of
assigning three particles, labeled a, b, and c, over two cells. (This illustration
reproduces the exercise of flipping three coins and recording the head/tail outcome
for each coin.) The macrostates are the four different pairs (n u n 2 ) of cell occupation
numbers. (This list replicates the complete summary of heads/tails possibilities for the
88 Photons

three coins.) We can assume, a priori, that each microstate has an equal chance to
occur (just as head-head-head has the same likelihood as head-head-tail); however, we
can see that the various macrostates have different probabilities (as three heads are
less probable than two heads/one tail).

A system of particles can occupy a certain microstate at a given time and then
change its microstate repeatedly thereafter because of particle collisions. We assume
that all such microstates of the system are equally probable as a basic hypothesis. This
assumption means that over a long time scale any one complete specification of every
particle's state is expected to occur as often as any other. Of course, every system has
rare configurations of particles; these are rare because there are very few ways of
achieving these configurations as macrostates. Hence, macrostates are not equally
probable because they are usually realized by differing numbers of microstates. As
time passes and microstates change, the most frequently occurring macrostate, repre-
senting the most probable configuration of the system, is the one that corresponds to
the greatest number of microstates. We can accomplish our objective and learn how
the cell variables n t
and e, are related by implementing this simple idea.
The statistical problem is first of all a question of counting. We want an expression
for the number of microstates corresponding to a given macrostate whose cell

occupation numbers are denoted by (n ,,..., n r ). This number is expressed as

W N (n ,. n r )
x
and is called the thermodynamic probability for the macrostate in ques-
. . ,

tion. We deduce W
N by first recalling that the number of ways to assign A particles
r

(the number of permutations of N objects) is given by the product of the A

r

descending integer factors

N(N - l)(N - 2)
••• = N\.

Therefore, the number of distinct ways to distribute N particles so that n x

are in cell
1 , and the rest are not in cell 1 , is

AH
n x
\(N-n y/ x

Note that the number AM alone overcounts the n x

\ permutations of particles within
cell 1 as well as the (N — n x
)\ permutations of particles outside cell 1, and so these
numbers are factored out of A!. We continue counting in this fashion by arguing next
that the number of ways to distribute the remaining N — n x
particles so that n 2 are in
cell 2, and the rest are not in either cell 1 or cell 2, is

(N-n x
)\

\(N — — '

n 2
nx n 2 )\

and so on, until all N particles are distributed over all r cells. The grand total number
of such formations is given by the product of the corresponding r factors:

AH (N- n )\x
(N- n, - ••• -n r _,)!

n x
\(N - n )\ n
x 2
\{N - n x
- n 2 )\
n r
l{N - n x
- -n r
)l'

The result can be simplified in an obvious way to give the final number of microstates

WN {n„. ..,*,) = — —
n,\ ... n.
-. (2-23)
 2-3 The Maxwell- Boltzmam Distribution 89

We get this answer by introducing the relation

n, + •• +n = r
N (2-24)

as a condition that constrains the occupation numbers and accounts for the total
number Note that the definition 0! = 1 is also used.
of particles.
Now that we know the number of ways to form the macrostate («,, n ), we . .
.
,
r

next want to determine the most probable of all such distributions. The desired
macrostate is evidently the one that maximizes N We observe that the same W .

distribution is determined by the solution that maximizes In N and that the function W
lnW^ is more convenient to consider than N itself. Equation (2-23) is converted for W
this purpose to read

\nWN {n x
,...,n r ) = In AH- ln^!- ••• -ln« r !

= lniV!- £ Inn,-! (2-25)

i = i

by employing some of the well-known properties of logarithms.

Let us take advantage of the large number of particles and assume that each n t
is

large enough to justify a few approximations. Quantities like \nn\ can be very
accurately approximated with the aid of Stirling's formula:

In n\ —» n In n — n for large n. (2-26)

This substitution enables us to rewrite Equation (2-25) as

\nWN (n x
,...,n r )
= N\nN - N - XX^lnn, - ».)

= N\nN - 2>,ln« ( ,
(2-27)
i

where we express the approximation as an equality and again use Equation (2-24).
W
We maximize In N by taking integer increments in each n and seeking the largest t

result. Since the increments are so much smaller than the n's themselves, it is

reasonable to treat each n as a continuous variable.

l
We would then seek our solution
by requiring

— lnW^=0
for every n t
, if the variables (n 1 ,...,n r ) could all be regarded as independent. In
fact, we know that two restrictive conditions exist among the variables so that only
r — 2 of them are actually independent. One condition fixes the total number of
particles to equal N, as in Equation (2-24). Let us call this the jV constraint and
rewrite the condition as

X>, = N. (2-28)
i

The other restriction fixes the total energy of the system to equal E. Let us call this the
E constraint and express the condition as

Y.*i*i = E> (2-29)

90 Photons

It would appear that at the last moment our problem has taken on a complication
that prevents us from treating all the variables symmetrically and forces us to select
two arbitrarily as the ones that are not independent.
The constraints can be handled by means of an elegant symmetrical procedure,
devised by J. L. Lagrange in the 18th century. We do not directly use lnWy a ,

function of r variables where only r — 2 are independent, but instead introduce

another quantity

F(« l5 ... ,n r a, P)
,
= \nWN ( ni ,...,n r )
- «( £«, - N )
-
#( X>,e,- - E^
i i

(2-30)

a function of r + 2 variables where all r + 2 are independent. The procedure then

requires that we maximize F over all the variables n 1 ,...,n r ,
a, and ($.

We find that the conditions

—
dF
da
= and
8F
— =
dp

immediately reproduce the TV constraint in Equation (2-28) and the E constraint in

Equation (2-29). These conditions tell us that F ultimately reduces to In N when F is W
at its maximum. We also obtain

dF
-— = for all i = 1 to r, (2-31)
3n,

so that the net effect is to maximize \nWN , as required, and simultaneously satisfy the
two constraints. The advantages of Lagrange's procedure are twofold; the entire set of
r occupation variables appears on the same footing, and the extra variables a and ft

enter as new quantities with their own physical significance.

Let us now proceed to our objective with the aid of Lagrange's method. The
combination of Equations (2-27) and (2-30) produces the expression

F=AMnAf- XXlnn, - «( X>, - n\ - fil £>,£, - e) ,

i i i

and so the maximizing condition in Equation (2-31) becomes

—=
3F
dn.
-ln«,. - 1 - a- j3e. = Q. (2-32)

We can solve this equality for the /th occupation number to obtain

e-i-oe-to (2-33)

This is essentially the desired result except that the quantities a and fi remain to be
identified. If we use the N constraint in Equation (2-28) to eliminate a we find
 2-3 The Maxwell -Boltzmann Distribution 91

/here

*«!« -&, (2-34)

Equation (2-33) can then be rewritten as

A'
-J-* (2-35]
Z
the final expression for the Maxwell -Boltzmann distribution function.
Our concluding formula specifies the number of particles in the zth energy cell for
the macrostate of maximum thermodynamic probability. It can be argued that the
system tends to this configuration in the approach to thermal equilibrium. We know
that the maximizing state cannot represent a static final situation because of the
continual rearrangement of the particles among the cells. The conclusions suggest
instead that large departures from the most probable macrostate are expected to be
highly improbable.
Equation (2-34) defines a new quantity Z called the partition function This definition .

plays a recurring role in many of the applications of statistical physics. The expression
for Zdepends on the manner in which e, varies from one cell to another, and so the
explicit ft dependence of Z can only be expressed by examining separate cases. The
variable (3 itself remains to be identified. A variety of arguments can be used to obtain

l> (2-36)

One such demonstration of this result is given in the second illustration below.

Example

The approximation in Equation (2-26) follows directly from Stirling's formula

for the factorial function

x\= J2ttx\ - 'I

-

Let us gain some feeling for the approximation by inspecting the graph in
Figure 2-10. We can invoke the properties of the logarithm to write

In n ! = In n + \n(n - 1 ) + • • •
+ In 1

and then identify the sum of terms with the area of the rectangles shown in the
figure. The area under the curve In x is a good approximation to the area of
the rectangles if n is large enough. The rest of the construction is summarized in
the following steps:

In a dx = ( x In x - x ) |
,
= n In n — n + 1 -* n In n - n for 1 arge n.

It is obvious that this approximation can save enormous amounts of computa-

tional time when n has very large values.
92 Photons

Figure 2-10

Approximation of In n! by the integral

/," In xdx. This construction leads to Stirling's
approximation.

In x

Example

The energy cells with a discrete index in Equation (2-35) can readily be adapted
for application to the case of free particles with a continuous energy. We
accomplish this by letting a very refined incremental cell of definite energy e be
identified withan infinitesimally thin spherical shell in the space of the three
velocity components (v x v vz ). These variables are connected by the formula
, ,
y

for the energy of a free particle,

\mv l = \m(v* + v; + °?).

and so the radius of the shell in velocity space is given by

$ + v] + v1 =

The thickness of the shell dv is related to the energy interval de by differentiat-

ing:

2vdv = — de.
in m

The shell then determines an element of volume in velocity space

2e de
dr = 4irv
2
dv = 4w

The number dn of particles in this energy cell is proportional to the cell volume
drv and is also proportional to the Maxwell -Boltzmann factor e~" e according to

Equation (2-35). We can therefore set

dn = Ae~ Pe dTv ,

where A is a proportionality constant. We have just seen that dr lt

is proportional
 24 The Quantum Hypothesis 93

1//2
to e de, and so we can reexpress the number of particles in the cell as

x/2 pi
dn = A'£ e- de,

where A' is another proportionality constant. Two definite integrals are needed
at this point. We get the first from a table of integrals,

r x
l/2
e-
px
dx= iv^/r 3/2 (Dwight 860.04),

and we derive the second from the first,

r>v*<&= -4
Jn
-'(i dB
r x ^ e-^dx= Jn
2
i^p-
5/2
.

These formulas enable us to calculate the average kinetic energy per particle as
follows:

3'2
£dn i '-**'
J J ifrB-^ 3_
(C>
x 3/2 ""
hdn f e
l
^e-^de "
^fi~ 2jB
•'o '0

We know from kinetic theory that the average kinetic energy per particle is

^kftT; hence, our result leads us to the conclusion

as asserted above in Equation (2-36).

2-4 The Quantum Hypothesis

Rayleigh's result for the spectral energy density u v {T) was certainly not the correct
answer to KirchhofTs problem. The fault was found to be the lack of a frequency-
dependence in the classical expression for the average energy (e). It was apparent
that (e) should decrease sharply with increasing v so that the predicted blackbody
distribution could rise and then fall with frequency as observed in Figure 2-2. A
drastic revision of the high-i' behavior was obviously needed to make the integral over
4
the spectrum converge and give the desired T" prediction for the total emittance.
Planck discovered the proper v dependence in his empirical studies of the blackbody
problem and, on these grounds, proposed the following formula for the spectral
energy density:

"' (r) = —
877J>~

,*/*"•-!
hv
• (2 " 37)

The second group of factors in the formula was deduced to represent the average
 ~

94 Photons

energy per mode at frequency v,

replacing the classical equipartition result k B T. Planck's construction of (e) guaran-

teed the required asymptotic behavior of u v (T) and also reproduced the known
low-frequency limit where the classical expression was regarded as acceptable. The
construction contained two constants, now known as Planck's constant h and Boltz-
mann's constant k B and provided experimental determinations for both parameters.
,

The values obtained from Planck's investigations of the blackbody data were not very
different from the currently quoted figures

h = 6.6260755 X 10
34
J •
s and kB = 1.380658 X 10" 23 J/K.

Planck's constant made its first appearance as the basic new parameter of quantum
physics on this occasion.
These findings were recognized as an inspired contribution. The proposed blackbody
formula was an accurate representation of experiment and, as such, was a satisfactory
response to KirchhofFs long-standing challenge. Planck did not let the issue rest at the
empirical level, however. He turned his attention to a theoretical derivation of his
formula and in the process gave the quantity of energy hv an interpretation of
fundamental significance to the quantum theory.
Planck recognized that cavity radiation should be treated as an equilibrium
problem involving an exchange of energy in the cavity between the radiation fields
and the particles bound to the walls. He accepted the view that the bound particles
could be modeled as oscillators, like masses connected to springs, with arbitrary
frequencies of oscillation. The familiar classical outlook permitted these oscillating
particles to have a continuous range of energies corresponding to a continuous variety
of possible amplitudes of oscillation. This meant that the particles could exchange any
amount of energy with the radiation fields in the cavity. Unfortunately, the classical
assumptions led to the undesirable Rayleigh result, as we have seen in Equation
(2-21). In desperation Planck proposed that the energy exchanged between the
oscillators in the walls and the radiation in the cavity must vary in discrete rather than
continuous amounts. The proposition implied that the radiation in the cavity at each
frequency v could be represented as a large collection of quantized elements of energy

e„(v),whose designation could be labeled by means of an integer index n. Planck

wanted e n to depend on v so that the average energy (e) would have a v dependence
capable of averting the Rayleigh catastrophe at large values of v. He argued that en

should correspond to n multiples of a fundamental unit of energy proportional to v

and wrote

e n (v) = nhi> (2-39)

to express his hypothesis. The fundamental unit of energy hv for radiation of

frequency v was called a quantum of energy, in which Planck's constant h was
introduced as the proportionality factor relating energy and frequency. With this

assertion the quantization of a dynamical quantity, the energy, appeared in physics for
the first time.
 2-4 The Quantum Hypothesis 95

Our analysis of the blackbody problem implements Equation (2-39) by treating the
collection of quantized energies as a statistical system. The procedure follows an
interpretation of Planck's reasoning along lines developed by P. J. W. Debye in 1910.
We adopt this picture because it is easier to present than Planck's thermodynamic

oscillator theory and because it draws us toward a more immediate understanding of

the nature of the radiation.
Our model of cavity radiation is based on a collection of standing electromagnetic
modes inan enclosure bounded by perfectly conducting walls. The effect of Planck's
hypothesis is to restrict these modes to a discrete set of allowed energies in which the
energy of a particular mode at frequency v occurs as an integral multiple of hv in
accord with Equation (2-39). This restriction is obviously a radical departure from the
classical point of view. The energy of an oscillating mode depends on the squares of
the components of the amplitude E appearing in Equations (2-17); these amplitudes
are regarded classically as continuously varying quantities, implying continuous
values of the energy.
We should also make clear the thrust of the quantum hypothesis as a device for
making the blackbody distribution fall with increasing v. Let us fix the temperature T
and consider a certain total amount of energy to be distributed over all modes at all
frequencies. The Maxwell -Boltzmann distribution function determines the probabili-
ties for the assignments of energy to the various modes at frequency v. Let us denote

the governing factor in the distribution function as

f(e) = e-^\ (2-40)

This expression gives the likelihood, in Debye's interpretation, for the occurrence of a
given energy e in the distribution of energies in the cavity. Figure 2-1 1 shows how the
larger energies are exponentially suppressed by the behavior of /(e). The modes at
large v are similarly suppressed because of the Planck relation between energy and

Figure 2-11
= *" r
Maxwell-Boltzmann distribution factor /(e) e~
f
giving the relative likelihood for an
energy e in a distribution of energies at temperature T . Quantized energies nhv are sampled
and weighted by the distribution factor for three different values of hv.

/(G)

hv « kR T hv » kR T
96 Photons

frequency. The figure indicates the details of this suppression for three different
number of multiples of hv are sampled
choices of frequency. For hv <£ k B T, a large
by /(e) before the value of the function drops to l/e. For hv k B T, the reverse is »
true and even the first allowed quantum of energy is greatly suppressed. The case
hv = kB T is also included, showing the weight of the first quantum to be /(e) = l/e.
Thus, the direct connection between energy and frequency in Planck's hypothesis
accomplishes the suppression of high frequencies in the blackbody spectrum through
the influence of the thermal distribution of energies.
Let us now proceed with the derivation of Planck's formula for (e). At frequency
v, the average energy per mode is computed as the sum of the various weighted

energies, with weights given by the likelihood factors, divided by the sum of the
weights:

IX/(0
L/(0

Since we have discrete energies to average, the averaging process involves discrete
summations in which the sums range from n = to n = oo. When Equation (2-39) is
incorporated, the expression for the average energy becomes

nhv/k » r ~" x
Y,nhve Y. nxe

< e> = -^ TTT^F- = kB T ^ > (2-42)

/here

hv
(2-43)
kB T

We establish the functional form of (e) by starting with the denominator and writing

00
~" x x 2x
Z{x) = E= e = I + e~ + e~ + .

We recognize this summation to be a geometric series in which the ratio of successive

x
terms is e~ . The sum of the series is

Z(x)
V
= .

'
1 - e~
x

Next, we note that the numerator in Equation (2-42) is found from Z(x) by
performing the following derivative operation:

-x —d Z{x) d _
= -x—Y,e- nx = xY,ne- nx
^ .

dx dx n

Finally, we assemble the results of these observations and carry out one last series of
 24 The Quantum Hypothesis 97

maneuvers:

k R Tx d d
(e) = ——Z{x) = -k B Tx— InZ(x)
Z\x) dx dx
x
k B Tx
k B Tx —d \n{\ - e~
x
) = k B T)x-
e~

— —
dx 1 e " e* 1

Planck's formula for (e) is then obtained when Equation (2-43) is reinstated in this
result.

The remarkable formula for the spectral energy density in Equation (2-37)
encompassesall that we might wish to know about blackbody radiation. The following
examples illustrate this with derivations of Wien's law and the Stefan-Boltzmann law.

Example

We analyze Wien's law in terms of the wavelength spectrum of the blackbody

emittance, as shown in Figure 2-3. Equations (2-6), (2-8), and (2-37) may be
combined to give

2
hv 2irhc
M,(T)= -- hv / k B T
I

2
A 4 c
3
e - l A
5
e
hc/XkBT - 1
'

using v = c/X. This expression can be made more compact by recalling the
dimensionless variable x from Equation (2-43) and rewriting x in terms of A:

he
x =
xk B r
The wavelength distribution then becomes

2ir{k R Tf
M {T)=
X
he\
g( x ),

where

*(*) =
e
x
- 1

The function g{ x ) describes the universal shape of the wavelength spectrum for a
blackbody at any temperature. A spectral curve is defined with a single peak
occurring at the special value of x given by

x = 4.965.

To prove this assertion, let the derivative of g(x) vanish and solve for x:

dg \

dx e
x
— 1 \ 1 — e * J 5

We can use a calculator to get x = 5 as an approximate solution and then

98 Photons

obtain x = = 4.965 from there by trial and error Wien's law pertains to the
. peak
of M (T)
X at X = X m Since
. dMx(T)/dX = when dg/dx = 0, the parameters
X m and x are immediately related by the equs ility

he

Kk B T'
A final ca culation gives

" 34 8
he (6.626 X 10 T •
s)(2.998 X 10 m/s)
\ T— ~ 23
xk B 4.965(1.381 X 10" J/K)
= 2.897 X 10" 3
K • m,

in excellent agreement with Wien's constant ir Equation (2-7).

Example

The derivation of the Stefan -Boltzmann law begins with the formula for the
frequency spectrum of the emittance. Equations (2-8) and (2-37) are consulted
to get

2 77 h
M (T)
V
c
>
e
hv/k B T _ j
'

The total emittance is then found by applying Equation (2-1):

3 4 3
• oo 27r/z v dv 2-nh I k B T\ /.oo x dx
M(T)= /
- „hv/k B T
2 x
-
1
1 '
1
i. * 1

in which Equation (2-43) is again used, this time to change the variable of
integration. The dimensionless integral in the computation has a known value,
tabulated as

x dx
(Dwight 860.33).
f 1")

Therefore, the T dependence of the integrated emittance has the form

M(T) = oT\

where the constant a represents the accumulation of factors

2ir 'k B 2tt' (1.381 X 10~ 23 J/K)'

15/*V 34 8
15 (6.626 X 10 J •
s) (2.998 X 10 m/s)

= 5.676 X 10' 8 W/m K 2

•
4
,

in excellent agreement with the value of the Stefan -Boltzmann constant in

Equation (2-4).
 2-5 The Photoelectric Effect 99

Example

Suppose that the radiation from a blackbody cavity at 5000 K is being

examined through a filter that passes a 2 nm wavelength band centered at the
peak of the blackbody wavelength spectrum. Our problem is to compute the
radiated power transmitted by the filter, given a 1 cm radius for the circular
aperture of the device. We proceed by locating the wavelength peak from
Wien's law,

2.90 X 10" 3 K m •

= 580 nm,
5000 K

and noting that the filter passes wavelengths in the interval 579-581 nm. The
transmitted portion of the blackbody emittance would usually be found by
integrating the distribution M
X {T) over the wavelength range
of the filter. In
this case, the range narrow enough to permit an approximation in which
is

M X (T) is evaluated at
X = X m and multiplied by the wavelength interval
AX = 2 nm. We then obtain the transmitted power when we multiply this result
by the area of the filter aperture. Thus, the final formula for the power reads

2
2-nhc 1

P= irr
2
M x (T)AX = mr
1

I
AX.

Note that we have used the relation between X m and x from our first example.
The final calculation gives

-2 2 8 2
(10 m) (6.63 X 10" 34 J •
s)(3 X 10 m/s) (2 X 10" 9 m)
P= 2m
(5.80 X 10- 7
m)V 96
- 1)

= 25.3 W.

We have already remarked that the use of a broad-band filter would necessitate
an integration over the relevant wavelength interval. This task would probably
have to be done numerically.

2-5 The Photoelectric Effect

Planck's quantum hypothesis was a radical concept whose effects were discovered in a
very complicated setting. Real inspiration was necessary to recognize the influence of
quantization beneath the surface of the blackbody problem, and further inspiration
was needed to ascertain the meaning of quantization as a new physical principle.
Planck's contribution was not immediately acknowledged as a major turning point in
theoretical physics. Planck himself was among those who hesitated over the question
of interpretation, while Einstein was the one who came forward with the next
definitive idea.
Planck's assumption allowed oscillating particles and radiation fields at frequency v
to exchange energy only in integral multiples of the quantum of energy hv. Einstein's
proposal interpreted the radiation directly as an intrinsically discrete system composed
of these quanta of energy. (Our analysis of the blackbody problem has already been
100 Photons

Figure 2-12 Figure 2-13

Schematic representation of the photoelectric Investigation of the photoelectric current as a

process. function of the applied voltage.

Incident Ejected Frequency

light electrons
Photocathode Collecting
anode
<£y
Metal surface

^y-^f- Current
Voltage

Applied voltage

adapted The notion that light should have a

to this interpretation in Section 2-4).
discrete composition was greeted with skepticism. Everyone was inclined to resist such
a reckless proposition because it seemed to contradict the established picture of wave
behavior. Einstein looked for indications from experiment that supported his conjec-
ture and found the desired evidence in 1905 in the photoelectric effect. (We should
recall that he also put forward his special theory of relativity in the same remarkable
year.) In time his proposed quanta of light came to be known as photons.
The photoelectric effect is one of the many phenomena that involve the interaction
of electromagnetic radiation with matter. Figure 2-12 shows a sketch of the process, in
which the incidence of light on a metal surface causes electrons to be ejected from the
body of the metal. A collecting plate at a higher potential can be added to the picture,
as in Figure 2-13, so that the photoelectrons can be detected and a photoelectric
current can be measured in an external circuit. This simple mechanism is the basis for
several familiar electronic devices found in everyday use. The process also occupies a
prominent position in the development of 20th century physics.
The first observation of the photoelectric effect was made by Hertz in 1887, very
soon after his demonstration of the electromagnetic nature of light. Like so many early-

discoveries, the effect was noticed by accident. The light-ejected negative charges were
proved to be electrons in experiments conducted by J. J. Thomson in 1899. The
puzzling aspect of the phenomenon was the fact that the energy of the emitted
was quite surprising
electrons did not vary with the intensity of the incident light. This
since was thought that electrons with greater energy should be seen if the metal
it

surface was exposed to a greater flux of electromagnetic energy. The photoelectron

energy did show an increase, however, when the frequency of the incident light was
increased.
These results bewildered everyone but Einstein, who recognized the process as a
concrete application of his light-quantum hypothesis. In his view the effect occurred
 2-5 The Photoelectric Effect 101

when a single incident quantum of light was absorbed in the metal and all its energy
was given up to a single electron. The electron could then be ejected if it acquired
enough energy from the absorbed photon to separate the particle from the metal and
release the excess energy as free-electron kinetic energy. An increase in the intensity of
the light would flood the metal surface with a greaterof quanta and cause number
more would produce a greater photoelec-
electrons to be ejected. These photoelectrons
tric current but would carry no more energy individually unless more was delivered to

them by the incident photons. An increase in the frequency of the incident light would
result in a greater photon energy. The photons would then have more energy to give
up to the electrons, and so each ejected electron could leave the surface with greater
kinetic energy. Thus, Einstein was able to explain every aspect of the puzzle by
assuming an interaction between light and matter, represented by the absorption of
discrete quanta of light. The photon concept eventually gained credibility in the
decade that followed, as Einstein's predictions were confirmed in a series of photoelec-
tric experiments undertaken by R. A. Millikan.
Let us examine Einstein's predictions in the context of a typical photoelectric
experiment, following the procedure illustrated in Figure 2-13. We take light of fixed
frequency and variable intensity to be incident on a photocathode, and we let the
liberated electrons be accelerated to a collecting anode by applying a difference in
potential between the two elements. An ammeter records the observation that the
photoelectric current increases, and eventually levels off, as the applied voltage is
increased for a given light intensity. This saturation of the current indicates a limiting
regime where the ejected photoelectrons are being collected at their maximal rate. An
increase in the intensity of the light causes the incidence of photons and the liberation
of electrons to proceed at a greater rate so that the photoelectric current rises to a
higher saturation level. If we reduce the applied voltage to negative values we observe
that the negative potential difference retards the collection of photoelectrons at the
anode until the current finally vanishes at a particular applied voltage — <f>
. The
quantity <$> is called the stopping potential. Its value provides a direct measure of the
maximum kinetic energy for an ejected electron,

*w = «*b. (2-44)

because the applied voltage — <J>

must be such as to retard the fastest electron leaving
the cathode. (Note that the electron charge is expressed as —e to obtain this equation.)
We observe that the graph of current versus voltage follows a different curve for each
intensity of the light and that the various curves have varying levels for the saturation

current but the same values for the stopping potential. We therefore conclude that <J>

does not vary with the flux of the incident radiation as long as the frequency of the
light remains fixed. This striking feature of the experiment is at odds with classical
expectations and bears out Einstein's proposition.
The light-quantum hypothesis describes the incident light at frequency v as a
stream of photons, each with energy

e = hv. (2-45)

A photoelectron is ejected from the metal surface of the cathode whenever it absorbs a
photon, provided enough energy is acquired to release the electron from confinement
inside the metal. The basic mechanism is expressed as

y + e
bound free
102 Photons

Figure 2-14

Stopping potential versus frequency as

predicted by Einstein's equation. The slope of
the straight line gives the value of the ratio
h/e.

where the symbol y refers to the absorbed photon. A portion of the absorbed energy e
is spent to remove the electron from the metal, and the remainder appears as
free-electron kinetic energy. The minimum energy required to free an electron by this
process is called the photoelectric work function W This quantity. is characteristic of
the specific material in the surface so that W varies from one type of metal to
another. Every electron leaving a given metal with maximum kinetic energy must pay a
cost in energy equal to W in order to obtain its freedom. We can account for the
energy absorbed in this case by writing

h*=WQ + tf max or K max = hv - W . (2-46)

The second formula is Einstein's equation for the photoelectric effect.

We can combine Equations (2-44) and (2-46) to obtain a prediction for the
stopping potential:

h W
4>
=-p Q
.
(2-47)
e e

This result tells us that the experimental value observed for <f>
should increase linearly
with an increasing light frequency v. Figure 2-14 shows a representation of the
straight-line relation between <p() and v. The graph is typical of those found for any
given metal and is representative of the results obtained by Millikan in confirmation
of Einstein's hypothesis. Note that the slope of the straight line is predicted to be h/e
in Equation (2-47). A photoelectric experiment can therefore provide another de-
termination of Planck's constant, by a method completely different from Planck's
blackbody approach. Note also that the figure indicates a minimum light frequency
below which the photoelectric effect cannot occur. This threshold frequency vxh is
obtained by setting = in Equation (2-47) to get
<J>

hvth = W . (2-48)

Light with this frequency contains photons with just enough energy to release
electrons from the metal with zero speed of ejection. Light of lesser frequency cannot
produce photoelectrons no matter how intense the illumination might be.
 2-6 XRays 103

Example

Lithium is one of the metals studied by Millikan in his tests of Einstein's

equation. The Li photoelectric work function has the tabulated value WQ
= 2.42
eV. Equation (2-48) gives the threshold frequency for the emission of photoelec-
trons as

=
W (2.42eV)(l.60 X 10" 19
J/eV)
V,u = 5.84 X 10
14
Hz,
~h 6.63 X 10" 34 s
J -

in good agreement with Millikan's original results. The corresponding maximum

wavelength for the photoelectric effect in Li is then given by

8
X 10 m/s
A,.
th
= —c

p tb
=
5.84
3

X 10
-
14
Hz
=514 nm,

a value in the visible range. Suppose that a 1 W monochromatic source of light

with this wavelength illuminates a Li surface at a distance of 1 m. The number

of photons emitted by the source per second is

U/s
= 2.58 X 10
18
photons/s.
(2.42 eV/photon)( 1.60 X 10~ 19 J/eV)

The corresponding number striking unit area of the Li surface per second is

18
X
2.58 10 photons/s
-
2
— - = 2.06 X 10
17
photons/s •
m 2
,

47r(l m)

assuming a uniform distribution of photons over a sphere of 1 m radius.

2-6 X Rays

The quantum hypotheses of Planck and Einstein pertain to frequencies and wave-
lengths of radiation across the entire electromagnetic spectrum. Quanta of energy in
the electron-volt regime are associated with wavelengths of light in the visible range,
where the photoelectric effect is observed as an important process. Longer wavelengths
in the infrared and microwave regions of the spectrum correspond to quanta whose
energies fall below the photoelectric thresholds of matter. These forms of radiation
make their appearance in other kinds of photon interactions. An altogether different
domain of interesting radiative processes is found at the shorter wavelengths where the
corresponding photon energies are of kilo-electron-volt order. The radiation known as
x rays occurs in this part of the electromagnetic spectrum.
X rays were detected for the first time in 1895 by W. K. Roentgen. The discovery
was a by-product of experiments on the behavior of electron currents, or cathode rays,
in the space between the terminals of a rarefied gas tube. The radiation was observed
to come from the high-potential end of the tube and was found to have a remarkable
ability to penetrate material and cause ionization in matter. The nature of the
radiation remained obscure until 1912, when x rays were conclusively demonstrated to
104 Photons

Figure 2-14

Electromagnetic spectrum. Frequencies and

wavelengths are plotted on logarithmic scales
and satisfy the relation v\ = c = 3 X 10 8 m/s.

Frequency
v= 10' Hz

n J\ -
;= -16
i= 24 f_

-14 -
22 7 ray
-12
20 -

-10 Xray
L8

8
Lb
- Vis Ultraviolet
-6
14
Infrared
-4
12

2
Id

Microwave
8 and
radio
2
6

4
4

;= 6
i= 2 >
1

Wavelength
A= 1
;
m

have wave properties by M. T. F. von Laue. These

as a result of experiments devised
studies involved the diffraction ofbeams of x rays using crystals whose lattice spacings
were small enough to accommodate the nanometer wavelengths of the radiation. The
wavelengths were observed to become shorter as the applied voltage on the x-ray tube
was increased through kilovolt values. The radiation was also shown to have propa-
gation and polarization characteristics in common with other kinds of electromagnetic
waves.
Let us examine the principles of x-ray diffraction at this point so that we can have
the results on hand for later reference. We use classical wave optics and present the

Figure 2-15

Bragg reflection of x rays from neighboring

crystal planes.

'rfsin 8
 2-6 XHays 1(15

arguments with the aid of Figure 2-15. The diffraction of x rays by a crystal lattice is

described in terms of the interference of waves reflected from parallel crystal planes. A
crystal plane is defined by a particular two-dimensional array of atoms at their lattice
sites inside the crystal. Incident waves are scattered by all the atoms in the crystal, and
of course each atom scatters radiation in all directions. The role of the crystal plane is

to single out a certain direction for the scattered waves such that the angle of
scattering equals the angle of incidence, as in the law of reflection familiar from
geometrical optics. Atoms in the crystal produce this collective effect because waves
scattered from individual atoms are in phase and interfere constructively if their
direction corresponds to reflection from a crystal plane. The resulting wave geometry
is illustrated in the figure.
The figure goes on to show two equal-angle reflections from neighboring parallel
planes. Waves reflected from planes with lattice spacing d undergo a second stage of
constructive interference at reflection angle 6 if the optical path difference for the two
reflected waves equals a whole number of wavelengths. The figure tells us that the
difference between paths is given by 2d sin 6, and so we expect to observe constructive
interference whenever the angle obeys the relation

2d
sin 6 = an integer. (2-49)

This formula can be employed to determine x-ray wavelengths using crystals of

known lattice spacing and, conversely, to investigate crystal structures using x rays of
known wavelength. The formula in Equation (2-49) is called the Bragg condition, and

the reflection angle in the formula is called the Bragg angle. These methods of x-ray
analysis are named after W. H. and W. L. Bragg, pioneers (as father and son) of the
science of x-ray crystallography.
Figure 2-16 shows a sketch of a certain type of x-ray tube in which the x rays are
produced in the collisions of energetic electrons with a metal target. The electrons boil
away from a hot filament and are accelerated through a large potential difference to
the target, where they collide with the heavy atoms in the metal and undergo an

Figure 2-16

Elements of an x-ray tube and features of an

x-ray spectrum. The spectrum consists of
continuous and characteristic components.

Figure 2-17

Bremsstrahlung process for an electron

X-ray entering the field of an atomic nucleus.
spectral
intensity K'

Target _
nucleus()
 .

106 Photons

abrupt deceleration. Much of the electrons' loss of energy goes into heating the target,
while the rest is emitted directly in the form of radiation. The observed x rays exhibit
all wavelengths above a certain minimum value, as illustrated by the distribution of
x-ray intensities in the figure. This spectrum shows a superposition of two distinct
kinds of x-ray distributions. The radiation has a continuous component containing all
wavelengths A above the minimum value A mjn the shape of this distribution is
;

essentially the same for any kind of metal target in the x-ray tube. A discrete
collection of sharp wavelengths is also observed in the spectrum; these x-ray lines are
characteristic of the target and differ from one metal to another.
The continuous distribution of x rays is called a bremsstrahlung spectrum, from the
German word for "braking radiation." This component is associated with the classical
radiation that results from the acceleration of charged particles, as the electrons are
brought to a sudden stop in the metal target. The minimum wavelength is explained
by including the quantum hypothesis in the description. Let us refer to Figure 2-17
and visualize the process in terms of a single electron entering the target, encountering
an atom, and emitting a single x-ray photon. (Actually, the nucleus of the atom is
responsible for the indicated Coulomb attraction and acceleration of the radiating
electron.)
The basic process of energy loss may be described as

e
—* e + y near a nucleus,

a sort of inverse to the photoelectric effect. We identify the energy of the emitted
photon as the difference of kinetic energies shown in the figure:

hv = K- K'.

Note that the recoil energy of the atom can be neglected because the nucleus of the
atom is very massive. The energy of the photon is a maximum for those collisions in

which the electron is brought to rest. In this situation we have

K' = =* hv mA% = K.

The kinetic energy of the incoming electron is determined by the voltage <f>
across the
terminals of the x-ray tube:

K= e<j>.

We know that a maximum frequency corresponds to a minimum wavelength because

of the relation v = c/X. We can therefore obtain the quantity A min by assembling the
-
relations that define v n

In

= hv m *x = <*

and so

he
A mm = — ,
(2-50)
v '

It is obvious that K' is free to assume any value from zero on up to the value of K.

Therefore, v must vary continuously between zero and vmax while A ranges continu- ,

ously between A mm and infinity.

 2-7 The Complon Etlecl 107

It was noted long ago that a measurement of the threshold wavelength in a

bremsstrahlung spectrum could be used in conjunction with Equation (2-50) to furnish
another accurate determination of Planck's constant. Studies of the short-wavelength
limit were conducted for this purpose in experiments performed by W. Duane and
F. L. Hunt in 1915.
The discrete lines in the x-ray spectrum are peculiar to the specific metal in the
target of the x-ray tube. These characteristic x rays are significant because they offer
direct evidence for the quantum properties of matter.
X rays have enjoyed a wide variety of practical applications as a result of their
remarkable penetrating power. X-ray sources have been put to use as diagnostic and
therapeutic devices in medicine and in dentistry. The radiation has also been
employed in industry to examine structures for possible hidden defects.
X rays have recently been observed from sources in the universe beyond the solar
system. Galactic sources of the radiation are believed to exist in binary stars, where
bremsstrahlung x rays are supposedly produced as ionized matter streams from one
star to the other. The exciting new field of x-ray astronomy has developed out of these
discoveries.

Example

The combination of constants he appears often enough in atomic physics to

warrant a separate calculation:

(6.626 X 10" 34 J •
s)(2.998 X 10
8
m/s)(l0 9 nm/m)
19
1.602 X l(T J/eV
= 1240 eV •
nm = 1 .240 keV •
nm.

We can apply the result immediately to Equation (2-50) and express the
short-wavelength cutoff for the continuous x-ray spectrum as

1 .240 kV •
nm
rnin ,

Thus, a 40 kV x-ray tube has a cutoff at

1.24
nm = 0.031 nm

and produces a continuous spectrum of x rays containing all longer wavelengths.

2-7 The Compton Effect

quantum theory of light proposed that the photon be regarded only

Einstein's original
as a quantum of energy. His conception of the photon continued to evolve until 1917,
as he came to believe that a notion of directedness should also be incorporated in his
idea. He made provision for this by letting the light quantum have characteristics of
momentum as well as energy. It might seem odd that the father of special relativity
should hesitate for more than a decade to bring together these complementary
108 Photons

Figure 2-18

Compton scattering of radiation. The scattered wavelength A' is longer than the incident
wavelength A. In the classical picture, the incident plane wave and the scattered spherical wave
have the same frequency and wavelength.

relativistic properties, but such was Einstein's provisional attitude toward the develop-
ing quantum theory. He looked for support from experiment to establish momentum
and energy same hypothesis and was not able to find immediate
as joint aspects of the
evidence. A test of his revised photon concept was finally proposed by Debye and,
independently, by A. H. Compton. The decisive experiment was then performed by
Compton in 1923.
The Compton effect pertains to the scattering of monochromatic x rays by atomic
targets and refers to the observation that the wavelength of the scattered x rays is

greater than that of the incident radiation. Figure 2-18 illustrates the process and
identifies the Compton wavelength shift in terms of the wavelength difference A' — A.
This quantity is observed to vary as a function of the scattering angle 6 shown in the
figure. The experiment is performed with x rays because the short wavelengths are
needed to have an observable effect. A pronounced x-ray wavelength shift is associ-

ated with a scattering of the x ray by an electron in an atom rather than by atom as
the
a whole. We demonstrate this experimentally by finding that the shift does not depend
on the identity of the atomic scatterer, and so we attribute the effect to the electron as
the common constituent of all target atoms. Our discussion of the Compton effect is
given in terms of the scattering of an x ray by a free electron, since an x-ray quantum
carries enough energy to make the distinction between a bound electron and a free

electron essentially irrelevant.

The figure goes show how the phenomenon presents another unexplainable
on to
problem for classical The classical mechanism for the scattering of an
physics.
electromagnetic wave is explained in a radiation theory developed by (and named
after) Thomson. His model assumes that the incident wave comes in at frequency v
and causes the target electron to oscillate and radiate the outgoing wave. The
oscillation frequency is also given by v since the electron is driven at this frequency by
the incoming wave. The outgoing classical radiation oscillates at the frequency of the
source and therefore has to have the same frequency v. Thus, the classical picture

cannot account for the observed wavelength shift.

The quantum theory of radiation treats the x-ray beam as a stream of photons. For
x rays of wavelength A the photon energy is given by

he
£ = hv= — . (2-51)
A

The photon is also assigned a momentum according to Einstein's revision of the

 27 The Complon Effect 109

Figure 2-19

Kinematics of Compton scattering.

Before After S , P'

e .p

>
E , P

photon concept:

hv h
(2-52)

Note that this assignment of energy and momentum reproduces the relativistic
relation given in Equation (1-39). Recall that the equation holds for a particle of zero
mass whose speed is equal to c in all Lorentz frames. Thus, the revised light-quantum
prescription begins to attach some of the properties of a massless particle to the
behavior of a photon.
The Compton process is then described in terms of a relativistic collision involving
the elastic scattering of a photon by an electron,

y + e — > y + e

We proceed by imposing the familiar conservation laws for the total relativistic
momentum and energy, where the various kinematic quantities are identified in
Figure 2-19. We take the electron to be at rest initially and to have energy and
momentum E and P after the collision. These variables are related by the relativistic
formula given in Equation (1-35):

(2-53)

We may write conservation of momentum as

p - p' = P

and square the equality to get

2
p - 2c p
2 2
c • p' + 2
c p'
2
= c
2
P2 .

Since cp = e and cp' = e', the result can be rewritten as

e — Zee cos a + e = E~ — my ,

where Equation (2-53) is used to eliminate P 2 We . also employ conservation of

110 Photons

relativistic energy by writing

e + m e
e
2
= e' + E.

Rearranging and squaring produce the following equality:

e
2
- 2ee' + e'
2
= E 2 - 2Em e
e
2
+ m 2e 4 .

The two quadratic equations represent information obtained from independent con-
servation laws. We subtract equalities to get

2ee'(l — cos 8) = 2m e
c
2
\E — m e
c
2
)

= 2m e
c
2
(e — e'),

and we divide by 2ee' to obtain

1 1

1 — cos 6 = mx "'

A' A
I
— — —
he he

using Equation (2-51) at the last step. Finally, we solve for the wavelength difference
and find

h
AA = A'- \= - -(1 - cos0) (2-54)
m (
c

as the desired result for the Compton wavelength shift.

It is interesting that the shift in wavelength depends only on 6 and does not
vary with the wavelength of the incident radiation. This feature of the result is seen
clearly if we rewrite Equation (2-54) in the form

AA = A c (l - cos0).

The parameter X c is known as the Compton wavelength of the electron, a constant

defined in terms of fundamental constants as

h
A c.= --. (2-55)
m c e

This quantity is numerically equal to 0.00243 nm, a length that sets the scale for the

wavelength shift in the Compton effect. It is clear that the incident wavelength must
be comparable to A f if A' is to be noticeably different from A. For this reason the
.

effect is not detectable for visible light and only begins to be measurable for x rays.
Compton's experiment was performed with incident radiation at one of the
characteristic wavelengths of molybdenum, taken from a Mo target in an x-ray tube.
These x rays were scattered from graphite, and the scattered radiation was observed in
a detector set at 90° with respect to the direction of incidence, as shown in Figure
2-20. Compton's data confirmed his prediction of a wavelength shift and thereby
verified the formula in Equation (2-54) as a valid consequence of the premises
 2-7 The Compton Effect 111

Figure 2 20

X-ray scattering at 90°. The observed

distribution of scattered wavelengths shows
Compton scattering by electrons at A' = A +
A r and Thomson scattering by atoms at A'=

Detector |

X-ray tube

underlying Equations (2-51) and (2-52). Further studies at several values of A

supported the conclusion that the shift was independent of wavelength. These results

firmly established the quantum nature of electromagnetic radiation with respect to

both energy and momentum aspects of Einstein's proposition.
Let us draw a final connection between these conclusions and the classical

treatment of the scattering of radiation. We have alluded to the latter viewpoint, and
to Thomson's classical theory, in our discussion of Figure 2-18. The classical picture

requires A' = quantum picture predicts AA <s: A and A' ~ A for A

A, while the Ac » .

This observation tells Compton scattering becomes Thomson scattering in the

us that
limit where the wavelength becomes much larger than the Compton wavelength. We
can see the Thomson limit in another guise by referring to the lower part of Figure
2-20. The observed wavelength distribution for x rays scattered at 90° exhibits a peak
at A' = A, in addition to the result expected at A' = A + A c The second peak agrees .

with the Compton prediction in Equation (2-54) for = 90°. The first peak represents
no shift and evidently corresponds to photon scattering from the atom as a whole. In
this circumstance, the factor h/m e c in Equation (2-54) is replaced by h/Mc, where M
is the mass of the atom. The Compton wavelength of the atom is much smaller than

A c since M
is much larger than m
e
Hence, even x-ray wavelengths experience no
.

observable shift in scattering from the whole atom, and the corresponding feature of
the data exhibits the classical Thomson prediction.
The photon is often called a particle because it occurs in radiation discretely and
because it has energy and momentum properties appropriate for a relativistic particle
of zero mass. We refrain from adopting this usage in all its implications, however. We
especially avoid contemplating any sort of localization of the photon, as we might
imagine in the case of ordinary types of particles. None of our applications of the
light-quantum concept includes any notion of electromagnetic energy and momentum
at some localized position in space. We learn that the photon is absorbed by an
 ~

112 Photons

electron in the photoelectric effect and is scattered by an electron in the Compton

effect. The electron can be expected to have certain localization properties, but the
interaction of the electron with the photon does not require the photon to have any
localization of its own. Thus, when we speak of radiation as a system of photons with
particle attributes, we realize that we are beginning to entertain a new quantum-particle
idea in which discreteness and localization are entirely separate considerations.

Example

Let us begin with Equation (2-55) and compute the value for the Compton
wavelength of the electron. We use the electron rest energy and the convenient
constant he to get

he 1240eV-nm
Ac = = 0.002427 nm,
me 2 " 0.5110 X 10
6
eV

as quoted above. If we then let the incident x ray have wavelength A = 0.0711
nm as in Compton's 1923 experiment, we find from Equation (2-54) that the
wavelength of the x ray scattered at 8 = 90° is

A' = A + Ac = (0.0711 + 0.0024) nm = 0.0735 nm.

Figure 2-20 shows how this feature would appear alongside the classical
Thomson component at A' = 0.07 nm. (The broadening of the observed
1 1

wavelengths may be attributed to the fact that the target particle is not
necessarily at rest, as assumed in the analysis.) For 90° x-ray scattering, the
recoil of the electron has momentum components, parallel to the incident
photon and antiparallel to the scattered photon, given by

h 6.63 X 10" 34 J •
s
P.-P- = 9.32 X 10" 24 kg •
m/s
A
"
0.711 X 10~
10
m

and

4
6.63 X 1 *
J •
s
4
P,-P'- = 9.02 X 10 ~ kg •
m/s.
A' 0.735 X 10 lu
m

We can compute the electron recoil angle <J>

from these quantities:

9.02
tan<£ = 0.968 <t>
= 44
c

9.32

This calculation provides further illustration of the Compton effect as an

exercise in relativistic elastic collisions.
 2-7 The Campion Effect 113

Figure 2-21

Doppler effect for a photon from a moving

source.

6', p'
Light
source
Observer
in S

Example

Let us take the photon's energy and momentum from Equations (2-51) and
(2-52) and introduce a momentum four-vector for the photon as

/*
=
iz/c
P
where p = - =
f
—
hv

c c

We know how the four-vector ft

transforms under the Lorentz transformation to
produce the photon's energy and momentum in another Lorentz frame. We can
use this approach as an elegant alternative to our earlier derivation of the
Doppler shift for the frequency of light, since both e and p are directly related
to the frequency v. Figure 2-21 shows the notation for the case of a light source
of frequency v Q at rest in S', where S' moves with speed u toward an observer at
rest in S. We let the photon be directed at the observer so that we need only
treat two components of the photon's momentum four-vector in the two Lorentz
frames. Since S' is the rest frame of the source, the primed four-vector is

hv.
P
IE /

The corresponding components in S are found by applying the inverse of the

Lorentz transformation defined in Equation (1-66):

= y -iyfi P'
fi
= se~ y tyfi y ie'/c

where

Y
= and fi
'1 - ft''

We let the observed photon frequency be called i> m S and perform the
transformation as follows:

hv 1 hv 1 -ifi 1

c i c ifi 1

hv 1+/? hvn
= Y
;
y(i +fi)
c i(l+fi)
114 Photons

The calculation tells us that v and p are related by the formula

1 + j8 1+

in agreement with our previous result in Equation (1-9).

2-8 y Rays and Electron- Positron Pairs

Photons with extremely large energy are found in the y-ray regime, beyond the x-ray
region of frequencies in the electromagnetic spectrum. In practice, any wavelength of
nanometer order or less refers to y radiation, so that the x-ray and y-ray regions of the
spectrum actually overlap. High-energy y rays appear abundantly in nature in
certain very energetic physical processes. Some of the nuclear reactions that take place
at very high temperatures in stars produce y radiation. An appreciable y-ray
component is also present in the secondary cosmic radiation that results from
high-energy particle interactions in the Earth's atmosphere. Nuclear y rays are also
observed in the laboratory when accelerated particles are used to excite nuclei and
stimulate radiation.
Antimatter can be formed in the interactions of y rays if the radiation has
sufficiently large energy. The production process occurs when an incident y-ray
photon is absorbed in the vicinity of an atomic nucleus, and a matter-antimatter pair
of particles is created from the absorbed photon's energy. The least massive of these
pair systems consists of the electron and its antiparticle, the positron. Typical
particle antiparticle properties are observed for the electron and positron; the two
species have equal mass m and
e
opposite charge — e and +e. The electron and
positron are denoted as T and e
+
, and the pair-production process is expressed as

—» e~+ +
y e near a nucleus.

Figure 2-22 shows a sketch of the reaction in which a high-energy incoming photon
disappears and materializes into massive particles of opposite charge. Pair production
takes place in the Coulomb field of the nucleus, where the photon can be absorbed

Figure 2-22

Electron- positron pair production. A high-

energy photon is absorbed in the field of an
atomic nucleus, and an e e^ pair is created.
 2-8 y Rays and Electron- Positron Pairs //5

and where the nucleus can act as a massive body to ensure the conservation of
momentum and energy. The nucleus is an essential participant as a spectator to the
process. It is clear that a spectator is needed because, if the photon could sponta-
+
neously convert into an e~e pair in empty space, a Lorentz frame could then be
found which e~ and e + would have equal and opposite momenta, and y would be
in
at rest. Such a conclusion is untenable since y rays must have speed c in all frames.

To analyze pair production we consider a large photon energy that is still small
compared to the very large rest energy of the nucleus. We are then allowed to neglect
the recoil kinetic energy of the spectator and account for the energies shown in the

figure by writing
hv = E_+ E +
= K^+ K + +2m e
c
2
,
(2-56)

+
where K_ and K + are the kinetic energies of e~ and e . The photon energy must
exceed a minimum value in order for the y ray to initiate pair production. We obtain

hv mm = 2m/ (2-57)

from Equation (2-56) when we set K_= and K+ = 0. This formula determines the
threshold for pair production in the limit of infinite mass for the spectator nucleus.
The numerical value of this threshold y-ray energy is 1.02 MeV. The corresponding
maximum y-ray wavelength is given by

c h
A_
max
'
=
vm 2m c
,„
nun

a result equal to half the Compton wavelength of the electron. Radiation of shorter
wavelength contains photons whose energies exceed the threshold and produce elec-
trons and positrons with nonzero kinetic energy.
Pair creation has a reverse process known as pair annihilation. This reaction occurs
at any energy when a positron encounters an electron and the two particles disappear,
converting their total energy to y radiation. Positrons suffer this fate
relativistic
+
inevitably whenever they come into proximity with matter. The e~e system cannot
annihilate into a single y ray because the photon would then be found at rest in the
CM frame of the e~e
+
pair. Pair annihilation occurs most rapidly in the two-photon
mode
+ ->
e'+ e 2y,

although annihilation into three y rays is also possible for certain configurations of the
electron-positron system.
+
An interesting e~e system actually exists in the form of positromum, in which e~
+
and e are bound together by the force of Coulomb attraction. This quasiatomic
structure has been synthesized in the laboratory and has been analyzed thoroughly in
experiment and in theory. Positronium has a very short lifetime because of the
10
pair-annihilation mechanism; the system lives only 10 s on average before decay-
ing by its 2y annihilation mode. Figure 2-23 shows an illustration of the decay in the
positronium rest frame, where the indicated photon energies are determined by the
relation

2hv = 2m/.
116 Photons

Figure 2-23

Positronium annihilation into two photons.

CM at rest

2m/ 2 , hv

Before After

It follows that each y-ray wavelength is equal in value to the electron Compton
wavelength h/m/ in this particular frame.

We have discussed certain photon phenomena in this chapter as episodes in the

growth of the early quantum theory. The photoelectric effect, Thomson and Compton
scattering, and pair production are especially important examples of photon interac-
tions because these processes determine how radiation energy is dissipated in its

passage through matter. To illustrate, let us consider a beam of radiation of given

intensity impinging on a material medium, and assume radiation of a definite
wavelength with a corresponding photon energy hv. The different photon interactions
cause different kinds of attenuation in the beam intensity as the radiation penetrates the
medium. The beam direction, and the
scattering processes deflect photons out of the
photoelectric and pair-production reactions remove photons from the beam. These
three possibilities are drawn schematically in Figure 2-24. Each process has a range of
values in the variable hv, where the particular interaction acts as the dominant cause
of beam attenuation. We have just learned that pair production has a y- rav threshold
near MeV. This process is the primary contributor to attenuation of the beam when
1

hv exceeds 10 MeV. Of course, the other two processes are the only ones possible when
h v is less than MeV. The photoelectric effect dominates below 100 keV, while
1

scattering takes over in the intermediate range above and below MeV. We can make 1

these qualitative assertions more specific after we have learned how to measure and
compare the various processes.

Figure 2-24

Attenuation of a beam of photons in matter.

 2-8 y Rays and Electron - Positron Pairs 1 1

Example

The threshold formula for pair production in Equation (2-57) holds in the
limiting case of an infinite-mass spectator. The nucleus of an atom approximates
this limiting condition quite satisfactorily. Let us instead consider pair produc-
tion in the neighborhood of an electron, so that we are compelled to account for
the kinematics of all participants in the reaction

y + e~ — > e~-\- e~+ e

+
.

The threshold formula turns out to be quite different in this case. We express the
situation at threshold by assigning the incident photon an energy e = hv min and
by letting the three final particles have the same speed u in the same direction.
Momentum conservation requires

3m u
(*)
c ]/l - u
2
/c 2 '

and energy conservation requires

o 2
3m c
e + m e
c
2
= - e

o ^
. (**)
yl — «/r

Dividing ( * ) by ( * * ) results in a determination of the speed u:

e u

e + m.c c

and so

u 2emc 2 + m 2,c*
2 2
c (e + m e
c )" (e + m p
c
\

We insert these results in ( * ) and get

e = ,

'l
3m
- u
uc

2
=
/c 2
= 3m c
e + m/
e

2
\jm f c (2e
e

2
+ mc
+ m e
c
2
)

or

J2e + m (
c
2
= 3{m/~ .

Squaring then leads to the final result:

9m t
c
2
— m e
c
2

e = hv mtn = = 4m c

The methods of Section 1-11 can also be used to obtain the same conclusion.
118 Photons

Problems

1. Show that the universal function in Kirchhoff's theorem is identical with the spectral

emittance of a blackbody. Prove that, for an arbitrary radiating object, the theorem can
be stated as

E „(r) = «,(r),

an equality between the spectral emissivity and the spectral absorptance.

2. Calculate the power received from the Sun at the Earth, the total power radiated by the
Sun, and the temperature of the Sun. The following data are provided:

5 = 1350 W/m 2
solar constant,

r
E
= 6.37 X 10
6
m radius of the Earth,

R = 1 .50 X 10" m radius of the Earth's orbit,

r
s
= 6.96 X 10" m radius of the Sun.

At what wavelength should the peak in the solar spectrum occur?

3. As a hypothetical situation (call it "radiation in flatland"), consider standing electromag-
netic waves in a too-dimensional "cavity," letting the enclosure be square as shown.
Assume that E has only two components, E t
and E r
, and that B must be perpendicular to

the plane of the enclosure. Obtain expressions for the components of the electric field,

subject to the condition £ tan = at the boundaries. Determine the allowed frequencies of

the standing-wave modes.

Continue with the hypotheses of Problem 3, and show that the number of modes at

frequency v per unit frequency interval is

27:1'

K = —a, c

where A is the area of the enclosure.

Still continuing, let "radiation" be emitted from a small opening in the enclosure, noting
that the opening is on^-dimensional so that the radiation streams across an arclength. Let
M v
be the energy emitted per unit time per unit arclength per unit frequency interval,

and let «,, be the energy stored in the enclosure per unit area per unit frequency interval.
Show that these quantities are related by

M„=-u„

Itemize all the microstates for the assignment of four particles into three cells. Organize
these according to macrostates of the system and verify that the number of microstates
 Problems 119

corresponding to each macrostate is in agreement with the general formula for the
thermodynamic probability.

7. Consider the application of the Maxwell- Boltzmann distribution to a system of classical

oscillators representing the radiation modes in a cavity. Classically, a continuous range of

the energy e is allowed for each oscillator. Assume that the number of modes dn per unit

proportional to the factor e~'

u (and not /e* _ " e as in the particle
energy interval de is ,

case). Show that the average energy per mode is

<«> =
^ = kB T

by making the appropriate averaging calculation.

8. Show that the Planck result for (e), the average energy per mode, agrees with the
classical equipartition result k B T in the limit of small frequency.

9. A 50 g mass hangs from a spring whose spring constant is 80 N/m. The oscillations of the
mass have amplitude 10 cm. Can it be argued that this macroscopic classical oscillator is a

Planck oscillator by assigning the system to a quantized energy state whose energy is a
multiple of hv? How accurately would the energy of the oscillator need to be known in

order to insist on this interpretation?

10. The wavelength distribution of a 5000 K blackbody radiator is studied for a range of

wavelengths extending to either side of \ m The endpoints

. of the range (A min ,A mlx )

correspond to the values of X where the spectral emittance is half the peak value.

Determine the values of A min and X max -

11. For a blackbody, the frequency distribution peaks at vm and the wavelength distribution
peaks at \ m Consider the derivations of the dependence of vm and \ m on the temperature
.

to prove that vm \ m =£ c. Obtain the actual expression for the product vm \ m .

12. The peak value M x at the wavelength \ m in the distribution of blackbody radiation
increases with temperature as indicated in Figure 2-3. Show that M^ depends on T as

MXm = CT",

determining the exponent p and the constant C.

13. Continue with " flatland radiation" following Problem 5, and deduce a formula for the

frequency dependence of M v
. (Should the Planck formula for (e) be different from the
case for a three-dimensional cavity?) Integrate M v
over all v to obtain the total emittance
M. Cast the integration in a form that contains the dimensionless integral

/•oo x dx

Jq e* - 1

as an explicit factor. Establish the form of the Stefan- Boltzmann law for "flatland," and
determine the analogue of the Stefan-Boltzmann constant in terms of the dimensionless

integral and other constant factors.

14. Determine the range of photon energies that corresponds to visible light, with wavelengths
lying between 400 and 700 nm. Repeat the calculation for radiation in the ultraviolet

range from 5 to 400 nm, and in the infrared range from 700 to 500,000 nm.
15. Radio station Will (Amherst) broadcasts at 1430 kHz with 5 kW power. Calculate the
energy of a WTTT photon and the number of photons broadcast per second.
120 Photons

16. Estimate the number of photons emitted per second by a 100 W light bulb, assuming the
average wavelength for the light to be 500 nm. At what distance from the source is the
photon flux equal to 100 photons per second per square centimeter?

17. Consider the photoelectric process for a free electron,

y + ffree ~~
*
f
free '

and prove that the process is not possible.

18. A 40 W ultraviolet light source of wavelength 248 nm illuminates a magnesium surface

2 m away. Determine the number of photons emitted from the source per second and the
number incident on unit area of the Mg surface per second. The photoelectric work
function for Mg is 3.68 eV. Calculate the kinetic energy of the fastest electrons ejected
from the surface. Determine the maximum wavelength for which the photoelectric effect

can be observed with a Mg surface.

19. The radiation from a 500 K blackbody strikes a metal surface whose work function is

0.214 eV. Determine the wavelength for which the peak of the blackbody spectrum
occurs, and determine the longest wavelength in the spectrum capable of ejecting
photoelectrons from the surface. What portion of the blackbody 's total emittance M(T) is

effective in producing photoelectrons from the metal surface? Express the result in terms

of a dimensionless integral over the Planck distribution.

20. A y ray with wavelength 0.005 nm is incident on an electron at rest and is scattered

straight backward. Calculate the wavelength of the scattered y ray and the kinetic energy

(in keV) of the recoiling electron.

21. Ay ray of wavelength 0.0062 nm is incident on an electron initially at rest. The electron

is observed to recoil with kinetic energy 60 keV. Calculate the energy of the scattered y
ray (in keV), and determine the direction in which it is scattered.

22. Obtain a formula for the fractional loss of energy (e — e')/e for a Compton-scattered

photon in terms of the incident wavelength A and the Compton shift AX. Calculate
values of this quantity for 90° photon scattering as A varies from 0.1 nm down to 0.001

nm.
23. Consider Compton scattering of photons with wavelength A, and show that the scattered
photon direction 6 and the recoil electron direction </> are related by the expression

cot-
/
=11 +
M
y tamj.,

where A c; is the electron Compton wavelength.

24. Bremsstrahlung x rays of the shortest wavelength from the target in a given x-ray tube

have just enough energy to create an electron- positron pair in a dense medium. Deduce
the value of the voltage on the terminals of the x-ray tube.

25. In pair production, a photon of energy hv is absorbed in the neighborhood of a particle of

mass M to make an e~ e +
pair, each with mass m r
. The threshold photon energy for this

process is known to be

kvmm
m -
= 2m,c
f
2
for M— * oo

and

hv„ : „ — \m,c for M=m r .

 Problems W
Derive a formula for hvmm that is valid for any M, and show that the result gives

agreement in these two special cases.

26. Consider the Compton scattering of photons from a beam of electrons, as shown in the

figure. Let a photon and an electron collide head-on with relativistic energies e and E,
respectively, and derive an expression for the energy e' of the final photon, in the special

case of backward photon scattering. Show that, for E » m t

c~ , the result reduces to

1 + my/ieE

Calculate the value of e' for the collision of a 700 nm photon with a 20 GeV electron.

-0
Before After
 THREE
INTRODUCTION
TO
THE
ATOM

(/uantum physics began to receive enthusias-

tic attention in 1911 on the occasion of the First Solvay Congress. The most prominent
names in physics convened and gave the new theory a forum, where all in attendance
could respond to the radical ideas of Planck and Einstein. It was clear to adherents

and skeptics alike that the quantum theory was in need of a proper formulation and
that the theory was likely to have applications to matter as well as radiation. It was
generally recognized that the structure of the atom presented the next urgent problem
to be solved.
The modern view of the atom began to develop during the same year. E.
Rutherford was the one responsible for devising the basic model and for conducting
the decisive experiment. Rutherford's conception of the atom drew upon classical
principles aloneand contained a serious flaw that posed another insoluble problem for
classical The remedy was found by appealing to quantum concepts to
physics.
complement the classical picture. This next major contribution to the quantum theory
was introduced in 1913 by N. H. D. Bohr. The proposal had the effect of broadening
the new theory into a combined quantum treatment of matter and radiation. The
Rutherford atom and the Bohr atom were the most important developments in physics
during this period.

3-1 The Reality of Molecules and Atoms

The molecular and atomic nature of matter attracted speculative interest long before
the real existence of molecules and atoms could be proved. These constituent particles
were believed to exist as identical units in a given substance and were supposed to
make up the composition of any sample of that substance. This belief began to gain
ground on two fronts during the 19th century. The concept of submicroscopic units
was given consideration in chemistry in a scheme to organize the regularities of the
elements and was directly employed in the kinetic theory in a model to describe the
behavior of gases. Skeptics could still argue, however, that even the most successful

122
 3- I The Reality of Molecules and Atoms 123

Ernest Rutherford Niels Bohr

scheme or model could not establish the actual existence of the particles. This
skepticism had to be overcome by building up the internal consistency of the whole
molecular picture.
The periodic table of the elements was conceived during this period. The idea was
originally put forward in 1869 by D. I. Mendeleev as a device for arranging the
known chemical elements in order of increasing mass. In time the atomic number
supplanted the atomic mass as the more relevant ordering index, although the
ultimate interpretation of the ordering scheme was not made clear until much later.

Mendeleev's table listed the atomic numbers in rows and columns, where each row
contained a series of elements whose chemical valence varied in a pattern from left to

right, and where each column contained elements whose valence was the same from
top to bottom. This organization of the chemical species achieved order out of
disarray, as elements were arranged according to common chemical properties and
vacancies were left available for undiscovered elements. The demonstration of these
regularities supported the belief that different varieties of atomic particles were to be
associated with the various species.
Avogadro's hypothesis was among the first assertions of the reality of molecules and
atoms. The principle stated that equal volumes of gases at fixed pressure and
temperature must contain equal numbers of molecules. Avogadro's number was not
immediately determined by either theory or experiment. The eventual determination
of this quantity proved to be a decisive influence on the credibility of the molecular
theory.
A discovery early in the 19th century by the botanist R. Brown played an
important part in these developments. Brown used a microscope to examine grains of
pollen suspended in a fluid and observed that the microscopic particles executed a
distinctive random motion. The explanation for this effect came decades later, after
the formulation of the kinetic theory. The movement of pollen grains was seen as
evidence for the thermal motion of particles in the suspending fluid, as the collisions of
124 Introduction to the Atom

fluid particles with suspended particles resulted in the observed Brownian motion.
Einstein analyzed this behavior in 1905 (again, his phenomenal year) and showed that
the conclusions could be used experimentally to deduce a value for Avogadro's
number.
We can reproduce Einstein's treatment of Brownian motion in a few steps by
following P. Langevin's more elementary analysis of the derivation. Let us consider a
large number and mass m, suspended in a
of identical spherical particles with radius a
fluid of viscosity and examine the forces that act in one direction on one of the
tj,

particles. The force of viscous damping depends on the velocity of the particle
according to the law of G. G. Stokes:

dx
F™=-Pj
K,= -fi
t
>
(3" 1 )

where

= 6irt)a. (3-2)

The suspended particle also experiences a random force Fcol whenever it collides with
particles in the suspending fluid. Newton's law for the mass m takes the form

d 'x
a^ /o n^

since there are no other forces acting on m. (We neglect gravity and buoyancy because
these effects tend to cancel each other.)
We are not concerned with a detailed solution for x( t ), the instantaneous position
of the suspended Such a function would be rather difficult to predict because
particle.

of the complex t dependence of the random external force Fcoi Instead, we are .

interested in averaged quantities associated with x, where the averaging operation ( ) is

computed over the large number of suspended particles. The average of x(t) can be
expected to vanish since the random motion causes positive and negative values of x
to occur with equal likelihood over the collection of particles. Hence, the fluctuation of
suspended particles about zero displacement becomes the main quantity of interest.
We define this notion by means of the averaged variable (x ). The fluctuation
corresponding to motion in one dimension is then given by

* rms =/<^7> (3-4)

the root-mean-square (rms) displacement in the x direction.

Provisions are made for this analysis by casting Equation (3-3) in terms of the
variable x
2
. We use the relations

2
d 2x
d dx
—d dx *

x
2 _ 2x—
dt
and
dt
-x
2
2
= 2x—
dt
2
+ 2
I
—
dt
dt \

and then multiply Equation (3-3) by x to obtain the equality

2
1 d Idx^ P d
-tf-- («)
lit 2 * ' dt ? y*.
The next step is to average this result over all the suspended particles. We note first

that the term xFco[ must average to zero because of the random nature of the collisions
 3- I The Reality ol Molecules and Atoms 125

throughout the suspending fluid. The force Fco |

drops out of the equality at this point;

however, the mechanism for Brownian motion is still present in one of the other
remaining terms. Note that the second contribution on the left is twice the kinetic
energy of the particle for one degree of freedom. We recall that the average of this
energy is given by \k B T, where T is the temperature of the suspending fluid. Thus,
when we introduce

dx
m\—\ ) =k HD T J

dt

for the average of the term in question, we find that thermal-equilibrium aspects of
the problem are still securely in place. The averaging procedure is finally performed
as follows:

m d2 (i d \ I I dx \
2
\ m dg fi
X
-
+ " + = T
2^ 2 7<*T\"U)I -27, -2 S k"
'
(3 - 6)

where the final equation is written with the shorthand notation

d
t<0 -«<*•>

Note that m and /? are common to all particles and therefore act as constants when
the averages are taken.
Wedraw our main conclusion from this differential equation for g(t) by passing
immediately to a certain limiting case. The phenomenon of Brownian motion becomes
more and more pronounced for diminishing values of the mass of the suspended
particle, so that Equation (3-6) describes the situation of interest in the m — > limit.

The dg/dt term then drops out of the equation, and so the solution for g( t ) assumes
the simple limiting form

d 2k R T

We take (x
2
) = 0at< = and obtain the t dependence of the Brownian fluctuation
by integrating Equation (3-7):

T T
<*
2
>=^=T^ 2k B kR
(3-8)

using Equation (3-2) at the last step. We obtain the final formula

RT
<*
2 = 1 (3- 9
> a, IT
S m]aN
>

when we introduce the relation

R
k B=

to eliminate Boltzmann's constant in terms of the universal gas constant R and

Avogadro's number.
saw that his result for (x 2 ) could be applied in a suitably designed study
Einstein
of Brownian motion to make an accurate determination of Avogadro's number N^.
126 Introduction to the Atom

This remarkable deduction was the basis for a series of experiments undertaken by
J. B. Perrin in 1908. Perrin's measurements of NA were reasonably close to the current
value

NA = 6.0221367 X 10
23
molecules/mole.

It soon became clear that all sorts of different determinations of N 4

were in essential
agreement. The fact that a consensus prevailed among many types of measurement
constituted a strong case for the existence of molecules and atoms as real constituents
of matter.

Example

Brownian motion can be investigated with the aid of a microscope, a stopwatch,

and a fluid containing very small spheres of the same known size. An estimate of
the expected fluctuation serves to illustrate the ideas. Let the suspending fluid be
water at room temperature (17°C), and suppose that spheres of 1 /xm radius are
~
observed for 1 min. We take 17 = 10
2
poise = 10
3
N s/m
•
2
for the viscosity
of water and consult Equation (3-8) to obtain

X 10-'23
k B Tl (1.38 J/K)(300K)(60s)
<*
2
>
= 26.4 X 10" 12 m
3vTT)a 3t7(10"
3
N s/m
•
2
)(l0"
6
m)

Equation (3-4) then gives the rms displacement as

x rms = 5.13 X 10~ 6 m,

or approximately 5 /xm after 1 min.

3-2 The Electron

The atom was believed to have an internal charged structure even before the real
existence of atoms could be firmly ascertained. Several pieces of evidence supported
this belief. Faraday's electrolysis experiments detected the presence of charged atomic
particles, or ions, in solutions. Radiation from atoms suggested the influence of some
kind of oscillating charge inside the atomic system. Radioactivity demonstrated the
ability of some atoms to change certain aspects of their internal composition. These
indications of structure were already in evidence before 1900. At the end of the 19th
century the electron was finally identified as a universal charged constituent that
appeared in the construction of all atoms.
Electrons were discovered in electrical discharges in gases at low pressure. These
phenomena were observed in the application of a potential difference to gaseous
systems containing electrons, ions, and neutral atoms. The electrons in a discharge
tube could be accelerated by an applied voltage to produce a beam of cathode rays, so
called because the negative charges moved in the applied field toward the anode and
appeared to originate at the cathode. The beam particles were known to have
negative charge because the deflection of the beam by transverse magnetic and
electric fields could be detected and correlated with the sign of the charge. The
identity of the particles was established by Thomson in 1897, in an experiment
designed to measure the charge-to-mass ratio e/m of the cathode rays.
 3-2 The Electron 127

Figure 3-1

Thomson's cathode ray tube. Electrons are accelerated from the cathode to the anode and are
collimated by the slit to produce a beam. The electrons are deflected by the transverse field
applied to the beam on its way toward the phosphorescent screen.

Cathode

Screen

A sketch of Thomson's cathode ray tube is shown in Figure 3-1. Let us recall the

familiar details of the classic e/m experiment by referring to Figure 3-2, where we
describe the path of a negative charge —e in a transverse electric field. We regard the
strength E of the deflecting field as known, given a plate separation d and an applied
voltage <£>:

E=

The velocity in the x direction is equal to the speed v of the particle as it enters the
field, while the acceleration in the y direction is equal to eE/m since eE is the
magnitude of the force on the mass m. If we let the particle traverse the field in time t

we get

x = vt

for the distance across the field and

1 eE 5
E e
(3-10)
2 m 2 m \

for the vertical deflection of the beam as it leaves the field. The speed v is determined
by a separate procedure at another stage of the experiment, where a magnetic field of
strength B is also applied in a direction perpendicular to both v and E. The desired
configuration of v, E, and B is such that the electric and magnetic forces cancel, so

Figure 3-2

Electron deflection in an electric field.

+ +

O^ E
~
128 Introduction to the Atom

that the particle moves through the fields undeflected. We tune the B field to ensure
the equality of forces,

eE = evB,

and use this condition to obtain the velocity

(3-1D
.-f
Equations (3-10) and (3-11) are then combined to produce a formula for the ratio e/m
in terms of measurable quantities.
Thomson's determination of e/m for the electron gave a value that was rather
different from the current figure

—
m
= 1.7588196 X 10" C/kg.
r

His result was significant nevertheless, because the order of magnitude was too large to
be interpretable in terms of ions (given what was known at the time about ionic
charges and masses) and because the value did not vary appreciably when different
gases and cathodes were used in the tube. It was clear that he had discovered a unique
particle of smallmass whose occurrence was common to atoms of all species.
Since the cathode rays in Thomson's discharge tube were electrons with negative
charge, it would follow that ions with positive charge should also be detected drifting
through the gas in the opposite direction. These ions were in fact observed in a similar
kind of tube in which the cathode was perforated to allow the reverse flow of particles
with positive charge. Thomson called the particles positive rays. Rutherford proposed
that the most elementary ions should be those obtained from hydrogen atoms, and he
gave these the name protons. An e/m experiment of the Thomson type would find all

such atomic ions to have charge-to-mass ratios thousands of times smaller than the
value of e/m e .

Another experiment was needed in order to determine the quantities e and m e

separately. The magnitude of the electron charge was measured next by Millikan in a
series of studies beginning in 1906.

The famous Millikan oil-drop experiment is like its partner, the Thomson e/m
experiment, to the extent that both employ concepts from classical physics and both
produce information for the modern era. A sketch of Millikan's device in Figure 3-3
shows an oil drop of mass M
suspended in air in an electric field E between a pair of
charged metal plates. We let the selected drop have a net positive charge q, and we
express the charge as n multiples of the electron charge unit e. A microscope is used to
observe the and fall of the drop through a fixed fiducial region as indicated in the
rise

figure. The forces on the drop are the weight Mg, the Stokes-law force Bv due to the
viscosity of air, and the electric force neE. We assume that the motion in the fiducial
region occurs at terminal velocity for all observations of rise and fall. The forces acting
on the drop are therefore in equilibrium so that the drop moves with constant speed v.
The procedural aspects of the experiment are described in the figure. First, we
examine the fall of the drop with the electric field turned off. The figure tells us that
 32 The Electron 129

Figure 3-3

Schematic plan of Millikan's oil-drop

experiment. A droplet of mass M and charge
q is allowed to rise and fall in air between a
pair of charged plates. The forces are in
equilibrium, so the motion is at terminal

velocity, in the fiducial region labeled by the

vertical distance y. The drop falls with E
turned off in time and rises with E turned
l
()

on in time t. The damping force due to the

viscosity of air acts upward on the falling
drop and downward on the rising drop.

1 i

M k

E y
q = ne

Fall Rise

neE
P»o = PTn

pv =
j8f
'Mg Mg^

the equilibrium of forces is expressed as

y
(3-12)

where t is the measured fall time. Next, we measure the rise time t with the electric
field turned on. The figure shows the equilibrium condition to be

y
—
neE = Mg + ft

i i

= h — + -

where Equation (3-12) is used to get the final expression. We then alter the charge on
the drop by exposing the air gap to a burst of x rays. The ionizing radiation changes
the charge multiple from n to ri and introduces a new measured rise time t'. The
previous equation changes accordingly into the new form

( 1 1

n'eE = (3y

The desired formula for the analysis of the experiment is obtained by subtracting the
130 Introduction to the Atom

last two results and solving for the difference in charge:

(3-13)

We insert data into this formula for a series of repeated trials, corresponding to a
variety of integer differences n' — n, and thus deduce the value of e from the resulting
survey.
The results of a Millikan oil-drop experiment and a Thomson e/m experiment can
be combined to determine the mass of the electron. More current experimental
methods are also available in which greater accuracy is achieved in the measurement
of e and m r The values quoted for these basic parameters
. of the first known
elementary particle are

e = 1.60217733 X 1(T
19
C and m =
t
9.1093897 X 1(T 3 kg. '

The fundamental constant e is especially significant in view of the quantization of

charge since the parameter gives the basic charge unit for all known observable
particles.

Example

Let us get a feeling for the numbers involved in a Thomson e/m experiment by
choosing the following reasonable values for the measurements. Take the
deflection plates in Figure 3-1 to be at 200 volts with a 2 cm separation so that
the deflecting electric field is

200 V
= 10
4
V/m.
d 0.02 m

Let the length of the plates be 4 cm and let the vertical deflection of the electron
beam be 0.5 cm so that the speed of the electrons is found from Equation (3-10)
to be

4 1/2
Eex
2
10 V/m)(l.60 X 10- ,9 C)(0.04mV
2 my 2(9.11 X 10" 31 kg)(0.005m)
7
1.68 X 10 m/s.

The strength required for the B field may then be computed from Equation
(3-11):

E 4
V/m
B=-
v 1.68
10

X
— m/s
10
=
7
= 5.95x10 4
T,

corresponding to an approximate 6 G field.

Example

We need to know B in order to use Equation (3-13) in a Millikan oil-drop

experiment, and Equation (3-2) reminds us that B depends on the droplet radius
a as well as the viscosity ?] for air. Let us eliminate a in terms of other known or
 3-3 The Huclear Model of the Mom 131

measurable quantities, since the radius of the drop is not measured directly. We
assume a spherical drop and express the mass as

M= 3
f77a p,

where p is the density of oil. We then recall the formula for /? from Equation
(3-2) and rewrite Equation (3-12) in the form

y 4
677170 — = —irapg.
t 3

This equality allows us to calculate a from other more accessible parameters.

3-3 The Nuclear Model of the Atom

By 1900 it was generally acknowledged that Thomson's electrons were present

somewhere within the structure of every atom. The distribution of the internal charge
of the atom was the next important issue to be decided. The decade leading up to
1910 was a time for atomic models to be put forward so that specific predictions could
be tested by experiment. Classical principles were the only tools available for the
construction of these models. Quantum physics was still an infant science and would
have nothing to contribute until the classical picture of the atom had had a chance to
develop.
It was accepted that an atom was electrically neutral in its normal state and that
the removal of electrons from an atom resulted in the formation of a positively
charged ion. Every atom of a particular element was supposed to contain a certain
number of electrons to form a full complement. The chemical significance of this
number, the atomic number Z, did not emerge until somewhat later. It was clear,
however, that a given atom with Z electrons could be neutral only if the atom also
contained positively charged matter with a total charge equal to + Ze. Furthermore, it

was known that the electron was thousands of times less massive than any atom, and
so it was obvious that almost all the mass of the atom had to reside in its positive
component.
Thomson visualized the distribution of charge and mass in the atom by means of a
spherical model, shown in Figure 3-4, in which the whole atomic volume was supposed
to filled by the massive positive component, except for isolated locations throughout
be
the volume where the Z electrons were to be found. He assumed that the electrons
were subject to the Coulomb force and were able to move about positions of

Figure 3-4 Figure 3-5

Thomson's model of the atom. Rutherford's model of the atom.

132 Introduction to the Atom

equilibrium in their charged environment. The emission of light by atoms was

believed to be attributable to the motion of the atomic electrons. Thomson hoped that
the observed frequencies of the light could be explained in terms of the periodic
motion of his embedded electrons. This enterprise was doomed to fail, as the Thomson
atom was soon proved by experiment to be incorrect.
Direct tests of Thomson's model were carried out by means of scattering experi-
ments. The observed process involved the elastic collision of charged particles, in
which the Coulomb force between the incident and target particles could act as a
probe for the distribution of charge in the structure of the bombarded particle. The
scattering of a beam of particles was analyzed to determine the dependence on the
scattering angle and the beam energy. This information provided a test for specific
predictions of the atomic model as well as a method for exploring unknown features of
the scattering process. The first investigations of the structure of the atom by these
techniques were Rutherford's a-particle scattering experiments.
Rutherford made his monumental contribution to the understanding of the atom as
an outgrowth of his studies of the radioactive elements. These earlier experiments
enabled him to explain radioactivity as a characteristic change of properties in certain
atoms, accompanied by the observed emission of very energetic particles. Greater
achievements followed, as Rutherford undertook the exploration of the atom using a
particles to probe the unknown structure. He had discovered a particles in the
radioactive disintegrations of certain heavy elements and identified the radiated
particles to be fully ionized helium atoms stripped of their two electrons. Rutherford
realized that these energetic positive particles could be used for probing matter on an
atomic scale. In 1909 he and his associate H. W. Geiger began their program of
a-particle scattering experiments. These studies refuted Thomson's model and estab-
lished an entirely different picture for the structure of the atom.
Rutherford proposed the nuclear model of the atom in 1911. He assumed that the
massive positive component of the atom was contained within a very small region of
the atomic volume, called the atomic nucleus. A scale of size could be determined for
the nucleus by a-particle scattering. The atomic
radius was known to be of order
10
m m, and was found from experiment to be of order 10 14 m.
the nuclear radius
The atomic electrons were supposed to move in stable orbits around the nucleus, as in
Figure 3-5. Thus, the Rutherford atom resembled the solar system, with the force of
gravity replaced by the force of Coulomb attraction and with the system reduced to
atomic scale.
The famous Rutherford scattering experiment was laid out according to the plan
described in Figure 3-6. A radioactive source provided a particles with energies of

Figure 3-6

Design of the Rutherford a-particle scattering experiment.

Detector

_^£&Y*^
€) Foil

Collimator
 3-3 The Nuclear Mode! of the Atom 133

several MeV, and a collimated beam of these particles was directed at a very thin foil

target. Scattered particles were detected on a scintillating screen that responded to the
arrival of a charged particle by emitting a burst of visible light. The distribution of the

scattered a particles was studied at fixed energy as a function of the scattering angle 6
shown in the figure. Different beam energies were obtained by using various a sources,
and different atoms were probed by substituting foils of various metals. The purposes
of the experiment were to determine the angular behavior of the scattering and to
compare observations with predictions in order to assess the validity of the atomic
model. Two qualitative conclusions were immediately drawn from the first experi-
ments. Almost all the incident particles were transmitted through the foil with very
little deflection, and a very few incident particles (approximately 1 were
in 10,000)

scattered backward into detectors located on the beam side of the foil. These amazing
observations were explainable only in terms of a nuclear model of the atom.
Let us see how this evidence bears on the choice of atomic models. We note first

that it is safe to ignore atomic electrons when a particles are incident on atoms
because the electrons are too light to cause appreciable scattering of the much heavier
a particles. The observed scattering is therefore attributable to the interaction between
the a particle and the massive positive component of the atom. This interaction is

expected to have very different effects in the two models of Thomson and Rutherford.
The Thomson atom has a very diffuse distribution of positive charge, and so the
encounters between beam particles and target particles are likely to result in only
small random deflections as the a particles pass through the target atom. Rutherford's
model of the atom adopts a very concentrated distribution of positive charge so that
most of the atom presents itself as empty space to an incident particle. Therefore, most
encounters with the Rutherford atom also result in small deflections, except for the rare
occasion when the encounter between the a particle and the target nucleus is nearly
head-on. These collisions produce the rare backward scattering events that distinguish
the Rutherford atom from the Thomson atom. Thus, the qualitative predictions of the
nuclear model are borne out in the experimental results, while the diffuse model is
decisively refuted. The details of the Rutherford scattering problem are analyzed
quantitatively in Section 3-4.

Example

We discover other failures of Thomson's model when we look at the Thomson

version of the hydrogen atom. Let the single electron of hydrogen be embedded
in a spherical medium having radius R, constant charge density p, and total
charge e. These quantities are connected by the formula for the charge

e = 3
\<irR p.

The force on the embedded electron depends on the charge ^mr zp, the portion of
the total positive charge that lies within the electron's instantaneous location at
radius r. Gauss' law determines this force to be

F= --—fa r
>
9
)L 1 t
477e r

where the sign denotes an attractive force directed toward the center of the
134 Introduction to the Atom

atom. We note that F is proportional to the variable r as in the case of the

restoring force of a spring:

F= -kr
with effective "spring constant"

1 1

k = npe
477£ 3 47re R3
We therefore expect the electron to execute simple harmonic motion with
frequency
1 Fk
f
=

and we also expect the oscillating electron to emit radiation of the same
frequency. These considerations have nothing to do with reality, as the spectrum
of hydrogen has infinitely many frequencies and indicates a very different
physical picture.

3-4 Rutherford Scattering

We treat the scattering of a particles by atomic nuclei as a two-stage problem in

classical physics. The first part of the analysis pertains to the orbit of a single charged
particle under the influence of a force of Coulomb repulsion. The second part deals
with the behavior of a beam of particles whose individual orbits are known from the
first stage of the problem. We cast the treatment in terms of a particle beam because
our ultimate concern is the experimental question of detecting many scattered particles
as the beam impinges on many target nuclei. This approach leads us to the important
concept of the scattering cross section.
Nonrelativistic principles are more than adequate here since the kinetic energy of
the a particles much smaller than their rest energy. We begin by studying the
is

scattering of a single beam particle by a single target nucleus, with charges denoted by
ze and Ze, respectively. (Since a particles are ionized He atoms, the corresponding
charge index is =
Both charges are positive and so the
actually given by z 2.)

scattering is caused by a repulsive Coulomb interaction. We let refer to the mass of M

the incident particle, and we take the mass of the target particle to be much larger
than M. We do this for simplicity so that we can assume a picture in which the target
charge Ze remains fixed at the origin and does not recoil during the collision. (The
no-recoil assumption does not reduce the generality of our treatment. We comment
briefly on this point again in Section 3-6.)
Let us look first at the special case of a head-on collision. The repulsive nature of
the force entails a distance of closest approach that varies with the kinetic energy of the
incident beam. We call this useful parameter D and define the distance with the aid of
Figure 3-7. The total energy of the system is beam kinetic energy K when
equal to the
the particle is at the extreme position r = oo and is equal to the Coulomb potential
energy when the particle is at the turning position r = D. We use conservation of
energy to equate the two quantities,

1 Zze'
K=
47re D
 3-4 Rutherford Scattering 135

Figure 3-7

Distance of closest approach in a head-on collision.

,, 1 ,, -j Infinite mass

Te ©—
r = oo r =
^D (l)ze

and then solve for the distance to the turning point:

2
1 Zze 2 1 2 Zze
D= = -. (3-14)
47T£ K 477£ My

The speed of the particle at r = oo appears in the final step through the nonrelativis-
tic expression for the beam kinetic energy, K= t,Mv".
We turn next to the general case of a non-head-on collision and consider the orbit
of a scattered particle. Figure 3-8 shows how the incident particle is initially directed

along an incoming asymptote that passes the target at a distance b, known as the
impact parameter. This distance is an important property of the orbit in any scattering
problem. The conservation laws of energy and angular momentum require the
outgoing asymptote to have the same impact parameter. It then follows that the orbit
is symmetrical about a bisector that divides the motion into incoming and outgoing
parts. These features of the orbit are indicated in the figure. We note that the orbit in
Figure 3-8 can be identified with the path of the scattered particle in Figure 3-6 and
that the same scattering angle 6 appears in both figures. Our main objective in this part
of the analysis is to establish the relation between the impact parameter and the
scattering angle.
Angular momentum plays a major role in the solution for the orbit. A conservation
law holds for the angular momentum vector L = r X p because the Coulomb force is

a central force that imposes no torque on the particle. Therefore, the direction of L
is fixed (so that the orbit lies in a plane containing the origin), and the magnitude of L

Figure 3-8

Orbit of a charged particle in a non-head-on collision. The orbit has incoming and outgoing
asymptotes parametrized by the impact parameter b and the scattering angle 6. The polar
coordinates r and cp denote the instantaneous orbit variables for the scattered particle.
 , .

136 Introduction to the Atom

is a constant of the motion given by

L = Mvb. (3-15)

We by examining the orbit at either of its two extremes. Let us also

find this result
specify the conserved quantity L at an arbitrary point along the orbit, where the orbit
variables are denoted by the polar coordinates r and qp as in Figure 3-8. The
component of velocity perpendicular to the position vector r is given by rdcp/dt, and
so the constant of the motion takes the form

L = Mr 2 —
dcp

dt
(3-16)

We can use this formula immediately to eliminate the unknown variable (p from the
dynamics.
The desired solution for the orbit is supposed to be an expression for r as a function
of <p. Newton's law leads us instead to a description in terms of the joint variables r(t)
and <p(t), where the time serves as a variable parameter. We recall that the radial

acceleration contains the expected contribution from the / dependence of r as well as

the familiar centripetal term:

d 2r I d<p\ 2

a '~ ~
2
It '

' \~dij

We then introduce the Coulomb force on the mass M and write the radial equation of
motion as
2
d2r I d<p\ 2
1 Zze
M 2
(3-17)
dt '
\ dt 47re r

This expression can be manipulated into a more recognizable differential equation by

making the change of variable

(3-18)
u

and by using the relation

dtp L L
It ' 'Ah
2 " ~M

from Equation (3-16). The following maneuvers are executed to change the variables
from r(t) and <p(0 to the single unknown function u(cp):

du d<p du L L du
dr dr 1

2
dtp
—
M u
)

d.

~M dtp
'

It tin d<p dt U

and

d2r d L d2u L

V —M
I dip
-1 u
2

Hi2 '
d<p{ dt -J ~~M
 34 Rutherford Scattering 137

We insert these results in Equation (3-17) and find

L2 d2u 1 L2 Zze
2

M 2
u
2
.

M" dq>- u M~ 477C

We then divide by the factor —L"u'/M and obtain a differential equation for u((p):

—+„=--
d^u Zze 2 M
— . (3-19)
d<p~ 477-f L"

The constant on the right can be rewritten in a more compact form by consulting
Equations (3-14) and (3-15) and by using K = 2
-.Mv :

Zze
2
M M D
477e L 2 ~ M 2 2
v b
2 " 2b
2
'

These steps lead us to the final version of the equation for w(<p):

d2u D
x
2
+„=-_.
+ = u (3-20)
d<p 2b

Our equation of motion is now in a form amenable to immediate solution.

The second-order differential equation for u((p) is solved by noting that — D/2b" is

a particular solution of the given equation and by observing that sin qp and cos cp are
independent solutions of the corresponding homogeneous equation. We obtain the
general solution of Equation (3-20) by combining these special solutions as

u((jp) = A sin(p + B cos (p — —D - . (3-21)

2b"

This result is subject to two conditions, both imposed at r = oo on the incoming portion
of the orbit in Figure 3-8. We specify the first requirement,

u = when <p = 0, (3-22)

to designate the initial position on the orbit. We also observe that the incoming
velocity is

dr L du

dt M dq)

and so we specify the second requirement,

—=—
duMv
d(pL
= -
1

b
when <p = 0, (3-23)

to designate the initial derivative on the orbit. The resulting orbit equation for u(<p)
 . .

138 Introduction to the Atom

must therefore be given by the solution

- = -sin? -
1
—Dj(l - cos<p), (3-24)
r lb

because this expression has the structure of Equation (3-21) and obeys the conditions
in Equations (3-22) and (3-23).
Our final result contains more information than we need, since the orbit equation
describes every point on the orbit of the particle. In a typical experiment, a beam of
particles is directed onto a target and the scattered particles are counted in a detector
far from the target, so that only the asymptotes of the orbit are under actual
observation. We recall from Figure 3-8 that these asymptotes are described by the
orbit parameters b and 8, and we note that the orbit equation tells us how b and 8 are
related. When the orbit reaches the outgoing asymptote we have

r = 00 and <p = ir — 8

Equation (3-24) becomes

1 / D
= -sinC (1
y
+ cos0)
b\ 2b
8 8 D J
= —
1

b\
/

2 sin — cos— —
2 2
—
2b
2cos —
2

for these values of the orbit variables. The desired relation between the scattering
angle and the impact parameter follows as a direct result:

sin—
8

2
— —D cos— =0
2b
8

2
=> cot—
82b
—
2D = (3-25)

We need only this much information from the orbit equation to continue our analysis
of Rutherford scattering.
The first stage of the problem has been devoted to the collision of a single beam
particle with a single target nucleus. Let us now turn to the second stage and consider
the observational aspects of the scattering process. An experiment usually involves a
beam many incident
carrying particles with the same kinetic energy and a target
sample containing many nuclei of the same species. We identify two factors pertaining
to these considerations — the number of nuclear scatterers exposed to the beam and the
rate of incidence of particles onto the target. The factors are deduced from properties
of the beam and the target as follows. First, introduce p and m as the density and
atomic mass per mole of target material, and assemble these quantities along with
Avogadro's number to form the number of nuclei per unit volume

Then, let 8 be the thickness of the sample and suppose that a surface area A of target

is exposed to the beam. The number n of nuclear scatterers is evidently equal to the
product of these accumulated factors:

pN,
A 8. (3-26)
m
 3-4 Rutherford Scattering 139

The beam intensity I is defined as the number of incident particles crossing unit area
per unit time, and so the number N ofbeam particles incident on the target per unit
time is written as

NQ = I A . (3-27)

The parameters introduced in the last two equations are controlled in the design of the

experiment.
The scattered particles are counted by a detector system that has an axis of
symmetry along the direction of the incident beam. Figure 3-6 shows a small detector
at the scattering angle 0, where scattered particles are collected at a rate that does not
vary with the placement of the detector around the beam axis. All particles scattered
at angle 6 are therefore detected uniformly over a thin ring of detectors around this
axis. Let the ring lie on a sphere of radius R centered at the target, and let the small

width of the ring be specified by means of the angular increment dd as indicated in

the figure. The element of area swept out by this detector is given by

dS= (2irR sin 8 )(RdO).

The distance R from the target to the detector has no significance in the interpretation

of the scattering distribution. Only the direction of the scattered particles is of interest,
and so the factor R~ is removed from the element of area to define

dtt = —
dS

R
= 2
2ir sin0 d6 (3-28)

as the more effective measure of the scope of the detector. This definition introduces
the element of solid angle as a mathematical quantity whose span takes in all directions
that emanate from the and pass through the detector at the angle 6. The solid
target
angle dQ, is dimensionless and is conventionally given in steradians, by analogy with
the angle d6 given in radians.
We let dN denote the number of particles scattered per unit time into a given solid
angle dSl. This measurable quantity is proportional to dQ, so that the ratio dN/dQ, is

independent of the size of the subtended solid angle. The resulting number of counts
per unit time per unit solid angle varies with the scattering angle 6 and the beam
energy A'. Hence, the ratio dN/d& gives the angular distribution of scattered particles,
the main object of immediate experimental interest.
Particles are scattered into dQ, by every target nucleus exposed to the beam. Figure
3-9 shows how a single orbit is influenced by one nucleus and how the behavior of all
such orbits is incorporated in the treatment of a beam containing many particles.
According whose impact parameter lies between b
to the figure, every incident particle
and b + db follows an orbit whose scattering angle lies between and 6 + dO. Axial
symmetry applies to this statement, so that all particles entering the axially symmetric
element of beam area 2mbdb are scattered by the one nucleus into the indicated
element of solid angle dQ,. We implement this essential observation with the aid of
quantities introduced in the preceding paragraphs. The number of particles incident
per unit time is given by the product of factors

2-rrbdbI ,

and the number scattered into dSl per unit time by a single nucleus is given by the
140 Introduction to the Atom

Figure 3-9

Ingredients in the definition of the scattering cross section. All particles passing through the
beam area 2mbdb are scattered into the solid angle dSl. The relation between the scattering
angle 9 and the impact parameter b is such that dO and db have opposite sign.

db

Nucleus

Element of beam area

2nbdb
Element of solid angle
dCi~ 2n-sin 6 dfl| |

ratio

dN
n

These two expressions are set equal, and the beam intensity I is divided out, in order
to define the scattering cross section

dN
da = — =
riL,
2irbdb. (3-29)

The identification of this new quantity is the final goal in our analysis of the scattering
problem.
Let us examine the significance of the cross section by recalling Equation (3-27)
and rewriting Equation (3-29) as

dN I n

K T
da

We can interpret this expression for da in the following words:

# particles scattered into dQ/t\me / # target nuclei encountered

# particles incident/time area of beam

()!

# scattered into d£l by one nucleus/* incident per unit area of beam.

The interpretation tells us that the cross section has units of area; this simple
observation leads us to the basic meaning of the new concept. The cross section da
represents the effective target area presented to a single beam particle by a single
target nucleus for scattering into the solid angle d£l. Cross sections are given in barns,
 3-4 Rutherford Scattering 141

where the unit of area is defined as

" 28
1 barn = 10 nr.

A direct proportionality always holds between da and dQ so that the ratio da/dQ, is a
more basic quantity. This ratio is called the differential scattering cross section, a function
of scattering angle and beam energy, given in units of barns/steradian (b/st). The
definition of da/dQ, removes the last experimentally controlled ingredient from the
measured counting rate dN. Removal of the factors n, I and dil begins in Equation ,

(3-29) and serves to divide out those elements of dN that are peculiar to a particular
experiment. The result da/dSl is left behind as a measure of the basic two-body
process that is common to all such experiments.
The definition of the cross section holds generally for any kind of elastic scattering.
We apply the concept directly to the Rutherford scattering problem by recalling the
relation between b and 6 for Coulomb scattering and by implementing Equation
(3-29). We relate db and dO by differentiating Equation (3-25) to find

6 dO
-esc 2 = —2
2 2/) db. (3-30)
v '

We note that db and dO are of opposite sign. This property of the orbits can be seen in
Figure 3-9, where the repulsive nature of the Coulomb force causes particles incident
with impact parameters larger than b to be scattered through angles smaller than 6.

We insert Equations (3-25) and (3-30) into Equation (3-29) and obtain the formula
for the cross section in the following series of steps:

D I D ,0 dd\
da = 2tt — cot— esc
2

2 2\ 2 2 2/
77 sin(0/2)cos(0/2)
4 V ;
4 sin (0/2)
it smd\d6\
2
4
8 sin (0/2)

D 2
d&
4
' (3-31)
16 sin (0/2)

The solid angle expression in Equation (3-28) is used at the final step. We can then
recall Equation (3-14) and immediately write the differential cross section as

da D 2

4
(3-32)
dQ 16 sin (0/2)

These two famous formulas describe the angle and energy dependence of the
Rutherford cross section.
Geiger and Marsden completed a very painstaking series of a-par-
his student E.
ticle scattering experiments in 1913. They made observations over an angular range
from 5° to 150° and counted more than 10 5 scattered particles on a zinc sulfide
scintillating screen. Their results verified the predictions of the Rutherford formula as
142 Introduction to the Atom

4
to the csc ( 0/2) behavior in the scattering angle and the \/K l dependence in the
a-particle energy. They also established that the scattering was proportional to the foil
thickness 8 and the square of the atomic mass of the foil material. This last

observation was taken as an indicator of the expected dependence on the nuclear

charge factor Z, since the atomic mass was believed to be proportional to Z. These
findings confirmed Rutherford's theory in all predictable respects.
The nuclear model of the atom treats the nucleus as a core of small but finite size,

while the analysis of Rutherford scattering assumes a point-like nucleus. The deriva-
tion is valid nevertheless, provided the a particle does not have enough energy to
penetrate the volume of the nucleus. The two spherical particles interact through the
Coulomb force between point charges until the beam energy becomes sufficiently large
to cause penetration, whereupon the strong nuclear force takes over and becomes the
dominant effect. These considerations suggest a way of using Rutherford scattering to
deduce the radius R of a particular nucleus. We employ the energy-dependent
distance D for reference and compare results from experiment for the differential cross
section with predictions from Equation (3-32) for da/d^l. Agreement implies the
validity of the Coulomb scattering assumption, and this in turn implies that D exceeds
R. We then reduce D by increasing K until we observe the onset of a departure from
the Coulomb prediction. The corresponding critical value of D provides a determina-
tion of the nuclear radius R.
Let us finally be reminded that the derivation of the Rutherford formula is based
entirely on classical principles. It is reasonable to wonder whether Newtonian mechan-
ics should apply on a scale as small as the atomic nucleus, particularly because we
anticipate the influence of quantum principles in atomic and subatomic systems. It
happens that a proper quantum mechanical treatment of nonrelativistic Coulomb
scattering leads to exactly the same conclusion as the classical Rutherford derivation.

Example

Let us generalize the notion of solid angle by identifying an element of area dS

on a sphere of radius R according to the construction in Figure 3-10. In this case
we define dS with two variables, a polar angle 6 and an azimuthal angle <£,

unlike the ring of surface area used to derive Equation (3-28). The figure gives

the area as

dS = R 2 sm6d9d<t>,

Figure 3-10

Element of surface area dS on a sphere of

radius R. The element of solid angle is defined
by dQ, = dS/R 2

R sin $d<t>
 3-4 Rutherford Scattering 143

and so the definition of the solid angle becomes

dS
d&= —j = smO d6d<j>.
R2

We obtain the total solid angle by integrating dSl over the range of the angular
coordinates, < < it and < <p < 2ir. Let us first integrate over <f>
to get

2
dtt= CsinOde f "d<t> = flirsinedd,
f J J J
•'all Q,

a result to be compared with the expression for the ring in Equation (3-28). The
final integration over 6 gives

77

f dti = 2mfsinede = -277COS0 = 47T,

•'all U J

so that the total solid angle is equal to 47: steradians.

Example

Rutherford scattering by choosing calculations based on

is illustrated nicely
beam of 5.30 MeV a
typical a-particle scattering experiments. Let us consider a
particles incident on a gold foil as a good example of such an experiment. We
begin by computing the following useful combination of constants that recurs
continually in atomic physics:

e
2
(8.988 X 10
9
N m2/C 2 )(l.602
•
x 10 19
C)~
l9
477e 1.602 X 10" J/eV
= 1.440 X 10" 9 eV •
m.

We then take z = 2 and Z= 79 and consult Equation (3-14) to find the

distance of closest approach:

e
2
Zz (1.44 X 10" 9 eV- m)(79)(2)
D= = ,
6
' =4.29X 10
14
m.
4t7e A 5.30 x 10 eV

The density and molar mass of gold are

p = 19.3 X 10
3
kg/m 3 and m= 197 g/mole;

therefore, the number of Au nuclei per unit volume is given by

pNA (19.3 X 10
3
kg/m 3 )(6.02 X 10
23
nuclei/mole)

m 0.197 kg/mole

= 5.90 X 10
28
nuclei/m 3 .
144 introduction to the Atom

Let the foil thickness be 2.10 X 10" 7 m and suppose that 10 4 a particles strike
the foil per second. Equation (3-26) determines the number of target nuclei
encountered per unit beam area as

—
PNA
m
8 = (5.90 X 10
28
nuclei/m 3 )(2.10 X 10~ m)
7

22
1.24 X 10 nuclei/m 2 .

Our main objective is to predict the total number AA' of a particles scattered
backward by the foil per second. The number dN scattered per second into solid
angle dO, is found by using the known Rutherford cross section in conjunction
with Equations (3-27) and (3-29):

dN = nln da = -N da.

The desired quantity AN is obtained by integrating this equality over the

backward solid angle, where the scattering angle ranges over 77/2 < B < 77. We
express the total number of backscattered a particles relative to the number
incident by recalling Equations (3-28) and (3-31) to get

AA n do r ir n D 2
2k sin 8 40
dtt =
-ibackward ^o "" K/'iA
/)
J-n 16 sin
4
(0/2)
'

il

The integration proceeds as follows

j it/2 sin
sin0 dd
An
r
I
cos{8/2)d6
t— —— = 477
f
/
J j 1/2
2du
3~
8 77
477.
(0/2) K/2 sin-*(^/2) U 2u'

using the change of variable ;/ = sin(^/2). Our final result for the fraction of

incident a particles scattered backward is

AA n D<
477" -(1.24 X 10 22 m" 2 )(4.29 X 10" 14
m) = 1.79 X 10" 5 .

A ()
A ()
16

We then find

AA = (10
4
a particles/s)(l.79 XlO~ 5 = 0.179a )
particles/s

for the predicted number of counts per second. This value is comparable with
the observations of Geiger and Marsden.

3-5 The Quantum Picture of the Atom

Rutherford's planetary model assigned the nucleus and the electrons to separate inner
and outer regions of the atom. The success of the model inspired Bohr to imagine a
corresponding separation of physical domains of influence, in which the electrons in
 3-5 The Quantum Picture of the Atom 145

the atom accounted for the chemical properties of the element while the nucleus was
responsible for any radioactive behavior. This picture began to reveal the correlation
between the number of electrons in the atom and the location of the element in the
periodic table. The meaning of the atomic number finally emerged after the construc-
tion of Bohr's model of the atom.
The Rutherford atom evolved into the Bohr atom in 1913. The evolution of models
resulted from the introduction by Bohr of certain quantum concepts in a new
treatment of matter. This revolutionary contribution to the understanding of the atom
initiated the next phase in the development of the quantum theory.
Indications of quantum behavior in matter had been accumulating long before the
time of Rutherford and Bohr. The best source of evidence was to be found in the
spectra of light emitted by atoms. Investigations of atomic spectra began early in
the 19th century, after J. von Fraunhofer discovered the existence of dark lines in the
spectrum of light from the Sun. These studies gathered impetus when it was learned
that heated samples of the elements emitted light whose wavelengths appeared in
discrete patterns. Kirchhoff showed was characteristic of
that each observed spectrum
the chemical species contained in the source of the light. Atomic spectroscopy came
into being, as investigators proceeded to measure and tabulate the wavelengths of
light in the spectra of the various elements. Cesium and rubidium were among the
new elements identified with the aid of these spectroscopic methods. Atomic spectra
gave precise experimental information in the form of a unique signature for each of
the atoms. These measurements offered access to the internal structure of the atoms,
once it was learned how the different spectra were to be decoded. The appropriate
decoding principles were eventually established in the quantum theory of atoms.
Most of our knowledge of the properties of matter has come to us through some
branch of spectroscopy. The oldest spectroscopic techniques employ optical types of
apparatus. We can describe how these instruments are used to observe emission and
absorption spectra by referring to the schematic illustrations in Figure 3-11. An emission
spectrum is the result of the spectral analysis of light emitted by atoms in a gas
discharge tube. The atoms in the tube gain energy in collisions with electrons and lose
energy by emitting radiation. The figure shows how the light from the tube is directed
through a slit to a prism spectrometer and is dispersed by the prism into different
component wavelengths. We see the resulting emission spectrum as a series of discrete
spectral lines, corresponding to different colored images of the slit. The positions of the
lines in the image plane of the spectrometer are unique to the atoms in the discharge
tube. An absorption spectrum is formed when atoms are used to remove certain
wavelengths from the familiar continuous spectrum of white light. The figure shows
how the light from an incandescent source is directed through a slit and is then
allowed to traverse a gas-filled cell before entering the prism spectrometer. The
dispersion of the prism produces a continuous spectrum of colors due to the thermal
radiation from the source, accompanied by a superimposed set of discrete dark lines
associated with the intervening gas. These dark images of the slit are just like the dark
lines seen by Fraunhofer in his observations of the solar spectrum. The absence of lines
is attributed to the absorption of specific wavelengths of the incident white light by the
atoms in the gas. Thus, the absent wavelengths are unique characteristics of the atoms
in the gas-filled cell. We find that the bright lines in the emission spectrum occur in
the same positions as the dark lines in the absorption spectrum if the gas in the
discharge tube is the same as the gas in the absorption cell.
Optical line spectra were collected, without further analysis or interpretation,
through much of the 19th century. The first successful empirical understanding of the
 1 —
146 Introduction to the Atom

Figure 3-1

Spectrometers for the study of emission spectra and absorption spectra. Focusing lenses are also
needed as additional elements in the two optical systems.
Bright spectral lines

Gas discharge tube

Dark spectral lines

Continuous spectrum

Incandescent source of white light

observed lines was achieved in 1885 in the case of hydrogen, the simplest atom. J. J.
Balmer showed that the visible spectrum of wavelengths in hydrogen could be fitted

by the formula

X = (3645.6 X 10" 10
m)— w = 3,4,.. (3-33)

His fit applied to the so-called Balmer series of lines in which the integers n = 3,4,...
corresponded to the spectral labels a,/?,... shown in Figure 3-12. The measured
 3-5 The Quantum Picture of the Atom 147

Figure 3-1

Balmer series of spectral lines in hydrogen. The observed wavelengths are in good agreement
with the indicated predictions from Bohr's model for the hydrogen atom.
— o <T> O CTi

id id oo
ro
o
-:
jo
ir> 00 g>

Nanometers

Series limit

Wavelength

wavelengths diminished in separation according to the given dependence on n and

converged to a series limit for the limiting value of the index n —> oo. Immediate steps
were taken to extend the fitting procedure to other series of lines in other elements.
The hydrogen result was generalized in 1890 by J. R. Rydberg, who rewrote Balmer's
prescription in the form

1 / 1 1

- =R,

and then interpreted his expression as a special case of the following more general
formula for hydrogen:

1 1 1

= Rr (3-34)

Rydberg's analysis reproduced the Balmer series for n' — 2, with a value for the
constant given by RH = 10972160 m '. This parameter has since been determined
with very great accuracy and has been named the Rydberg constant. Rydberg's
formula defined a double sequence in the two integers n and n', and so the
introduction of the new index ri raised the possibility of other as-yet unknown series of

hydrogen lines. The predicted «' = 3

series was discovered in the infrared region of

the spectrum by L. C. H. F. Paschen in 1908, and the fundamental n = series was 1

found in the ultraviolet region by T. Lyman in 1914. Other series were also revealed
later on, in the infrared spectrum and beyond. Thus, the empirical results of Balmer
and Rydberg successfully broke the spectral code for hydrogen and remained to be
properly explained in some more comprehensive theoretical framework.
It had become apparent by 1913 that the planetary model of the atom was in

urgent need of reevaluation. The atomic electrons were supposed to be moving in

orbits around the nucleus under the influence of the attractive Coulomb force.
Unfortunately, these orbiting charged particles were expected to emit classical radia-
tion as a result of their accelerated motion. The laws of classical electrodynamics
implied that the atomic system should undergo a radiative loss of energy, which would
cause the atom to be intrinsically unstable. Hence, the electron orbits would steadily
shrink in size and rapidly collapse onto the nucleus, while the radiation was being
emitted with continuously increasing frequency. This fatal flaw in the classical picture
threatened to undermine Rutherford's model of the atom. It turned out that the
picture was fundamentally flawed by the adoption of the classical point of view.
148 Introduction to the Atom

Bohr solved the problem of radiative instability by making a break with the
principles of classical physics. His proposed solution contributed another new idea to
the developing quantum theory, in the same spirit as the radical proposals put
forward by Planck and Einstein in the previous decade. Bohr believed in the nuclear
model of the atom but questioned whether classical electrodynamics should always
apply to the behavior of electrons. He began to entertain the possibility of a quantum
approach, thinking that Planck's constant h should have a natural place in the
description of the atom. He noted that the classical picture could not explain why all

atoms of a given species should have similar electron orbits, by the

as suggested
evidence obtained from atomic spectra. He also noted that Rutherford's model gave
no indication of the size of the atom, and he regarded this failure as a basic weakness
of the classical approach. was clear that a natural measure of length could not be
It

constructed from the physical constants of the problem unless h was included along
with the classical parameters. It was observed that the product of factors
2 2
(47TE /e )(h /m e ) gave an appropriate unit of length and an approximate order of
magnitude to use as a practical scale of length for the atom.
Bohr speculated that electron motion in the atom should have quantized properties
in which only certain states of orbital motion were allowed. He proposed a new

quantum condition by requiring discrete values of the energy for these allowed states.
He could then show that his requirement was consistent with the observation of
discrete wavelengths in the spectra of atoms. His idea was partially inspired by the
form of the Rydberg formula, Equation (3-34), in which the wavelengths in hydrogen
were expressed as differences of pairs of discrete-valued quantities.
The Bohr theory of the atom is based on the following two postulates. First, the

electrons in the atom may exist in a discrete set of stationary states of definite energy,
defined so that radiation is not emitted by an atom in such a state. Second, the atom
may undergo a nonclassical transition from one of these allowed states to another and
thereby emit or absorb a single quantum of electromagnetic radiation. The new
concept of quantization of energy in matter originates in these two propositions.
We can interpret Bohr's postulates with the aid of the illustrations in Figure 3-13.
The proposed set of stationary states is represented by a sequence of discrete levels of
increasing energy in an energylevel diagram. We can then exhibit upward or downward

transitionson such a diagram as quantum jumps between pairs of states with

quantized energies E n and E n An upward transition occurs with the absorption of a
,.

Figure 3-13

Energy level diagram for the stationary states of an atom. A transition to a state of higher or
lower energy is accompanied by the absorption or emission of a photon.

En'
 3-6 The Bohr Model of the One-Electron Atom 149

photon, and a downward transition occurs with the emission of a photon. In either
casewe obtain Bohr's formula for the energy of the photon by applying conservation
of energy in the overall system of atom plus radiation to get

hv = j = En - E„,. (3-35)

Only quantized energies appear in this expression, and so only certain allowed
wavelengths are predicted for the emission and absorption of radiation.
Bohr's postulated energy levels gave a natural explanation for the discrete char-
acteristics of atomic line spectra. His theory also offered a solution-by-decree for the
problem of atomic instability. The existence of stationary states and quantized energy
levels was simply declared, while the applicability of classical radiation theory was
simply denied, and no theoretical arguments were put forward to support these new
ideas. This treatment of the atom associated the phenomenon of atomic radiation with
the possibility of transitions between pairs of states, and not with the acceleration of
electrons in orbits. Consequently, radiation frequencies were not to be identified with
frequencies of orbital electron motion in the atom. We should note that the theory did
not say what the atom was doing while the radiative transition was in progress. This
classical question was at variance with the new quantum point of view and was not
supposed to have an immediate answer.

Example

We have suggested the following natural scale of length in the context of Bohr's
quantum treatment of the atom:

2 2 2

—
477e
t,
2
h
= —
4ire
7,
2
(he)
7T
2
= -,
(l240eV-nm)
r, b z r
= 2.090 nm.
e m r
e m t
c ( 1 .440 eV •
nm)(0.51 10 X 10 eV)

(Note that the electron mass is given in MeV/t 2 units in this calculation.) We
learn in Section 3-6 how a scale of length proportional to the suggested quantity
arises naturally in Bohr's model of the hydrogen atom.

3-6 The Bohr Model of the One-Electron Atom

Bohr's theory of the atom proposed the existence of stationary states; however, the
procedures needed to determine these states were not discovered until 1925. In the
meantime it was possible to make progress in quantum physics by judiciously blending
new quantum ideas with certain concepts carried over from classical mechanics.
Bohr
took such an approach in hydrogen atom.
1913 to develop his model of the
Our treatment of Bohr's model generalizes the case of hydrogen to cover any
system of two bodies bound together by Coulomb attraction. We let the charges and
masses be denoted as — e and m for the one particle, and +Ze and for the other. M
Our intention is to construct a model ofan arbitrary bound system containing one
electron, and so we intend to set m = m, and let M
range over a variety of choices.
The special case of the hydrogen atom is obtained if we take Z= 1 and choose M to
be the proton mass M p
.Arbitrary one-electron ions can also be described by choosing
150 Introduction to the Atom

Figure 3-14

Circular motion of two charged particles with

center of mass at rest.

other integer values of and other larger values of M. We restrict the discussion to
Z
and we take account of the motion of both particles. Of
particles in circular orbits,
course, we expect that the mass M
should remain at rest in the limit M/m -» oo, and
we know that the hydrogen atom is close to this limiting situation since the proton-to-
electron mass ratio is quite large:

M =
— P
1836.
m.

The small effect of a finite nuclear mass M is detectable in atoms and should
therefore be retained as a small correction. Allowance should be made for finite M
also as a matter of principle, because the properties of two masses in motion are of
some interest and because the effects can be incorporated without difficulty.
We take the center of mass of the two-body system to be at rest at the origin and
define position vectors for the two particles as in Figure 3-14. Our first objective is to
reduce the two-body problem to an equivalent one-body description in terms of a
single vector variable given by the relative coordinate

r = r, — r2 . (3-36)

The origin is located at the center of mass so that r, and r9 must satisfy the relation

wr, + Mx 2 = 0. (3-37)

We can solve this pair of equations to obtain the particle position vectors

=
M =
m
r, r and r2 r (3-38)
M+m M+m
 3-6 The Bohr Model of the One-Electron Atom 151

and then differentiate with respect to / to find the corresponding velocities

=
M =
m
v and v,2 v. (3-39)
v,1
M+m M+m
The relative velocity is defined as

v = -
dx
(3.40)

in passing from Equations (3-38) to (3-39).

We achieve our objective by casting the various two-body dynamical quantities in
terms of the relative coordinate and velocity. Equations (3-39) are used to reexpress
the total kinetic energy:

m M
— m I M \
2
M m
— /mM \
2 1

K= ,2
-vi + i _,.2
v
2
= - I \

v
d
?
+
.

M + m] v- i

M+m
\ 2
»
2 2 2\M+ mj 2 \ 2

Thus, we obtain the desired one-body expression for K in the form

K= l
2
fiir (3-41)

by defining the reduced mass of the two-body system as

mM
M=T7—
M+m (3-42)

This mass parameter also appears along with the relative dynamical variables in the
formula for the angular momentum vector L. The special problem at hand involves
two particles in circular orbits. We recall that the total angular momentum is a
constant of the motion because the force of Coulomb attraction is a central force. The
magnitude of the conserved total angular momentum is found by using Equations
(3-38)and (3-39) to get

L = mv.r, + Mv2 r = m\
(MY 2

vr + M\
i m \ 2

vr
11 "
\ M+m J \ M + mj
or

L = fivr (3-43)

as the final result. We can put the equations to further use and express the centripetal
force on each particle as

mv
F=— r,
2

L = ^
Mv 2
r
2
=
txv
^—
r
2

(3-44)

The potential energy for the system of two charges is given by the Coulomb formula

1 Ze 2
V=-~477£ r
.
(3-45)
152 Introduction to the Atom

We note that this final dynamical quantity is expressed directly in terms of the relative
variable r.

These results illustrate the consequences of a general theorem in mechanics. Every

two-body central-force problem is reducible to an equivalent one-body problem in
which the single particle is described by reduced mass ju, position vector r. and
potential energy V{r). In this instance the function V(r) is provided by the attractive
Coulomb potential energy given in Equation (3-45).
We observe in passing that the theorem has immediate implications in the analysis
of Rutherford scattering. The theorem allows us to replace the problem of scattering
from a target of finite mass by the problem of reduced-mass scattering from a fixed
repulsive center of force. Recall that the original treatment has been given in Section
3-4 in terms of scattering from a fixed target of infinite mass. We can apply the
theorem and adapt our fixed-target results simply by substituting the reduced mass for
the mass of the scattered particle. Our conclusions are then interpreted to hold in a
reference frame where the center of mass is at rest.
Let us return to the bound system in Figure 3-14 and evaluate the total energy of
the two charged particles. We need not include the rest energies of the particles in
these nonrelativistic considerations. The constituents of systems in atomic physics
always maintain and so the corresponding rest energies
their identities, act as constant
quantities in all such problems. With this understanding we express the total energy as

E= K+ V
and consult Equations (3-41) and (3-45) to find

1 1 Ze 2
E= —jxv
2
— .

2 47re r

The centripetal force in Equation (3-44) is identified with the attractive Coulomb
force as
v 2
—
ixv

r
2

= 7
4we
1
1 Ze

r
f. (3-46)

and so the total energy takes the form

1 \ Ze 2 1 Ze 2
E= --1
/
= . (3-47)
\ 2 / 477-e r 2 497C r

Note that E is a negative quantity because V is negative and because the potential
energy is larger in magnitude than the kinetic energy whenever the energies pertain to

a bound system.
The construction of the model has adhered to classical principles up to this point.
Bohr followed these steps to the same point and then introduced a new quantum
hypothesis in order to produce the desired stationary states. He argued that the orbits
in the atom should be discrete and that an allowed classical orbit was one whose
angular momentum L was an integral multiple of the quantum unit h/ltr. This basic
quantity was recognized to have dimensions of angular momentum and was found to
recur sufficiently often in quantum physics to warrant a special symbol, given by the
current value

h= —
h

2m
= 1
34
05457266 X 1(T J J •
s.
 3-6 The Bohr Model ol the One-Electron Atom 153

Bohr's quantum condition restricted the angular momentum of the atomic system to
quantized units of h according to the formula

L = tivr = nh. (3-48)

Thus, an integer n was introduced as a quantum number through the new concept of
quantization of angular momentum. Justification for this ad hoc rule came later in another
of the early developments in the old quantum theory.
We adopt Bohr's hypothesis and combine the classical expression in Equation
(3-46) with the quantum statement in Equation (3-48) to find

2*2
l
n h
v r
2 2 =
2
477€ () p /i

This remarkable result implies that the orbit radius r is a discrete quantity whose
allowed values are given in terms of fundamental constants as

n Arre^h'
r. = (3-49)
Z e~n

We rewrite this formula in the more compact form

n m
a (3-50)
Z JU.

by defining

477£ /r
3-51

The important parameter a is approximately equal to 0.05 nm and is called the Bohr
radius. This quantity appears in Equation (3-50) as a unit of length and serves as a
useful scale of length for all problems in atomic physics.
The energies in the various orbits must be quantized since the orbit radii are
discrete. The prediction of these energies is the main conclusion of the Bohr model.
We obtain discrete values for E by inserting Equation (3-49) into Equation (3-47):

1
Ze Ze Z e
2
u
E=-~
1 1

2 4i7e r
n
2 477e n 47re /r

The result can be written compactly as

En = ~ — ~E
m
n~
(3-52)
e

by introducing the Rydberg energy unit

£o= tM TT7- (3-53)

154 Introduction to the Atom

The parameter E is significant because it sets the scale for the energy levels in the
hydrogen atom. We note that E can also be expressed as

2 2
a2
E° =
9
I
1 /

\
i
47TE —r e

nc
\

J
m '
c
'

2 =
v^
2
f2 ' (3 " 54)

where the final form involves the electron rest energy along with a new constant given
by
2
e
a=-47re -. (3-55)
«c

This last combination of fundamental physical parameters is a dimensionless quantity-

known as the fine structure constant. Both E and a are known very accurately from
experiment:

E = 13.6056981 eV
and
1

- = 137.0359895.
a

We note that a also makes its appearance in Equation (3-51):

4ire () hc h 1 h
an = (3-56)

This observation tells us that the Bohr radius and the electron's Compton wavelength
h/m c are related by
t
a rather interesting numerical quantity.
The reduced mass jx appears explicitly in the formulas for r
n
and E n
via the ratio
\i./m t . This reduced-mass correction factor is very close to unity in almost all

applications. We recall that m stands for m e

in every case, and so Equation (3-42)
gives the factor as

H M
m t
M+m e

Thus, the ratio is equal to }f^ when M is set equal to M p

in the case of hydrogen and
is even closer to unity when M refers to other nuclear masses. The correction is

interesting nonetheless, because it is possible to observe the resulting small differences

in energy levels for atoms whose nuclei have the same value of Z but different values
of M. These nuclear species are called and the correction arising from the
isotopes,

factor [J./m r is called the isotope effect. The ratio n/m e becomes rather different from
unity in the special case of positronium. We describe this electron-positron bound
system in the context of the Bohr model by taking Z = 1 and setting = m e to get M
jj./m r = £. Obviously, the reduced-mass correction has an appreciable effect on the
energy levels in this instance.
Bohr's quantization condition for angular momentum has led us to discrete orbits
and quantized The corresponding allowed states of motion in
energies. the Bohr atom
are labeled by means of the single quantum number n, whose origin is traced directly
 3-6 The Bohr Model of the One-Electron Atom 155

to Equation (3-48). Quantization of energy presents the main results of the model in

terms of a system of energy levels ordered according to the values of n. Let us choose
Z= 1 Equation (3-52) so that we can visualize these results for the special case of
in
the hydrogen atom. The energy level diagram is shown in Figure 3-15 to consist of an
infinite sequence of values of E n as n ranges over all positive integers. The system has

a lowest level called the ground state in which

n = l and E =
x
E = - 13.60 eV.

Equation (3-50) gives the radius for the first (and smallest) Bohr orbit as

r, = — a .

Larger values of n refer to excited states with higher energies and greater orbit radii.
The limit n —» oo defines a special limiting state of the system in which

'oo = °° and E°c = °-

The two bound particles have infinite separation and no motion in this state.

Therefore, the limiting value of n corresponds to the configuration of the atom at the
threshold for ionization. The system is allowed to have all values of the energy above
this threshold; however, the associated states pertain to unbound particles in relative
motion and are not interpreted as states of the atom. The ionization energy is de-
termined by the difference in energy between the ground state and the ionization
threshold:

£, = —
m.
E = 13.60 eV.

This quantity represents the minimum energy that the atom must absorb in its natural
state in order to release the bound electron. The absorbed energy can be supplied in
the form of an incident photon, and so the ionization energy is equal to the work
function for the photoelectric effect in hydrogen.
Bohr's model is not based on a consistent set of quantum principles and does not
qualify as a genuine quantum theory. The model is remarkable nevertheless, because
the results provide correct predictions for the energy levels of the one-electron atom.
We can verify these predictions by examining the wavelengths in the emission
spectrum of the atom. Let us consider a radiative transition from an excited initial
state i to a less energetic final state /, and let us label the states by the quantum
numbers n t
and n
f
as in Figure 3-16. We adapt Bohr's basic formula in Equation
(3-35) to the notation in the figure by writing

he
hv = — = E,- E
f
. (3-57)

The energies are obtained from Equation (3-52), and so the wavelengths are given by
>56 Introduction to the Atom

Figure 3-15 Figure 3-16

Energy levels in Bohr's model of the hydrogen Emission of a photon in the transition ;

atom.The energies are given in terms of the E,

quantum number n by the formula E = rl

hi
-(EQ /n 2 )(fi/m t ),
where E is the Rydberg
energy unit and fi/m the reduced-mass
correction factor.
r
is
V

-0.85

-1.51

-340

13.60-

the expression

1 E-E f
1
H E 1 1

Z
X he \"i n
l

We can rewrite this result as

-=z>-r\-- -
I fx / 1 1

(3-58)
2
lit

if we define

a" mc
/?- = (3-59)
he 2 h

using Equation (3-54). The result in Equation (3-58) is essentially the same as

Rydberg's empirical formula. We car. make the identification with Equation (3-34) if
 3-6 The Bohr Model of the One-Electron Atom 157

we take Z= 1 and set

*H = R,

Thus, it is evident that the energy levels are correctly given by Bohr's model since the
predicted transitions are in agreement with the observed spectral lines. Both RH and
R are known with very great accuracy from experiment; the latter constant has the
current quoted value

R^ = 10973731.534 m-'.

(The notation can be understood with the aid of Equation (3-42); R^ denotes the
Rydberg constant for an atom with a nucleus of infinite mass M.)
Equation (3-58) describes families of spectral lines according to the various series

predicted by Rydberg. These series are classified by systematically choosing various

fixed values for the final quantum number n,. The choice n , = 1 designates the
Lyman series of transitions to the ground state from all initial levels in the range
n > 2.
t
Likewise, transitions to the n , = 2 state from n > 3 :
give the Balmer series,
transitions to the n
f
= 3 state from n i
> 4 give the Paschen series, and so on. The
scheme of transitions is shown for hydrogen in Figure 3-17. It is interesting to note

Figure 3-17

Transitions in the emission spectrum of hydrogen. The spectral lines are grouped into series
according to values of the quantum number. The final state of the atom has n = 1 in the
final

Lyman series, n = 2 in the Balmer series, n = 3 in the Paschen series, and so on.

• • •

-0.85 -4
-1.51
r 3
f Paschen

-3.40
Balmer

En (eV)

A, n

-1360
Lyman
158 Introduction to the Atom

Figure 3-18

Effect of atomic recoil in the emission of a

photon.

that Bohr's theoretical model predates the discovery of all the known series in
hydrogen except for the Balmer lines in the visible spectrum and the Paschen lines in

the infrared.
Let us now go back and look more critically at Figure 3-16 and Equation (3-57). If

we visualize the radiative transition according to the before-and-after picture in

Figure 3-18, we see that the recoil motion of the atom has been left out of the analysis.
Let us investigate this oversight and show that no serious error has been made in our
prediction of the photon energy hv. If the atom
assumed to be initially at rest, as in
is

the figure, then conservation of momentum requires the photon and the final atom to
have opposite momenta of the same magnitude p. We denote the energy difference
between the two states of the atom as

A£ = E, - E .

This quantity is the same as the difference in rest energies for the initial and final

atom. The kinetic energy of the recoiling atom given by p 2 /2M, where is the
is M
mass of the atom. Conservation of energy provides the determining relation among all
these quantities:

E =
i
hv + Ef +—.
P
(3-60)

Since the momentum of the photon is

hv
P= — c
,

Equation (3-60) becomes a quadratic equation in the unknown energy hv:

(hv)
hv + E,+
J/
2Mc 2
or

(hvf + 2Mc 2 {hv) - 2Mc LE =

2
0.

The desired solution for the photon energy is given by the root

2A£\'/ 2
hv = -Mc 2 + i/M'-V + 2Mc 2 lE = Mc 2 1 +
Mc'
 36 The Bohr Model of the One-Electron Atom 159

The ratio 2 b.E/Mc 2 is certainly very small if the energy difference A£ is in the

eV-to-keV range. Therefore, an expansion can be used to get a very good approxima-
tion:

1 2A£ 1 / 2A£ HE
hv = Mc' 1 + A£j 1
5 |. (3-61
2 Mc' 8 Mc 2Mc 2 '

This result tells us that Equation (3-57) should be modified by the correction factor
(1 — AE/2Mc 2 ). We conclude that the effect of recoil is negligible whenever the
transition energy A£ much smaller
is than the rest energy of the radiating system.
The Bohr model was a success for its time even though its limitations were
immediately apparent. The treatment could be generalized to noncircular orbits, but
the model could not be extended successfully to atoms with more than one electron.
The wavelengths in the spectrum of the hydrogen-like atoms could be calculated, but
the intensities of the spectral lines could not be predicted. All these deficiencies were to
be remedied in a more comprehensive quantum theory of matter and radiation.
Bohr regarded his model as a tentative blend of classical and quantum ideas. He
recognized that classical physics must have its domain of applicability, and he
believed that results from the quantum theory should merge into a correspondence
with classical predictions. Bohr formulated a correspondence principle in which he argued
that nature should be described by a quantum theory and that the theory should have
a limiting regime in which classical physics would become valid. He treated Planck's
constant as a small unique unit of quantum behavior and proposed that quantum
mechanics should somehow reduce to classical mechanics in the limit h —» 0. Oper-
ational evidence for such a limit was supposed to appear as a convergence of energy
levels for large values of the relevant quantum number.
Bohr's model of the one-electron atom provides an excellent illustration of the
correspondence principle in operation. Let us return to Equation (3-57) and consider
the frequency of the radiation emitted in the transition i -» /. Equations (3-52) and
(3-54) are used to obtain

E, — E (
a En j 1 1 \ a a 2 m,c 2 I 1 1
'
J_ >y 2 I — 72 '

2 2 2
h m e
h I n , n
J
m e
2h I nj n

We are interested in the specially defined photon frequency vn that corresponds to

transitions between the adjacent levels n = n and n = n — 1, and we are particularly
t
f
concerned with the behavior of vn for large n:

ju, a2 m tc 2 ( 1 \ Z~ /i cx~m ( c'

v. = Z2
m. 2h \{n-\\ n

Let us also consider the electron orbit frequency, given by

Z
— (XC Z72 m Z7 2 am/
2 2
r _ _
v„
= n
= _ _ J
jit ac e
c ju

2 3
m m
2irrn
2tt—
n

Z
— ju
e
a
n e
2tt h
! 66 Introduction to the Atom

To obtain this expression we recall Equations (3-50) and (3-56) for the quantized
radius r
n , and we employ a result for the quantized orbit speed vn as quoted in
also
Problem 14 at the end of the chapter. We know that the frequency of the emitted
radiation is not to be identified directly with the frequency of orbital motion.
However, these last two calculations demonstrate the equality of vn and fn for large
values of n, as required by Bohr's correspondence principle.

Example

Let us begin by computing all the basic parameters that arise in the Bohr model.
Equation (3-55) gives the fine structure constant:

2
e 2t7 1 .440 eV •
nm 1

-277 =
47T£ he 1240 eV •
nm 137.0

Equation (3-56) gives the Bohr radius in terms of the electron's Compton
wavelength:

1 h 137.0
a = = (0.002427 nm) = 0.05292 nm.
2770! m t
C 277

Equation (3-54) gives the Rydberg energy unit:

6
0.5110 X 10 eV
£,, = — mc 2 = 13.61 eV.
2(137.0)'

Equation (3-59) gives the Rydberg constant in the limit of an infinite-mass

nucleus:

D _
Ea _ 13.61 eV
00
= 0.01098 nm"
he 1240 eV •
nm

Next, let us choose Z= 1 and calculate the energy levels of hydrogen using
Equation (3-52). The reduced-mass correction for hydrogen can almost be
ignored since

/' M. 1836

/// M p
+ m t
1837

The four lowest levels have energies

"
1 13.60"
1836 1/4 3.40
(13.61 eV) eV,
1837 1/9 1.51

1/16 0.85

as indicated in the energy level diagrams in Figures 3-15 and 3-17. Finally, let

us look at some of the hydrogen wavelengths that follow from Equation (3-58).
 3-7 Characteristic X Rays 161

The formula for A becomes

HW 1837
I 1

il"
( 1 91.12 nm
1836(0.01098 nm ')
1/»J
- l/»?
I"/

In the Lyman series we have w, = 1, and so we find the longest wavelength for
n, = 2:
'

91.12 nm 4
A = = -(91.12 nm) = 121.5 nm,
1-1/4 3

an ultraviolet spectral line. In the Balmer series we have n^ — 2, and so we

obtain the following values for A:

36/5 656.1 3

16/3 486.0 1

100/21 (91.12 nm) = 433.9 for n, = 5

9/2 410.0 6
196/45 396.9 7

These wavelengths are included in Figure 3-12; all the values are within 0.1 nm
of Balmer's original results. Each series has a shortest wavelength that occurs in
the series limit as n —* oo. The limiting wavelengths are found from the formula
l

tn.

In the Lyman series

nf = 1 gives A, 91.1 nm,

and in the Balmer series

n, = 2 gives A. 364.5 nm.

All higher series have their limits in the infrared and beyond.

3-7 Characteristic X Rays

The spectrum of radiation from an x-ray tube is generally composed of continuous

and discrete wavelengths. A sketch of these superimposed distributions has been
furnished in Figure 2-16, and an explanation for the continuous component has been
given in Section 2-6. The discrete lines in the spectrum are peculiar to the specific
metal in the target of the x-ray tube. These characteristic x rays represent a signature
whose interpretation is similar to that of the optical spectrum for the given element.
162 Introduction to the Atom

Figure 3-19

Orbital model of atomic excitation and x-ray emission. The collision of a beam electron with a
target atom causes an atomic electron to be ejected from an inner orbit. Another atomic
electron fills the vacancy and emits an x-ray photon. The deexcitation of the atom occurs
between Bohr orbits labeled by the quantum numbers n, and n,.

The discrete lines are attributed in either case to transitions between the quantized
energy levels of the corresponding atom. X-ray spectral lines have short wavelengths
of nanometer order, and so x-ray transition energies of the atom are in the keV range.
The large energy required to excite the atom is supplied by the electron beam in the
high-voltage tube.
X-ray spectra are associated with complex atoms containing many electrons. This
apparent complication is not a serious analytical problem in the x-ray regime because

the excitation energies are large enough to remove a tightly bound electron from an
inner orbit near the nucleus of the atom. In this circumstance the emitted x rays are
assumed to result from the transitions of a single electron while the other electrons are
regarded as spectators. Bohr's simple one-electron model is quite useful in such a
situation.
Let us visualize the x-ray excitation and emission processes in the many-electron
atom in terms of a system of independent electrons occupying a collection of
quantized Bohr orbits. We label the orbits allowed for an individual electron by the
familiar quantum number n, in the manner of Equations (3-50) and (3-52). The
electrons of interest for the excitation process are those in the innermost orbits of the
atom, the so-called K and L orbits, where the quantum numbers are given by n = 1

and n — 2. Figure 3-19 shows a model of such a system in which the atomic electrons
are distributed over several different Bohr orbits.The figure also shows how the atom
becomes excited when the system an energetic incident electron, as in the
is struck by
bombardment of the target in an x-ray tube. The collision causes the ejection of an
atomic electron from an inner orbit, so that the resulting singly ionized atom is left in
a highly excited state. The ion deexcites when one of the remaining electrons makes a
quantum jump from an outer orbit and fills the vacancy left by the ejected electron.
This transition to a state of lower energy is accompanied by the emission of an x-ray
photon. The so-called K and L series of x rays result from all such electron transitions
to the n = 1 and n = 2 inner orbits of the ion.
The first comprehensive study of characteristic x rays was conducted in 1913 by
H. G. J. Moseley. He investigated the K and L spectra of many of the elements in the
 3-7 Characteristic X Rays 163

periodic table and based his analysis on the notion of inner-electron behavior in the
context of Bohr's model. His survey of the elements revealed regularities that finally
established the identity between the nuclear charge index Z and the atomic number
in the periodic table.
Let us show how the Bohr model is applied in Moseley's analysis. We refer to
Figure 3-19 and consider the transition of orbits for a single electron from n t
to n,,
ignoring all the other electrons in the atom. The wavelength of the emitted x ray is

given in terms of these quantum numbers by Equation (3-58). Let us rewrite the
formula as an expression for the x-ray frequency:

v = Zl {
/
cR\- -
i
—M . (3-62)

This equation contains an all-purpose Rydberg constant R representing the quantity

x ^oo/
l
m an d an
e
effective charge parameter Z eff
replacing the usual nuclear charge
index Z. We use Z eff
instead of Z because the electron in transition sees a nuclear
charge smaller than Ze as the other atomic electrons tend to screen the nucleus from
view. Even an inner electron in transition experiences this screening effect to some
degree. We can build the effect into the model if we introduce an empirical screening
constant z , and set

Z =
eli
Z-zf . (3-63)

It is expected that z, should increase with the final quantum number n,, because the
final orbit radius increases with n, and because the screening is greater for transitions
to larger final orbits. Equation (3-63) may be inserted into Equation (3-62), and the
result can be rearranged to give the following expression for Z eff
:

fv
z =
!
cR(\/n)- \/n])

This formula becomes

fv
with n { = 2,3,..., (3-64)
/<tf(l - 1/n?)

when we choose rtj = 1 and consider the K series, and becomes

fv
Z= zL +^= with n,.= 3,4,5,..., 3-65)

when we choose «y = 2 and consider the L series. The equations predict linear
relations between Z and f ,
with different intercepts and different sets of slopes in
each series. The K series includes Ka and K^ spectral lines for n t
= 2 and 3, with
corresponding slopes ^4/3cR and ^9/8cR . The L series includes La , Lp, and L y
lines for n t
= 3, 4, and 5, with slopes ^36/5 cR ^16/3^, and fQQ/2UR. Figure ,

3-20 shows sets of Z versus f graphs whose linear behavior reflects these predictions
of the one-electron model.
164 Introduction to the Atom

Figure 3-20

Graphs of the atomic number versus the square root of the x-ray frequency in Moseley's
analysis.

Aii

Moscley was able to change targets in his x-ray tube and observe the frequencies of
x rays for more than 40 of the elements between aluminum and gold in the periodic
table. He treated Z as the atomic number for each of the elements in the table and
plotted his observations in the manner of Figure 3-20. The linear relations between Z
and yp were confirmed, and the slopes were found to agree with expectations from the
Bohr model for the K a and L a lines.Approximate values were also deduced for the
intercepts of the straight lines in the two series:

= 1 and = 7.4.

Moseley's procedures resolved certain questionable assignments of elements in the

periodic table and eventually superseded methods for identifying
existing chemical
new elements. The most important work was the conclusive demonstration
result of his

that the atomic number, the nuclear charge index, and the number of electrons in the
neutral atom were all given by the same quantity Z.
Figure 3-19 can be used to describe two other related phenomena. Both of these
possible processes involve the ejection of two atomic electrons instead of the one shown
in the figure. The primary types of x-ray lines are produced in the transitions of singly
ionized atoms, as discussed above. Doubly ionized atoms can also be formed when
electrons collide with atoms in the target of an x-ray tube. The orbit structure in the
resulting ion is somewhat different from the singly ionized case, and so the radiative
transitions in this system produce x rays with correspondingly different frequencies.
These x rays appear in the spectrum as secondary satellites to the primary spectral
lines. The ejection of a second electron can also occur in an entirely different
radiationless process, first observed by P. Auger in 1925. The phenomenon, known as
the Auger effect, is initiated by the excitation of the atom to a singly ionized
configuration containing the usual sort of inner-electron vacancy. The ion does not
deexcite by photon emission, however; instead, the system spontaneously ejects
another electron and becomes a doubly ionized atom. In such a process the second
 3-8 Atomic Processes and the Excitation ot Atoms 165

electron carries away kinetic energy

K= £<" - Ef\

where the notation for the initial and final energies refers to the singly and doubly
ionized configurations. Thus, the system in the figure releases energy in the transition
n t
—*and the transition energy is immediately absorbed through an internal
n,,
conversionmechanism in which the second electron is detached and no radiation is
produced. The emission of an Auger electron is also called autoiomzation; this effect is
generally observed in competition with the emission of an x ray.

Example

Moseley's x-ray spectrum of zinc includes the wavelength A = 0.1445 nm. We

can analyze this particular line by choosing n ;
= 2 in Equation (3-64) to get

Z-z K =
(3/4)cA> V 3AA>

= 29.00.
3(1.445 X 10" 10 m)(l.097 X 10
7
m" 1

The intercept for the A' series is given empirically as zK = 1. Hence, our
calculation tells us that Z should be equal to 30, in excellent agreement with the
known atomic number of Zn.

3-8 Atomic Processes and the Excitation of Atoms

Every atomic system is represented in Bohr's theory by a set of stationary quantized

energy states. The all atoms of a given element to have the same
theory requires
ground and the same excited states, and so the basic observable properties of the
state
element must somehow reflect the energy level structure of the corresponding atom.
All sorts of atomic processes can be examined experimentally to deduce various
aspects of this structure.
The atom has been presented as a system of electron orbits in Figure 3-19. We
should regard the orbital picture as a primitive quasiclassical device and turn instead
to Bohr's discrete energy states for a proper quantum view of the atom. Let us
visualize the atomic processes in terms of this new language and look at some of the
different forms of interaction between the atom and radiation. Figure 3-21 illustrates
several of these phenomena, where each is initiated by an incident photon of energy
hv. We represent the atom by the associated set of energy levels, and we assume the
effect of atomic
recoil to be negligible in each case.
photon scattering appears in part (a) of the figure. The atom remains in its
Elastic
ground state as shown, so that the incoming and outgoing photons have the same
energy hv. No other form of interaction can occur if the wavelength of the incident
radiation is large compared to the size of the atom. The process is given the name
Rayleigh scattering in this circumstance because the results are adequately described by
Rayleigh's classical scattering theory for electromagnetic waves.
166 Introduction to the Atom

Figure 3-21

Atomic processes induced by incident

radiation.

(a) Elastic scattering

(b) Inelastic scattering

(c) Resonance radiation

(d) Fluorescence

Ik

(e) Photoelectric effect

'

(f) Compton scattering

 3-8 Atomic Processes and the Excitation of Atoms 167

The incident photonmay have an energy large enough to cause a transition of the
atom an excited state. This possibility is illustrated in part (b) of the figure. The
to
process is an example of inelastic scattering since the radiation loses energy to excite
the atom. The energy of the scattered photon is given by

hv' = hv - A£, (3-66)

where AE is the indicated excitation energy between the excited state and the ground
state. Each excited state of the system corresponds uniquely to an observable shift in
the frequency of the scattered radiation. Hence, a measurement of the shifts in
frequency constitutes a determination of the energy levels of the given scatterer. This
procedure is used extensively in molecular spectroscopy. The process is called Raman
scattering after C. V. Raman, discoverer of the effect in 1928.
The energy of the incident photon may happen to be equal to one of the excitation
energies of the atom. The fundamental absorption and emission processes of Figure
3-13 can occur in tandem at this energy, as indicated in part (c) of the figure. Elastic
scattering is the result since the initial and final photons have the same energy hv. The
phenomenon is called resonance radiation because the effect is similar to the resonant
behavior of a driven harmonic oscillator. The photon energy matches the energy
required to excite the atom, and so the cross section for elastic photon scattering is

enhanced, indicating a large response of the atom to the incident radiation.

The figure shows a situation in part ( d ) where enough energy is absorbed to excite
the atom into one of the higher-energy states. Deexcitation may then proceed in a
sequence of downward transitions, accompanied by a cascade of emitted photons. This
phenomenon is known as fluorescence. A common example occurs when an atom
absorbs ultraviolet light and deexcites by emitting several wavelengths of visible light.
The figure illustrates the effect by showing two fluorescent photons hv[ and hv. ,,
1
along
with the inelastically scattered photon hv'
Part (e) presents the photoelectric effect as the absorption of an incident photon
accompanied by the ejection of a bound electron. Note that the excitation produces an
ionized system with energy A' above the ionization level. Note also that the work
function of the atom is equal to the difference in energy between the ionization state
and the ground state.

Part shows the Compton effect for the atom in its ground state. The energy of
( / )

the incident photon is large enough to eject a bound electron and produce outgoing
radiation of longer wavelength. The energies in the figure obey the familiar Compton
relation hv — hv' = K.
The excitation of an atom does not always have to be a radiation-induced process.
Figure 3-22 shows how an atom may gain energy and become excited in a collision
with another We
have already spoken of excitations by collision in our
particle.
remarks about the gas atoms in a discharge tube and the target atoms in an x-ray
tube. Thecolliding particle is an electron in these applications and in the two
situations shown in the figure. We let the incident electron have kinetic energy K as
indicated, and we consider two possibilities for the behavior of the atom. The recoil of
the massive atom is again assumed to have a negligible effect in each case. The upper
part of the figure shows an elastic collision, where the atom remains in its ground state
and the electron scatters without change in kinetic energy. Inelastic scattering can also
take place if the initial kinetic energy is large enough to raise the atom into an excited
state, as in the lower part of the figure. In this case the scattered electron has less
168 Introduction to the Atom

Figure 3-22

Electron- atom collisions. The scattered

electron loses kinetic energy when the atom is

excited to a higher energy state.

Elastic scattering

\ <&"
nelastic scattering

kinetic energy, by an amount equal to the excitation energy of the atom:

K' = K-AE. (3-67)

We note that Equations (3-66) and (3-67) refer to parallel processes of excitation
whose net effectson the atom are exactly the same. The excited atom may give up
energy in either case by the emission of radiation.
The first measurements of collisional excitation in atoms were made in 1914 by J.
Franck and G. L. Hertz. Their experiment studied a current of electrons in a tube
containing mercury vapor and revealed an abrupt change in the current at a certain
critical value of the applied voltage. They were able to interpret this observation as

evidence of a threshold for inelastic scattering in the collisions of electrons with

mercury atoms. The behavior of the current was an indication that electrons could
lose a discrete amount of energy and excite mercury atoms in their passage through
mercury vapor, provided the electrons were given enough energy by the accelerating
voltage. They backed up their conclusion by detecting the emission of ultraviolet light
caused by the deexcitation of the mercury excited state. The Franck-Hertz observa-
tions constituted direct and decisive confirmation of the existence of quantized energy-
levels in atoms.
Figure 3-23 shows a picture of a typical Franck-Hertz experiment. The apparatus
consists of and anode terminals. A
a mercury-vapor tube equipped with cathode, grid,
variable accelerating voltage is applied between cathode and grid, while a smaller
retarding voltage is applied between anode and grid, as indicated in the figure.
Electrons can acquire full kinetic energy K from the accelerating voltage and reach
the anode to produce a current, provided they suffer no loss of energy owing to
inelastic collisions with mercury atoms. Inelastic scattering results in a lesser electron
kinetic energy K', as described in Figure 3-22 and Equation (3-67). The retarding
voltage is large enough to turn back any inelastically scattered electrons but is not so
large as to prevent the other electrons from reaching the anode. The two possible
types of electron behavior are denoted in the figure by the labels K and K' The .
 3-8 Atomic Processes and the Excitation ol Atoms 169

Figure 3-23

Schematic apparatus and results for a Franck-Hertz experiment.

Cathode Anode

Current

4.9 V
Accelerating
voltage

anode current is observed to grow with the accelerating voltage until the correspond-
ing value of K becomes equal to the mercury excitation energy A£. An abrupt
reduction in current occurs, signaling the onset of inelastic scattering, when the
voltage reaches this critical value. The sudden drop in the observed current is

illustrated in the lower part of Figure 3-23.

Example

The critical voltage for the Franck-Hertz experiment in mercury is given as 4.9
V. The wavelength of ultraviolet light from mercury atoms in the Franck-Hertz
tube is quoted as A = 253.67 ran. Let us verify the consistency of these two
measurements. The energy of the emitted ultraviolet photon is the same as the
excitation energy £±E, so that A and A£ are related by

//,

A£ =

according to Bohr's basic formula in Equation (3-35). Inelastically scattered

electrons have kinetic energy A" = at the inelastic threshold. Hence, Equation
(3-67) relates the critical voltage to the excitation energy through the equality

A' = kE.

Thus, the corresponding threshold value of the electron kinetic energy is

he 1240eV-nm
K = 4.888 eV.
253.7 nm

The critical voltage should therefore be 4. V, in agreement with the

measured value 4.9 V.
 170 Introduction to the Atom

Figure 3-24 Figure 3-25

Three fundamental photon-atom processes in Growth and decay of populations of atoms at

which hv = AE. two energy The atoms are
levels. in a radiation
Spontaneous emission field of frequency v = (E2 - E x
)/h.
n2
2

Cu „ n i
-
(A + E

Parameter A n, "
E,

Absorption

Parameter C

Stimulated emission

Parameter B

3-9 The Laser

Let us reconsider radiative transitions of the kind described in Figure 3-21 so that we
can bring together three basic types of photon-atom interaction. The processes of
interest are illustrated diagrammatically in Figure 3-24. In each case we are concerned
with a photon energy hv that exactly matches the difference in energy AE between
two particular atomic energy levels. We continue our practice of the previous section
and assume that the photon momentum is not large enough to cause appreciable
recoil of the atom.
The first two diagrams in the figure show the related phenomena of spontaneous
emission and absorption. We let A* denote an excited state of atom A and express the
two processes as
A* -> A + y and y + A -» A*.

We should recognize these familiar excitation properties of the atom by recalling

Figure 3-13. The third diagram introduces the new process of stimulated emission,

y + A*^>A + y + y,

in which an incident photon induces the deexcitation of the atom from a higher to a
lower energy state. The transition mechanism is such that the triggering photon and

the emitted photon occur together, necessarily with the same frequency v, in the final
 3-9 The Laser 171

state of the system. This simultaneous emergence of two photons from the deexcited
atom corresponds to the emission of coherent radiation in which two electromagnetic
waves are generated in phase. The emitted photons can proceed to interact in like

manner throughout a medium containing other excited atoms of the same species A.
The resulting cascade of photon-doubling transitions over the whole medium produces
monochromatic waves with the property of coherence on a large scale. This amplifica-
tion effect is the basis for the operation of the laser. (The word laser is an acronym for
light amplification by the stimulated emission of radiation.)

To generate the cascade of photons it is necessary that atoms in the medium be

found in the appropriate excited state. Since the atoms are in the presence of radiation
with frequency v, the population of the two relevant energy levels is governed by the
dynamical interplay of all three processes in Figure 3-24. The original analysis of
these interconnected phenomena can be traced to investigations by Einstein dating
back to 1917. We can discuss the problem with the aid of Figure 3-25 by considering
two energy levels E and E2 with time-dependent populations of atoms given by «,
t

and n 2 The population of the upper level is fed by the absorption process, so that the
.

indicated growth rate Cu v n is proportional to the number of atoms in the lower level
x

as well as the spectral energy density of radiation at frequency v. The population of

the lower level grows by spontaneous emission at a rate An 2 and also grows by
stimulated emission at a rate Bu^n.,. Both of these growth rates are proportional to the
number of atoms in the upper level. Notice, however, that the rate of spontaneous
emission does not contain the spectral energy density as a factor because this effect

does not involve the presence of the stimulating radiation field. The three constants A,
B, and C are called Einstein coefficients. These quantities have been assigned in Figure
3-24 to parameterize the quantum behavior of the three basic processes.
The growth and decay of the upper and lower populations are evidently described
by the rate equations

dn 2
= Cu„n - (A + Bu v )n 2
l
(3-68a)
~d~t

and
'hi
]

= {A + Bu v )n 2 - Cu v n v (3-68b)
~dt

The numbers «, and n 2 must approach constant values after a sufficient length of
time. Hence, the equations imply a relation between the final populations:

(A + Bu v )n 2 = Cu v n v (3-69)

Let us combine this result with other information about n l

and «, to learn some
properties of the Einstein coefficients. We can assume that the atoms are distributed
according to the Maxwell -Boltzmann distribution for a system in thermal equilibrium
at temperature T. It then follows from Equations (2-35) and (2-36) that n and n
2 x

obey a second relation of the form

E /kB T
x

(3-70)
 .

172 Introduction to the Atom

where hv = E 2 — E v An expression for the spectral energy density results from these
last two observations:

hv/h » T
A + Bu= Cu„e
hv/k » T - B
Ce

Let us now assume that the atoms are in the presence of radiation characteristic of a
blackbody field and recall the Planck formula from Equation (2-37):

8w v 2 hv
u.. =
3 hv/k B T _ j
•

: g

We can then deduce the following connections between the parameters A, B, and C
by comparing the two expressions for «,,:

C=B and
A
-
B
=
877Af

c
— (3-71)

(These arguments can be assembled somewhat differently to redirect the inferences.

For example, it is possible to derive Planck's formula if it is learned independently that
the parameters satisfy Equations (3-71).) We have pursued this question out of
curiosity. Let us turn next to applications and examine the practical consequences of
Equation (3-70).
The laser operates through an active medium of atoms whose energy states can be
populated selectively by radiative means. Equation (3-70) tells us that the lower state
in any pair of levels is preferentially occupied at thermal equilibrium. Consequently,
the basic laser process of stimulated emission cannot be operative unless some
mechanism is included in the system for pumping atoms to the higher energy. This
added feature must be introduced to maintain a population inversion that overturns the
normal thermal distribution. Figure 3-26 shows how a three-level laser incorporates
such a pumping scheme. An electrical discharge is used to raise atoms from the
ground state to the energy level E 3 and then a rapid spontaneous decay brings the
,

excited atoms down to the level E2 . This state is described as metastable since its

properties are such as to inhibit spontaneous decay back to the ground state. An
incident photon of energy hv = E2 — E can {
then stimulate the desired laser transi-
tion to the level E x
.

The ruby laser is an example of such a three-level system. Green light from a flash

lamp pumps chromium ions in the ruby crystal to an excited level, and nonradiative
deexcitation takes the ions promptly to a long-lived state at slightly lower energy.
Stimulated emission then follows, generating a coherent beam of red (694 nm) output
light.

Laser start-up cannot proceed in the three-level system until the ground-state
population has been reduced by more than half. Large input pumping power is

needed to achieve this condition. Further inefficiency results from the fact that
ground-state atoms in the medium are likely to absorb the radiation emitted by other
atoms. These problems do not arise in the four-level laser because the device is
 3-9 The Laser 173

Figure 3-26 Figure 3-27

Three-level laser with a pumping mechanism Four-level laser with a population inversion
for populating level E 2
at the expense of level between levels E3 and E2 .

E 3
—
Metastable level
Pumping
transition hv

designed so that the ground state cannot participate in the laser transition. Figure 3-27
shows a possible level scheme with such a property. Pumping raises atoms from the
ground state to level £4
and the rapid population
, of level £3 follows by spontaneous
emission. Laser transitions are stimulated from E 3
to E2 by photons of energy
hv = E 3 — E2 The . population inversion between these two levels is easily maintained
as atoms at E2 undergo rapid spontaneous decay to the ground state. It should also be
clear from the figure that atoms in the ground state are not able to absorb laser light
at the frequency v.

The He-Ne gas laser is a familiar laboratory instrument with the performance
properties of the four-level scheme shown in Figure 3-28. The active medium for this
device is typically a 10 : 1 mixture of helium and neon gases at low pressure (of order
1 mm
Hg). An electrical discharge pumps helium atoms to an excited state, which
happens to have approximately the same energy above the ground state as one of the
upper levels in neon. A resonant transfer of excitation energy occurs between helium

Figure 3-28

Highly schematic plan of the He-Ne gas laser.

Pumping
transition
174 Introduction to the Atom

Figure 3-29

Basic components of a gas laser.

Electrical discharge terminals

T ,

T^
S
Gaseous
medium Laser beam

Resonating Enclosure
Mirror Partially
transparent
mirror

and neon via the collision process

He* + Ne -» He + Ne*.

The Ne* level then deexcites through a photon-induced laser transition, as indicated
qualitatively in the figure. Helium is used for the pumping phase because the lowest
excited states of the helium atom are uniquely situated for the collisional excitation of
specific neon levels. A discharge in pure neon would pump atoms less selectively and
populate too many different neon states. The He-Ne laser generates a red (633 nm)
output beam as one of several monochromatic possibilities. The beam can deliver
quite large amounts of power per unit area in a very narrow wavelength interval.
A resonating cavity of suitable length is an essential feature of the typical laser.
Figure 3-29 shows how the resonant characteristics of a gas laser are achieved by-
means of parallel plane mirrors at the ends of the gas enclosure. The separation of the
mirrors is designed to store radiation whose frequency corresponds to the desired laser
transition. The reflection system can accomplish a well-defined separation of frequen-
cies even though the length of the resonating cavity accommodates many closely
spaced optical modes. One of the two mirrors is partially transparent and transmits a
portion of the repeatedly reflected light to give the output of the laser. The storage
system also tends to eliminate photons whose directions are not parallel to the axis of
the resonator. As a result the long dimension of the cavity determines a precise
directionality for the output beam.
All the properties of monochromaticity, coherence, intensity, and directionality are
attainable at extraordinary levels in the laser. Many unique applications have been
discovered for the use of laser beams. These include the modulation and signal-carry-
ing capability of noise-free light in laser communication systems, the accurate de-
termination of very large distances (e.g., from Earth to Moon) by the reflection of
laser light, the investigation of multiphoton interactions with atoms using the methods
of laser spectroscopy, and the proposed fusion of nuclei in samples compressed by laser
radiation.
We have already noted that the theory of the laser began with Einstein's analysis of
stimulated emission. These basic ideas were eventually put into use almost four
decades later. The first laser was actually a maser, built in 1954 by C. H. Townes to
generate coherent microwave radiation from laser transitions in ammonia. The first

instrument to operate at optical frequencies was the ruby laser, constructed in 1960 by
T. H. Maiman. The invention of the optical gas laser followed soon thereafter.
 310 The Quantum of Action 175

Example

It is apparent that stimulated emission competes with spontaneous emission to

depopulate the higher energy level in Figure 3-25. Let us examine this competi-
tion by constructing the ratio of the two rates from Equations (2-37) and (3-71):

Bu.
hv/k » T
'

A e - 1

The result may be recognized as the average number (ri) of photons with
frequency v in blackbody radiation. To see this recall Equation (2-38) for the
average energy (e) per mode at frequency v, and write

= =
<") T-
hv e
hv/k » T
- 1
'

We can readily assess the effects of frequency and temperature by evaluating

this ratio of rates for different operating conditions. Thus, for optical transitions
at room temperature we might consider hv = 2 eV and kB T = ~ eV and find

hv Bu„ 1

= 80
kB T A e™ - 1

It is clear that these conditions favor spontaneous emission over stimulated

emission by an enormous factor. The numbers are quite different for microwave
~4
transitions at the same temperature. If we change A£ and choose hv = 10 eV,
we obtain

hv
-3
Bu v 1

= 4 X 10 => > = 250.

kB T A hv/k B T

The conditions favor stimulated emission in this case.

3-10 The Quantum of Action

Bohr's quantum picture of the atom did not develop at once into a fundamental
quantum theory. Quantization of energy was soon accepted as a demonstrable
property of the states of matter, and yet the underlying quantum principles remained
unknown for more than a decade. Some tentative insights were provided by Bohr's
quasiclassical model of the one-electron atom. Similar methods were also adopted by
A. J. W. Sommerfeld in his attempt to formulate the basic quantum principles.
Sommerfeld's approach to the mystery of quantization was based on a generalizing
concept known as the quantum of action.
The new ideas were focused on periodic behavior since periodicity was a common
feature of the earliest quantum systems. The frequencies of Planck's oscillators and the
orbits in Bohr's atom were instances where aspects of quantization were linked directly
to periodic properties. This connection was the key to Sommerfeld's proposal of a
generalized quantization principle. His procedure employed phase space as a scheme
for unifying all forms of periodic motion in quantum systems.
176 Introduction to the Mom

Let us introduce the idea of phase space by considering the evolution in time of the
classical motion of a particle. The dynamical equations of motion determine a
complete specification and velocity at any instant, if the particle's position
of position
and velocity are prescribed at some initial value of the time. We may use position and
momentum as an alternative pair of variables for an equivalent description of particle
motion.
Phase space is spanned by a system of axes whose definition is given in terms of

these position and momentum variables. The axes are constructed in pairs by taking a
position axis and a momentum axis for each of the particle's degrees of freedom.
Hence, a point in phase space denotes all the physical conditions of the system at a
specific instant since the point is located by the instantaneous values of all the
components of position and momentum. The point moves with time so that the
evolution of the system is described by a directed path in phase space. This locus of
connected points forms a closed path that repeats itself in cycles for the special case of
continuous periodic motion.
Sommerfeld's proposal expresses a general quantization principle for any kind of
periodic motion. The principle constrains the motion for each pair of conjugate

phase-space variables (q, p ), where the notation refers to the coordinate and momen-
tum for a particular degree of freedom of the particle. Every (q, p ) plane in phase
space exhibits periodic motion as a cyclic path surrounding a fixed area. Sommerfeld's
rule employs Planck's constant as a unit of area and defines an allowed quantum state
of the system to be a locus of points in phase space whose enclosed area satisfies the
formula

/cycle Pq dq = n h.
q
(3-72)

This area integral over a complete cycle in phase space is called the action integral.
The units of action are evidently the same as the units of h, and so Planck's constant
appears in the formula as a primitive quantum unit of action. Thus, the rule associates
a quantum number with the coordinate q and specifies an allowed path in phase
n
space to be one of a discrete set of paths whose separation in area is given by the small
quantum of action h.
Let us illustrate Sommerfeld's idea by examining the one-dimensional motion of a
mass on a spring. Phase space is the (x, p) plane, and the oscillating time dependence
of the coordinate is given for amplitude A and phase angle 8 as

x = A cos( tot — 8).

The angular frequency is related to the mass and spring constant by the familiar
expression
'
k

The other phase space variable is the momentum of the particle,

dx
p = m — = —mijiA sin( ut — 8).
dt

These oscillating variables are connected through the definition of the conserved total
 310 The Quantum of Action 177

Figure 3-30

Loci in phase space for a harmonic oscillator.

The quantization condition separates

consecutive allowed paths by an annular area
equal to Planck's constant, the quantum of
action.
P

Area h

energy
he 2
/•: = (3-73)
~2
2m

where the conserved quantity is given by

mw K
k k
E --
A 2 sin2 (ut - S) + -A 2cos 2 (ut - 8) = -A 2 .

We can rewrite Equation (3-73) as

+ (3-74)
2mE 2E/k

and thus identify the closed path in phase space to be an ellipse parameterized by the
constant energy E. Figure 3-30 shows how two such ellipses are constrained by the
quantization condition in Equation (3-72). We avoid computation of the action
integral by recalling the formula for the area of an ellipse, and we write the condition
in terms of the indicated semimajor and semiminor axes as

.IE
ny2mE \j = nh.

Hence, the allowed values of the energy are quantized according to the formula

h k
E= n—\-m
277 V
/
a hi (3-75)

We recognize the condition for Planck's quantized oscillators in this result.

Let us turn next to Bohr's circular orbits and demonstrate another application of
the quantization principle. This special case of two-dimensional motion has only one
178 Introduction to the Atom

degree of freedom defined by the angle 6. The conjugate momentum variable pe is

identified as the angular momentum L. We write Equation (3-72) as

f
Ld8 = n l

cycle

and immediately use the fact that L is a constant of the motion to obtain

LJ dO =L 2tt = n B h.
cycle

We note in passing that this simple calculation is valid even when the orbit is not
circular. Our result takes the form

L = neh (3-76)

and thus reproduces Bohr's expression for the quantization of angular momentum as
written in Equation (3-48).
Sommerfeld's quantization conditions were of some interest in the days of the old
quantum theory. The principle found extensive use in the generalization of Bohr's
model to the case of noncircular orbits. Degrees of freedom were associated with both
and r in this case, so that phase space was enlarged to include the two pairs of
conjugate variables (9, pe ) and (r, pr ). The angular momentum quantum number n e
retained its validity, while a second quantum number n r was also introduced by
applying the quantization principle to the radial variables as well:

/
p r
dr = n r h,
cycle

The two quantum numbers were employed by Sommerfeld and others to account for
a broader array of quantized energy states in the analysis of the hydrogen atom. Of
course, all these quasiclassical considerations passed rapidly into history with the
coming of quantum mechanics.

Problems

1. Suppose that, in an observation of Brownian motion in water at 300 K, spherical particles

of 1 fim diameter experience an rms displacement of 12 fim in 3 min. Calculate the value
of Avogadro's number from these data. (Recall that the universal gas constant has the
value R = 8.314 J/mole •
K.)

2. Obtain the general solution to the differential equation for Brownian motion,

dg 2k H T
—
dt
+
m
fi
—g =
m
,

and compare the result with the particular solution

2k B T

for the limiting situation where m —* 0.

 Problems 179

Consider Thomson's e/m experiment, and let 6 denote the angular deflection of the

electron beam as shown in the drawing. Deduce a formula to show how 6 depends on the
ratio e/m and on other parameters of the experiment such as the field strengths E and B.

The figure shows what appears to be an e/m apparatus similar to Figure 3-1. This
conventional cathode ray tube generates electrons from a hot filament and accelerates the
particles through a potential difference <j>
{)
. The electron beam passes between plates of

length x and separation d, where a voltage <f>

is applied across the plates. Obtain an
expression for the vertical deflection of the beam, showing that this measurable quantity
has no dependence on either e or m e
.

—fcHz>*

5. Here are some data from a Millikan oil-drop experiment:

plate voltage = 5080 V rise time (field on) = 22.1 s

plate separation = 16.0 mm air viscosity = 182 [i poise

rise-fall distance = 10.2 mm oil density = 920 kg/m

fall time (field off) = 1 1 .8 s

Determine the radius and the mass of the oil drop, and use the known value of e to

deduce the number of electron charge units on the drop.

6. A Thomson model of the hydrogen atom predicts a unique frequency of oscillation for the

electron. Assume that radiation of the same frequency is emitted by the atom, and
compute the wavelength of the radiation. Take the radius of the atom to be R= 0.05 nm.

7. Prove that the a-particle orbit in Figure 3-8 has the same incoming and outgoing impact
parameters.

8. Refer to Figure 3-8 and show that the distance of closest approach min for
r a non-head-on
collision in Rutherford scattering is related to the scattering angle 6 by

d i e
'mm = ^1 1 + CSC-

where D is the head-on distance of closest approach. Check the validity of the formula by
considering the special case of a head-on collision.
180 Introduction to the Atom

9. Grains of sand are elastically scattered by a bowling ball as shown. Obtain a formula for
the differential scattering cross section. Let the total cross section be defined as

r da
a = / —dSt,
•'all a du

and show that a is equal to the cross-sectional area of the ball.

10. A 3 MeV beam of a particles strikes an aluminum target. Determine the distance of
closest approach between a particles and aluminum nuclei at this energy, and calculate
thenumber of aluminum nuclei per unit volume in the target. (Aluminum has atomic
number 13, atomic mass 27, and density 2.70 g/cm3 .)
11. Suppose that the a-particle beam in Problem 10 carries 10' a particles/s to the
-4
aluminum target, and let the target thickness be lO cm. Calculate the number of a
particles scattered per second into the backward hemisphere.
12. A beam of 6 MeV protons is scattered by a gold foil of 10 cm thickness. The proton
detector is ring shaped as in Figure 3-6. The ring collects protons scattered at 60° and
subtends a small element of angle equal to 1°. Calculate the distance of closest approach
between protons and gold nuclei at this energy, the number of gold nuclei per unit volume
in the target, the size of the solid angle subtended by the detector, and the fraction of
incident protons scattered into the detector. (Gold has atomic number 79, atomic mass
197, and density 19.3 g/cm'.)

13. Consider Rutherford scattering at beam energy A', and derive a formula for the fraction of

incident a particles scattered through angles greater than a given angle 6 ()

.

14. Show that the Bohr orbits have quantized speeds given by

Z
vn = — ac,
n

in which a is the fine structure constant. Use this result to assess the validity of the

nonrelativistic treatment of the Bohr atom.

15. In the hydrogen spectrum, the Brackett series and the Pfund series are sets of spectral lines
corresponding to transitions to the n = 4 and n = 5 levels, respectively. For these two
series calculate the maximum and minimum values of the emitted radiation energy,
frequency, and wavelength.

16. The photon of largest energy in the hydrogen spectrum occurs at the Lyman series limit.

Calculate the momentum of the photon, and determine the velocity of the recoiling atom.
27
Take the mass of the atom to be 1.67 X 10 kg.

17. Obtain values (in eV) for the energies in the energy level diagram for singly ionized
helium He ' . Identify all transitions in He + for which the emitted wavelengths are in the

visible range, 350-700 nm.

 Problems 181

18. The Z = 1 neutral atom has three isotopic species: hydrogen, deuterium, and tritium. The
nuclear masses for these atoms are (approximately) M, 2M, and 3M, with M= 1.67 X
~ 27
10 kg. Obtain a formula and calculate a value for the difference of the Lyman a
wavelengths for hydrogen and tritium.

19. What are the Bohr- model formulas for the energy levels and the orbit radii in positronium?
What are the orbit speeds for the electron and positron? Obtain a formula for the
wavelengths in the positronium Balmer series, and calculate the corresponding maximum
and minimum wavelengths.
++
20. The doubly ionized lithium ion Li is a one-electron atom having Z= 3. Identify all the
++
transitions in the Li emission spectrum that lie in the far-ultraviolet region of the

spectrum and beyond, where the wavelengths are less than 50 nm.

21. A muonic atom is formed when a negative muon replaces an electron in a normal atom.
Determine the radius of the first Bohr orbit and the ground-state energy in a muonic
hydrogen atom. The muon mass is 105.7 MeV/c 2 .

22. The following Ka wavelengths are found in Moseley's data:

0.8364, 0.2111, and 0.1798 nm.

Identify the elements responsible for each of these x rays.

23. The following La , Lp, and L y wavelengths are measured for one of the elements in
Moseley's survey:

0.4385, 0.4168, and 0.3928 nm.

Use the L a line to identify the element, and compare the Lp and L y wavelengths with the
values predicted from the Bohr model.

24. A Franck-Hertz experiment in hydrogen shows dips in the anode current at 10.20 and
12.09 V. What wavelengths should be observed in the radiation emitted from the
Franck-Hertz tube?
25. Consider the motion of a bead of mass m on a. wire of length a. The bead is free to slide
back and forth with constant speed between x = — a/2 and x = + a/2. What is the locus
of the bead's motion in phase space? Impose Sommerfeld's quantization condition to
determine the energies for the allowed states of motion.
 FOUR
MATTER
WAVES

T he goals of the quantum revolution neared

fulfillment in the years just before 1925. One of the decisive contributions of this
period came forward in 1924 in the doctoral thesis of L. V. P. R. de Broglie. The
dissertation proposed that matter should possess both particle and wave characteristics, in
parallel with the quantum properties of radiation. It was very bold to suppose that
discrete matter should have wave behavior since there were no known indications from
experiment to support the proposal. Fortunately, the skeptical response to de Broglie's
hypothesis was not shared by Einstein, who found the idea promising and urged that it

be given serious consideration. The matter wave continued to be controversial even

after experimental evidence for it was found. It was obvious that original insight was
needed to interpret this new nonclassical type of wave.
An altogether different approach was adopted in W. K. Heisenberg's treatment of
the quantum was more like that of Bohr, inasmuch as
theory. His view of the situation
classical concepts were kept in sight while waves were not directly employed. Devia-
tion from classical physics was a central theme in Heisenberg's thinking. He reex-
amined the meaning of the basic observable quantities in particle mechanics and
found that uncertainties were inherent in the measurement of such variables. He then
argued that the principles of dynamics should be given by a formalism that made
allowance for the act of measurement. The familiar classical variables were to appear
prominently in this theory, and the intrinsic observational uncertainties were also
supposed to be built into the definition of all the quantities. Heisenberg formulated
these ideas, and thus arrived at his version of quantum mechanics, in 1925.
Our main concerns in this chapter are de Broglie's matter wave and Heisenberg's
uncertainty principle. We anticipate some of the arguments of quantum mechanics to
interpret the matter-wave concept, and we look critically at certain notions from
classical physics when we take up the question of uncertainty.

4-1 De Broglie's Hypothesis

The matter-wave conjecture was motivated in part by the similarity between quan-
tized states and standing waves. The quantization of energies was associated with the

182
 4-1 Be Broglie's Hypothesis 183

existence of discretely allowed configurations in a quantum system. This phenomenon

was comparable to the occurrence of harmonic frequencies for discrete modes in a
vibrating medium, such as a length of string or a column of air. De Broglie's
proposition was also an appeal to symmetry. He noted that the quantum theory of
radiation was based on a coexistence of particle and wave attributes, and he argued
that the quantum theory of matter should adopt a similar kind of dual picture.
The reminded of the circumstances that attended the proof of
skeptics needed to be
the wave nature was originally thought that light traveled in straight lines,
of light. It
or rays, much like the motion of free particles. The wave properties of light were
demonstrated by detecting the effects of diffraction over intervals of space whose
extent was of the same order as the wavelength of the light. This observation
encouraged de Broglie to believe that a wavelength might be associated with a moving
particle and that the resulting diffraction effects were such as to have gone unnoticed
in the more conspicuous forms of matter.
The matter-wave hypothesis assigns a wavelength A to a particle with momentum
of magnitude p. These quantities are related by the formula

h
A= 7 ,
(4-1)
P

in obvious analogy to the relation for a photon given in Equation (2-52). Thus, a free
particle with mass m and speed v has a de Broglie wavelength

X = —
h
(4-2)
mv

for the special case of nonrelativistic motion. Equation (4-1) is understood to hold
more generally in situations where p denotes the relativistic momentum.
We can appreciate Bohr's condition for the quantization of angular momentum by
appealing immediately to de Broglie's relation. Let us suppose that an allowed orbit in
Bohr's model is such that the de Broglie wave for the bound particle is a standing wave
that just fits the circumference of the orbit. We illustrate this intuitive notion in Figure
4-1 and write the condition for the standing wave in terms of Equation (4-1) as

h
2ttt = nX = n— .

Figure 4-1

Standing de Broglie wave on an allowed

circular Bohr orbit.
A
 ,

184 Mailer Waves

The result can be rearranged to produce the desired expression for the angular
momentum:

L = pr = n —
2v
= nh

as stated without argument in Equation (3-48). Of course, we should be aware that

this construction is still only an ad hoc quantum rule applied to a classical system.
De Broglie did not explain the physical nature of the oscillations in his proposed
wave. It was obvious that the matter wave (or phase wave, in his language) could not

be identified with the vibration of a material medium because it would not be

mechanically possible to reconcile the integrity of a physical particle with the diffusing
property of a physical wave. An altogether new kind of wave was being introduced,
and the interpretation was being deferred for later reflection.

Example

Let us show how the de Broglie wavelength is used to distinguish regimes of

different physical behavior. An electron with kinetic energy 100 eV has momen-
tum

p = p.m,K = ^2(9.11 X 10~ kg)( 100 eV)( 1.60 X 10"

31 19
J/eV)

= 5.40 X 10~ 24 kg •
m/s,

and de Broglie wavelength

34
6.63 X 10 J •
s
A = - = -24
= 1.23 X 10- 10
m= 0.123 nm.
5.40 X 10 kg • m/s

This result is comparable with the wavelength of an x ray, so that a suitable

diffraction experiment should be sensitive to the proposed wave behavior of such

a particle. In contrast, a 1
g pellet with speed 100 m/s has de Broglie
wavelength

h 6.63 X 10" 34 J •
s

A = = 6.63 X 10" JJ m.
Mv " (l0~
3
kg)(l00m/s)

The value of A for this macroscopic object is many orders of magnitude smaller
than the actual size of the object, and so no experiment can be devised to
demonstrate its alleged wave properties.
 4-2 Electron Diffraction 185

Example

Itmight appear from Equation (4-2) that the de Broglie wavelength is always
larger than the Compton wavelength h/mc. This conclusion is false because
Equation (4-2) is applicable only for nonrelativistic motion. Let us adopt the
more general form in Equation (4-1) and observe that the de Broglie and
Compton wavelengths can actually be equated as

h
when p = mc
mt

This condition determines the corresponding relativistic energy of the particle:

\E 2 — m 2c 4 = mc 2 => E- i/2mc
2
.

The kinetic energy of the relativistic particle is then given by

K= (i/2 - \)mc
2
.

We have used Equations (1-35) and (1-37) to obtain these results.

4-2 Electron Diffraction

Evidence for matter waves was found in 1927 in two separate laboratories. The
investigators were C. J. Davisson and L. H. Germer in one of the experiments, and
G. P. Thomson in the other. Both experiments demonstrated the effects of diffraction

for beams and obtained results in agreement with de Broglie's wave

of electrons
predictions. (G. P. Thomson was the son of J. J. Thomson. It was noteworthy that the
one should discover the wave nature of the electron 30 years after the other had
discovered the electron as a particle.)
The apparatus of the Davisson-Germer experiment was laid out as in Figure 4-2.
Electrons from a hot filament were accelerated through various potential differences to
produce beams of different energy. The electron beam was directed onto a surface cut
in a single crystal of nickel, and the scattered electrons were observed at different

angles by varying the angular position of a detector with respect to the direction of the
incident beam. The distribution was plotted as a function of the indicated scattering

Figure 4-2

Design of the Davisson-Germer electron diffraction experiment. The electron beam experiences
wave-like Bragg reflection from parallel planes in the scattering crystal.

Electron beam

Detector

Bragg planes in the crystal

Ni crystal
186 Matter Waves

Figure 4-3

Intensity of scattered electrons versus

scattering angle <p in the Davisson-Germer
experiment. Distributions are shown for beam
energies of 40, 54, and 68 eV.
68
Beam direction

angle <p for each beam energy in the manner shown in Figure 4-3. These observations
indicated that the scattering of electrons from the crystal target was just like the
diffraction of x rays by the same crystal. The intensity of scattered electrons showed a
large background of backscattered electrons and revealed a pronounced diffraction
peak in a certain direction for a particular value of the beam energy. This peak was
detected in the original experiment at an angle <p = 50° for a beam energy of 54 eV,

as indicated in the figure.

We can explain these observations if we apply the matter-wave hypothesis to the
electrons and recognize the effects of Bragg re/lection in the resulting wave behavior.
The de Broglie wavelength varies with the beam energy, so that diffraction is observed
when this wavelength is comparable in size with the spacing between parallel crystal
planes in the nickel crystal. Thus, the matter wave exhibits the same diffraction
phenomenon as that found in the Bragg reflection of x rays. If we recall the Bragg
condition from Equation (2-49) and apply the formula to matter waves, we find that a
diffraction maximum is expected in a direction <p given by the prediction

'/

= sin i
(4-3)
•1,1

Note that Figure 4-2 has been consulted to obtain

77 OP
6= - - -
2 2

as the relation between the angle <p and the usual Bragg angle 6. Note also that the
spacing d between crystal planes can be regarded as known, since this quantity can be
measured separately by diffracting x rays of known wavelength from the given crystal.
Finally, observe that the Bragg angle is fixed in Figure 4-2 and that the diffraction
peak appears at this angle for a unique value of the beam energy.
 4-2 Electron Diffraction 187

Figure 4-4

Electron diffraction pattern from one of Thomson's experiments.

Thomson's experiment was a study of electron diffraction for electron beams of

greater energy and shorter wavelength. The first scattering targets were thin films
made of organic materials; these were later replaced by metals such as aluminum and
gold. The had no large-scale crystalline structure, so that the scattering
metallic films
of electrons was caused by minute crystals distributed at random in each of the
targets. Electrons transmitted through such a film formed exactly the same diffraction
pattern as that observed for an x-ray beam of the same wavelength. A typical pattern
was similar to the one shown in Figure 4-4. Concentric sharp rings of maxima and
minima appeared symmetrically around the beam axis, just like the diffraction
resulting from a small aperture or a small obstacle.
The demonstration of wave properties by beams of particles was an indication of
quantum behavior by free electrons. This discovery came at a time when most of the
investigations of quantum properties were focused on electrons bound in atoms. It
should also be remarked that the charge of the particle was not a relevant considera-
tion and that beams of neutral particles such as neutrons were later found to undergo
the same diffraction effects.

Example

Let us ask why diffraction is seen in the Davisson-Germer experiment at 54 eV,

but not at 40 eV, as Figure 4-3 suggests. We need the de Broglie wavelength at
each energy in order to answer this question. The momentum at 54 eV is

p = pm K f
= /2(9.11 X 1(T 31 kg) (54 eV) (1.60 X 10"'°J/eV)
= 3.97 X 10" 24 kg •
m/s,

and so the corresponding de Broglie wavelength is

6.63 X 10" J4 J •
s
X= - = = 1.67 X 10~ 10 m = 0.167 nm.
p 3.97 X 10~- kg 4
•
m/s
 :

188 Matter Waves

We find A at 40 eV by using the inverse proportionality between A and JK

* = V
V
—
40
(° 167 nm = )
°- 194 nm.

The Bragg condition compares these wavelengths with the quantity 2d. The
nickel crystal in the experiment known (from an x-ray determination) to have
is

interplanar spacing d = 0.091 nm, and so 2d = 0.182 nm. Equation (4-3) has no
solution when K = 40 eV, since A exceeds 2d in this case; therefore, no
diffraction peak is expected at this energy. The calculation at K= 54 eV gives

A 0.167 nm
cos- =
<p

2
—
2d
=
0.182 nm
= 0.918 => T =
o> 46.9°,

in rather good agreement with the Davisson-Germer measurement of 50°.

4-3 Particle-Wave Duality

Electron diffraction is a display of wave behavior by a beam of particles in a wave-type

experiment. The experiment is sensitive to the wave nature of the electron because the
de Broglie wavelength of the particle is of the same order of magnitude as the
interplanar spacing in the diffracting crystal. No diffraction is observed, however,
when an electron beam
same energy passes between the plates of a cathode-ray
of the
tube, because the wavelength and the plate separation do not compare favorably for
an observation of wave behavior. Thus, the same electron has matter-wave properties
in the one experiment and classical-particle properties in the other.
A similar dichotomy has already made its appearance in our discussion of radia-
tion. We know that the wave nature of light has been fully verified by interference
and diffraction experiments, and we have recently learned that discrete properties are
also in evidence in such quantum phenomena as the photoelectric effect and the
Compton effect.

It is clear that the discrete nature of matter and the wave nature of radiation do
not provide a complete description, as classical physics has led us to believe. We have
to allow for complementary behavior that is wave-like in matter and particle-like in
radiation, because we are confronted with these properties when we perform the
appropriate experiments. Quantum physics thus requires the dual aspects of particle
and wave to be present simultaneously in matter and in radiation. This concept of
particle-wave duality also embraces a principle of complementarity . The dual characteris-
tics are complementary since matter and radiation are completely described by
adopting both particle and wave points of view. These two properties are not found to
be in contradiction because it is not possible to devise a single experiment that tests
both particle and wave aspects at once.
Particle-wave duality introduces the notion of a quantum particle. The extraordinary

behavior of this new entity is quite unlike any of the usual phenomena encountered in
our previous experience with classical systems. To illustrate, let us consider the
electron as a prime example of such a particle and explore some of the further
consequences of its dual qualities.
We expect the wave nature of the electron to carry over from electron diffraction to

any wave-type experiment. Hence, the remarkable properties of the matter wave may
also be seen if a double-slit experiment is performed with a beam of electrons,
provided the de Broglie wavelength is of the same orderas the spacing between the
 4-3 Particle- Wave Duality 189

two Let us proceed by detecting many individual electrons at specific locations on

slits.

a screen, after the particles have passed through the pair of slits. We confirm our
expectation of wave behavior by obtaining a distribution of detected electrons that
conforms exactly to the familiar interference pattern produced by light waves in a
comparable Young's double-slit apparatus. If we reduce the incident intensity and
collect only a few electrons on the screen, we find that the sparse distribution of
collected electrons still resembles the original pattern to the extent that the inter-
ference minima are observed at the same locations as before.
The observations are totally different in a macroscopic double-slit experiment where,
for instance, a much larger pair of slits is used to transmit a beam of pellets. We recall

from a previous example that the de Broglie wavelength of such a particle is too small
to be detectable, and so we expect to find no interference effects. If we let the pellets
be embedded in a screen after passing through the slits, we see that the embedding
occurs in two regions of the screen directly downstream from the two slits. This
distribution tells us that each of the pellets has passed through one slit or the other, as
expected for a beam of classical particles.
The double-slit experiment for electrons cannot be interpreted to say whether a
given electron goes through a given slit. Instead, the two slits transmit electrons in the
manner of a wave passing through both slits at once. Let us suppose that the
experiment is altered by mounting a separate current loop around each slit. An
induced current can then be observed in one loop or the other to detect the passage of
an electron through the corresponding slit. This induced current affects the passing
electron, however, so that the particle is likely to be found at a different location on
the screen owing to the modification of the slits. Thus, we destroy the wave behavior
of the original two-slit interference experiment if we attempt to get classical informa-
tion about the particles by tracking the electrons through the separate slits. In fact, we
succeed in changing one wave-type experiment into another whenever we monitor the
two slits. The two-slit interference pattern appears when the monitoring device is off,

while two overlapping single-slit diffraction patterns appear when the device is on.
The real meaning of de Broglie's matter wave remains to be explained. We know,
of course, that the wave is not to be associated with the oscillations of a material
medium, but we are not yet in position to identify the actual oscillating entity. Let us
approach this ultimate question of interpretation in the quantum treatment of matter
by looking first at the implications of particle-wave duality in the more familiar case
of radiation.
The radiation field is and magnetic
a continuous system of propagating electric
oscillations. We and choose the electric field E(r, t to specify the
follow convention )

form of the propagating wave. We also assume a monochromatic wave so that the
oscillations have a single frequency and wavelength given by v and A. The flow of
radiated energy is expressed by constructing the electromagnetic Poynting vector in
terms of the total field E at a given point P in space. Thus, we find that the flow of
energy per unit time across unit area at P is given by the expression

ce E2 .

Figure 4-5 provides a specific example in which the monochromatic radiation field is

produced by the illumination of a double slit and the point P is identified by the
position of a small photoelectric cell. The total field E at P is the sum of coherent
waves E, and E2 arriving at the given cell from the two slits. An interference pattern
is observed in the flow of energy as P varies over an array of such cells. Constructive
interference occurs at a given cell if the two waves arrive in phase, as in the situation
shown in the figure. The indicated slit separation d, wavelength A, and direction 6
190 Matter Waves

Figure 4-5

Interference of electromagnetic waves in a double-slit experiment. The same interference

pattern is obtained with a beam of electrons.

Double slit

ptj Photocell

Monochromatic Interfering
plane wave cylindrical waves

then satisfy the condition

sin 6 = an integer, (4-4)

provided the interferenceis observed at a large distance from the slits.

The general expression ce E oscillates with time, and so a more useful observable
quantity is found by averaging with respect to time over a complete cycle. We
therefore define E^ as the time average of E~ at the point P and introduce the
radiation intensity

ce E^

to obtain a quantity whose value depends only on the position P. The figure shows
how this intensity varies with the location of the photocell in the case of double-slit
interference.
The implications of particle-wave duality emerge when these familiar results are
cast in terms of photons. We know that the photon carries radiation energy hv, and so
we may express the radiation intensity at P by means of the alternative expression

hvlp ,

where IP denotes the average number of photons entering unit area at P per unit
time. The conclusion is a simple equality between the two ways of writing the
radiation intensity:

hvlp = ce Ep. (4-5)

This formula is a statement of particle-wave duality since the left side is written in the

language of discrete quanta while the right side is written in the language of wave
fields. Note that our example in the figure adapts at once to the introduction of the
quantity IP because the indicated photoelectric cell is sensitive to the arrival of
individual photons.
 4-3 Particle- Wave Duality 191

numbers of photons
Double-slit diffraction for increasing levels of incident intensity. Increasing
random locations on a distant screen. The probability distribution of
are detected per second at
detected photons conforms to the wave diffraction pattern. The intensity of this pattern is given
at large distance by the angle-dependent function

,»n (<k/2)^—
2

4 /r ,cos" 2
2 (*./2)

where §d = (27rd/\)sm6 and <pa = (2wa/A)sin#.

i
sin 8

i;3;>S:&

Incident light sin e

^ d
Wavelength a
Intensity 7
a

Double slit 10 100 1000

Photons per second Diffraction pattern

The photon description on the left side of Equation (4-5) makes no reference to any
concept of path for the arrival of photons at position P. We entertain no such notion,
even when we imagine a very low level of intensity and consider only a single photon
in transit. Instead, the detection of a photon at a particular location is understood to
be a random event that represents the one and only operational specification of the
position of the photon. Our double-slit example illustrates this act of locating a photon
as a single random occurrence in which the photon is absorbed once and for all by an
atom in a photoelectric cell.
The wave description on the right side of the equation tells us where the random
events of photon detection are likely to occur. To draw this conclusion we let the
relation and IP establish a correspondence between an intensity distribution
between Ej>
for the behavior of waves and a probability distribution for the detection of photons. The
quantity IP is interpreted as a measure of the probability of observing a photon in a
small region located at P. The equation connects this probability to the square of the
field at that location. The familiar wave field E(r, is thus / ) interpreted as a
mathematical wave function, or guiding field in Einstein's words, that furnishes statisti-

cal information regarding the likelihood for the random arrival of photons. Our
double-slit experiment illustrates this interpretation even at very low levels of inten-
sity. The resulting photon distributions are very sparsely populated and show no
isolated events in anyregion where destructive interference occurs for the correspond-
ing wave. A more marked resemblance then develops between the photon population
and the interference pattern as the incident intensity increases.
Let us add two final remarks about the wave function E(r, t ). We recall that the
electric field for waves in free space satisfies the familiar wave equation in the form
192 Mailer Waves

given in Equation (2-15). We also know that E is an observable physical quantity

since we can determine the field by measuring the electrical force on a small test
charge.
The implications of particle-wave duality can be transferred by analogy from
radiation to matter. Let us explore the possibilities of such an analogy and gain a
preliminary understanding of de Broglie's matter wave. We anticipate the definition
of a mathematical wave function called ^(r, t) for matter, in place of E(r, t) for
radiation. We assume that ty is found by solving a certain wave equation, of a form
yet to be discovered. Observable properties of ^ are proposed according to arguments
analogous to the probability interpretation of radiation, as just deduced on the basis of
Equation (4-5). We suppose that a quantity symbolized as S^J is derivable from
first

^(r, t), as E,j, is derivable from E(r, /). We then interpret ^J as a measure of the
probability of finding a quantum particle in a small region located at position P. The
notation 4^ is introduced temporarily to convey the analogy with Equation (4-5), so
that the probability of finding the particle at P has the form of an intensity
determined by the square of the wave. The proposed wave function ^(r, / ) is the basic
element in a formal theory of a quantum particle. Since the formalism is based on a
treatment of waves, it is understood that the addition, or superposition, of waves is
supposed to be incorporated as a main feature. Interference and diffraction effects for
quantum particles are then immediately explainable in terms of a probability
interpretation of the observed wave behavior.
These anticipatory remarks are offered as a statement of our objectives. We know
that evidence for de Broglie's matter wave is to be found in electron diffraction or any
other wave-type electron experiment. Our arguments imply that such observations of
wave behavior are to be interpreted probabilistically, in the manner of the probability
interpretation of radiation. To illustrate, let us return once more to our double-slit
experiment for light in Figure 4-5 and recall our discussion earlier in the section
regarding an analogous experiment for a beam of electrons. Particle-wave duality
predicts a complete parallel between radiation and matter, as an interference pattern
is mapped out by an array of photoelectric cells in the one case and by a similar array
of electron detectors in the other. The common probabilistic interpretation tells us how
the observed pattern describes a distribution of discrete observations at each point P
in the array. A photoelectric cell at P measures the probability of detecting a photon
while an electron detector at P measures the probability of detecting an electron, as
random detection events in both instances.

Example

Both Thomsons, father and son, performed experiments with beams of electrons.
We should be able to understand why the father saw no evidence for matter
waves by computing the relevant de Broglie wavelength. A typical cathode-ray
experiment has been discussed in the first example of Section 3-2. The electrons
were found to have a speed of 1.68 X 10 m/s and were allowed to pass
between a pair of plates with 2 cm separation. The corresponding de Broglie
wavelength would have the value

34
h 6.63 X 10 J •
s
A = = -. -r. t-.
: = 0.0433 nm.
m t
v (9.11 X 10" 31
kg)(l.68 X 10
7
m/s)
 4-4 Determinism and Randomness 193

This wavelength would be far too small for an observation of diffraction effects

due to the 2 cm spacing of the pair of plates.

4-4 Determinism and Randomness

Newtonian mechanics describes the motion of a classical particle by means of a

well-defined time-dependent coordinate vector r( t ). The goal of classical dynamics is

to predict the time dependence of r( t) for a given applied force through the use of
Newton's law

d't
m —
dt
2
F.

Two pieces of initial data must be given if this second-order differential equation is to
have a unique solution. Such initial information may be expressed in terms of position
r and velocity v, or position r and momentum p, at time t = 0. The resulting

dynamical scheme is said to be deterministic or causal, since precisely specified initial

,

conditions control the prediction of a precisely determined particle trajectory.

These familiar principles and objectives are at variance with the considerations that
pertain to a quantum particle. Recall that this new conception of a particle is adopted
whenever the corresponding de Broglie wavelength becomes a detectable property.
Our illustration of double-slit interference for a beam of electrons is one example
where the observations in the experiment are not addressed by the predictions of
classical determinism. Single-slit diffraction for a beam of electrons is another instance
in which a wave-type phenomenon is controlled by the properties of the electron's
de Broglie wave. In either case the matter wave is responsible for an interference or
diffraction pattern, and the distribution of intensity is interpreted as a distribution of
probability. Thus, each electron in the beam has a likelihood to be collected in any of
the given detectors that map out the observed pattern. No concept of electron path is

involved in these observations. Instead, the detection of a particular electron is a

random event whose occurrence represents the one and only opportunity to specify the
location of the particle.
It is clear that there is no necessity for particle dynamics to be based on the analysis
of detailed motion if the experimental observations are not able to confront the
analytical predictions. We may take the random detection of electrons in double-slit
interference or single-slit diffraction to be representative of such an experimental
situation. The results of this type of experiment can be understood if we set

deterministic principles aside and turn instead to the question of predicting probabili-
ties. There is a clear necessity for the latter kind of particle theory whenever randomness
characterizes the observable behavior of the particle.
We have anticipated the formulation of this theory in the previous section by
referring to the expected properties of the wave function ^(r, in our interpretation t )

of the matter wave. The determination of ^(r, /) for the quantum particle becomes
the objective in quantum physics, replacing the problem of solving for r( /) in the case
of the classical particle. We incorporate the random detectability of the quantum
particle in the probability interpretation of ^ and make no reference at all to the
deterministic classical trajectory defined by r(/). Note that, while the detection of a
particle at a given location is an entirely random event, the probability of random
194 Matter Warn

Figure 4-6

Examples of classical particle motion.

raj-

rr

detection at any location is supposed to be predictable from the determination of the

matter wave.
Of Newtonian mechanics retains its applicability for macroscopic nonrela-
course,
phenomena. In fact, we need not hesitate to follow the deterministic approach
tivistic

even in certain cases of submicroscopic particle motion, as noted in the example of

Section 4-3. We can decide on the proper treatment of the particle by comparing the
de Broglie wavelength with the size of potentially diffracting components in the given
physical system. Figure 4-6 shows several situations in which diffraction effects are
regarded as unobservable on the basis of this comparison.
Let us suggest another way to assess the applicability of the classical theory by
noting that every theory is described in terms of measurable quantities. Classical
physics takes the approach that predictions can be confirmed by means of measuring
devices whose intrusive influence on the system of interest can be made arbitrarily
small. The predictions become abstractions divorced from reality, however, when the
act of measurement is so disturbing as to prevent the verification of the theory. Let us
consider these criteria in the context of the deterministic trajectory r(/), the precise
time-dependent position of a particle. We can measure this quantity by illuminating
the particle and observing the scattered radiation. We know, of course, that the
scattering of a photon can impart momentum to the particle in any random direction.
We should therefore ask whether this act of observation constitutes an intolerable
disturbance on the motion of the particle.
Figure 4-7 shows an example of a macroscopic object whose behavior can be
watched with the aid of visible light. The corresponding photon momentum is much
too small to have a detectable effect in this case. The figure also shows how we might
attempt to observe an orbiting atomic electron. X rays are used for the purpose since
short wavelengths are needed to achieve the desired high resolution. A very severe
disturbance results because the x-ray photon carries a large momentum and can
transfer enough energy to the atom to cause the removal of the electron from its
atomic orbit. Thus, we can easily verify a prediction of classical motion in the upper
part of the figure, but we cannot even contemplate such a verification in the lower
part.
 4-5 The Uncertainty Principle 195

Figure 4-7

Observations of particle motion by means of scattered illumination. When the incident

wavelength is accommodate the size of the particle, the momentum
reduced to transferred by
the photon becomes large enough to disturb the observed motion.

Visible light illuminating

a macroscopic obiect

X ray illuminating an
atomic electron

These considerations of the measurement process are fundamental to the under-

standing of quantum physics. We examine the specific consequences of the problems
of measurement in the next section.

4-5 The Uncertainty Principle

Heisenberg's formulation of quantum particle dynamics was introduced in 1925. His

picture of quantum mechanics contained the usual time-dependent dynamical vari-
ables, such as the coordinate r( / ) and the momentum p( / ), but not in the form of
ordinary functions of the time. Instead, the observable quantities of the theory were
represented by means of matrices whose mathematical properties were tailored to
allow for the problem of measurement. This theory of matrix mechanics was soon
joined by an alternative theory of wave mechanics based on the concept of
de Broglie's matter wave. The famous Heisenberg uncertainty principle was deduced
in 1927 as a common feature in the interpretation of the two equivalent formalisms.
We are not going to discuss Heisenberg's picture of quantum mechanics any
further because the alternative wave approach is easier to understand in a first

exposure to the theory. Since the uncertainty principle can be established in both
matrix and wave pictures, we can regard the resulting idea as a deduction fundamen-
tal to any version of the quantum theory.
The principle delimits our ability to make accurate measurements of the observable
properties of a quantum particle. It is proved in the theory that corresponding
components of the conjugate variables r and p cannot both be known with absolute
precision at the same time and must exist in their simultaneous
that uncertainties
determination. It is specifically shown that the conjugate quantities ( .v, p ) have x

uncertainties (Ax, Ajb v ), which satisfy the inequality

h
AxA A >-, (4-6)
196 Mailer Waves

Werner Heisenberg

and that identical statements hold for ( y, p y ) and (z, p,). The conclusion identifies a

minimum product of uncertainties, which constrains the allowed accuracy of specifica-

tion for one of the conjugate observables at a certain time, given the accuracy of
specification for the other at the same time. It is therefore possible to know either
coordinate or momentum with certainty only at the expense of total ignorance
regarding the other conjugate quantity. Note that the principle applies to conjugate
pairs of components such as x and px and does not relate uncertainties for noncon-
jugate variables such as x and p .

The minimum product of uncertainties in Equation (4-6) is proportional to the

small quantum of action. Figure 4-8 shows how this small lower bound defines a tight
boundary between prohibited and allowed regions of uncertainty. It is clear that the
uncertainty in the coordinate can be made quite small unless the uncertainty in the
momentum is nearly vanishing, and vice versa. The figure indicates a very thin
"neighborhood of certainty" in which values and px are simultaneously assigned
of x
with more accuracy than the principle permits for a quantum particle.. Again we see
the role played by the smallness of Planck's constant as we consider physical systems
of vastly different scale. The limitations imposed by the uncertainty principle can be
ignored when measurements are performed on macroscopic objects, because experi-
mental errors are always much larger for these systems. On the other hand, the
inequality can be expected to have a decisive influence in the treatment of quantum
particles such as electrons bound in atoms. These observations are quite consistent
with our remarks about the measurement problem in the context of Figure 4-7.
We should note that we have not yet given a mathematical definition for the
uncertainties Ax and hpx . In fact, we have not even defined the concepts of position
and momentum for a quantum and cannot do so until we have made some
particle
progress into Chapter 5. This shortcoming is not an immediate concern since it is
perfectly correct to think of the observables in terms of their measured values. The
 4-5 The Uncertainty Principle 197

Figure 4-8

Domain of uncertainties allowed by

Heisenberg's uncertainty principle. The origin
represents certainty in both variables. A
nearby point (Sx, Sp) denotes a pair of small
uncertainties on the boundary of the allowed
region.

Allowed region

6p^ to
8»

Sx 5p =

lack of a proof of Equation (4-6) should not concern us either, provided we recognize
Planck's constant as the main factor in the minimum product of uncertainties.
Thought experiments can be performed to illustrate the logic of the uncertainty

principle and explain the appearance of Planck's constant in the result. A simple
device for the purpose is the elementary thin-lens apparatus illustrated in Figure 4-9.
Let us use the device to form a real image of a particle and consider the uncertainties
involved in the determination of the particle's position. We orient the axis along the
vertical y direction and let the particle be illuminated vertically from below, as shown
in the figure. Formation of an image means that the particle must scatter at least one
photon into the aperture of the lens. The transverse x component of momentum of a
scattered photon may then have any value in the range

( —p sin#, p sin#),

where 6 is half the angle subtended by the aperture and p is the scattered photon
momentum. Planck's constant makes its appearance when we use p = h/X to express
the momentum in terms of the indicated wavelength. The act of measurement causes
the particle to recoil with an opposite transverse momentum. We therefore obtain

£ipx = 2p sin = 2 - sin 6 (4-7)

A

as the uncertainty in the x component of momentum of the observed particle.

The apparatus cannot fix the exact transverse position of the particle because
diffractionby the aperture of the lens causes the image to spread out. The lens sees a
formed by the central peak in the diffraction pattern of the
particle as a circular blur
aperture, and it sees two particles as overlapping patterns like those shown in the
figure. The images are said to be just resolved if they satisfy Rayleigh's criterion,
whereby the central maximum of the one image pattern coincides with the first
 .

198 Mailer Waves

Figure 4-9

Real image formation to determine the location of a particle. The position uncertainty Ax can
be reduced by enlarging the lens aperture, but the momentum uncertainty &px is made larger
as a result.

t Image

Lens

\ )/ Scattered
\ (I photon

Particle

llumination

minimum of the other. This condition is illustrated in the figure as the means of
defining the uncertainty Ax in the measurement of a particle's transverse coordinate.
We can use the geometry in the figure to construct an expression for Ax once we know
the indicated diffraction angle qp. The angle for the first diffraction minimum is found
from the wavelength and the lens diameter according to the formula

A
sintp = 1.22-
d

(We recognize the analogous formula d sin <p = A as the condition for the first

diffraction minimum due to a slit. The additional numerical factor 1.22 is needed in
the case of a circular aperture.) Two geometrical relations connect the various
distances and angles:

Ax H
— = tan<p
y

and

= tan 6.
y

The related quantities are the object and image distances y and Y and the image
separation H. We eliminate y and d as follows to get a result for Ax in terms of the
angles:

d 1.22A tan<p
Ax = y tan q>
= tan op = .

2tan0 sin (p 2tan0

 4-5 The Uncertainty Principle 199

The angle cp is intended to be quite small, so that the position uncertainty becomes

0.61A
A* = (4-8)
tan#

The other angle is constrained only by the condition 6 < 90° for a finite aperture.

Let us write our results in Equations (4-7) and (4-8) side by side as

0.61A 2/*sin0
Ax = and Aft
r" = (4-9)
tan X

and multiply the two uncertainties to get

kxkpx = (1.22cos0)A.

The result is an estimated product of uncertainties equal to Planck's constant times a

fixed nonzero numerical factor. This quantity cannot be reduced to zero, in agreement
is always bounded away from 90° for any
with the uncertainty principle, because 6
finite aperture. We
we can improve our image resolution by enlarging the
note that
aperture and introducing a larger value of 6. Equations (4-9) tell us that we then
succeed in reducing Ax, but at the expense of increasing A/? The wavelength can (
.

also be decreased to gain better resolution, with exactly the same result.

It is possible to examine the meaning by another

of the uncertainty principle
approach based on the wave nature of matter. Let us suppose that a beam of particles
is incident on a slit and that all the particles have the same momentum p with no

uncertainty. The associated de Broglie wavelength A = h/p refers to an incident

monochromatic matter wave, as illustrated in Figure 4-10. The infinite extent of this
plane wave corresponds to a uniform probability for finding a beam particle any-
where in the region to the left of the and hence represents complete uncertainty in
slit

position for any particle in the incident beam. The wave is diffracted by the slit and
produces a distant intensity distribution just like the pattern obtained for light. The
figure describes a distribution with a large central diffraction peak whose first

minimum is given in terms of the indicated angle and slit width by the formula

sin i

Figure 4-10

Diffraction of a beam of particles by a single slit.

Monochromatic Distant intensity

matter wave distribution
200 Matter Waves

We cannot predict the point of detection for any particle in the region to the right of
the slit. Instead, we use the wave intensity distribution to determine the probability for
detection of a particle at any given location. The slit localizes the probability of
finding the particle in the transverse y direction, as demonstrated by the intensity in
the central peak. We
may estimate the uncertainty in the transverse coordinate for
any such particle by setting

Ay = a.

The diffraction peak is actually broader than the slit, and so there must be a
transverse momentum uncertainty Ap to account for the divergence of the beam. We
may estimate this quantity for a particle in the central peak by referring to the sketch
shown in the figure and writing

Ap = psm6.

The product of these estimated uncertainties is

A y Ap = ap sin 8 =
h
a-
A
—=
X

a
h ,

again in agreement with the uncertainty principle. We note that a narrower slit

corresponds to a reduced uncertainty in the transverse coordinate. We also note that a

broadening of the diffraction peak results, indicating an increased uncertainty in the
transverse momentum.
The uncertainty principle imposes a conceptual limitation on our ability to
determine the properties of a particle. The foregoing illustrations refer to inaccuracies
of measurement that cannot be reduced arbitrarily by any amount of improvement or
ingenuity in experimental technique. Instead, the observed coordinate and momentum
are involved in a conspiracy that prevents us from knowing both conjugate variables
with arbitrary accuracy at the same time. We therefore regard these uncertainties as
operational qualities of the variables themselves. The basic principles of the quantum
theory must somehow embody this inherent feature of the observable quantities, since

the formalism is supposed to contain the uncertainty principle as a fundamental

deduction.

Example

Let us use Heisenberg's uncertainty principle to make quantitative statements

about the two situations shown in Figure 4-7. Suppose that a 10 g object is

visually observed with 1% accuracy to have a speed of 10 m/s. The momentum

of the particle is

p = mv = (0.01 kg)(l0 m/s) = 0.1 kg m/s,

and the experimental uncertainty in the momentum is

Ap = (0.01)/) = 0.001 kg m/s.

The minimum position uncertainty must be

X 10~ 34
A* =
h
= —
1.05
;
r
I • s
= 0.53 X 10" 31 m.
2Ap 2(10" 9
kg m/s)
 4-5 The Uncertainly Principle 201

This result of the uncertainty principle is far below any realistic measuring error
and has no practical significance for such a measurement. On the other hand,
imagine that an electron is to be observed in its orbit in a hydrogen atom. We
assume that we can make a position measurement with sufficient refinement to
distinguish between two adjacent orbits. Let us take Equations (3-50) and (3-56)
from the Bohr model, ignore the reduced-mass effect, and express the nth Bohr
radius as

n a,

Our stipulated maximum uncertainty in the measurement of an orbit radius is

2
Ar = r — r ,
:
-[n
2
-(n- l) ]
= - -(2«
amc

The corresponding momentum uncertainty must then be at least as large as

2Ar 2(2 n

We interpret this quantity to be the radial momentum imparted to the electron

when the radial position measurement is made. The magnitude of the electron
momentum in the «th orbit is found to be

am ,c

from Problem 14 at the end of Chapter 3. We note that Ap and m e vn are of the r

same order, and we conclude that the act of measurement is disruptive enough
to affect the orbit of the observed particle.

Example

We may specify the precise location of a particle if we are prepared to give up

all knowledge of the particle's momentum. Equal likelihood may then be
assigned to any momentum, no matter how large the value. We can achieve a
certain degree of boundedness in the momentum if we can tolerate a lesser
degree of localization. This argument implies that an increase in localization is
accomplished at the expense of an increase in energy, or simply that localization
costs energy. To illustrate, let us assume that an electron is to be located
somewhere within a region of atomic size. The position uncertainty is of order
Ax = 10" 10 m, and so the minimum momentum uncertainty is of order

h 1.05 X 10" 34 J •
s
LP = = 1.05 X 10 -
4
kg m/s.
A7 10- 10
m
The actual electron momentum may be at least this large; therefore, the kinetic
202 Matter Waves

energy of the electron may be as large as

_ '-'
4 2
(1.05 X 10 kg m/s)
K= -31
= 3.78 eV.
2m e
2(9.11 X 10 kg)(l.60 X 10"' 9 J/eV)

This result is quite reasonable since the order of magnitude compares favorably
with values of the total energy in the Bohr model of the atom. If we attempt to
localize an electron in a region of nuclear size, we find a considerable increase in
our estimate of the energy. A position uncertainty of order A.v = 10~ 14
m
implies a much larger momentum uncertainty A/?. The electron is now likely to
have a large relativistic kinetic energy, of a scale appreciably larger than that
found for nuclear particles. We are then able to argue that electrons should not
occur as constituents of the nucleus. The numerical details of this argument are
left to Problems 7 and 8 at the end of the chapter.

Example

The uncertainty principle can be used to estimate a lower bound for the energy
of a particle. Consider an oscillating mass m on a spring with force constant k.

The energy is a constant of the motion, given in terms of the variables x and p
by the formula
2 2

E= —p
2m
+
kx

2
.

Classical physics allows a minimum energy equal to zero for the trivial case of

an oscillator at rest at the origin, where p = and x = 0. This simple configura-

tion violates the uncertainty principle, as the oscillator must have some minimal
motion due to the necessary uncertainties in x p. We can represent the
and
constant value of E by means of averages of the kinetic and potential energies
over a cycle of the motion by writing

X 7
2m 2

The average values of x and p should vanish for an oscillating particle, and so
2
the average values of x and p can be identified with the squares of the
corresponding uncertainties:

<*
2
> = (A*) 2 and (p
2
) = (Apf =
2 A;

We set A* = 8 to abbreviate the notation and rewrite the energy as

E= —-
2
h k
2
+ -8 2 .

8mS 2

Figure 4-1 1 shows that this expression has a minimum for a certain value of 8.
 4-5 The Uncertainty Principle 203

Figure 4-1

Estimation of the zero- point energy for a linear

oscillator.

«o

We determine the minimizing uncertainty 5 by requiring

dE fr
= = + kS
4m8 :

to get

2
h
2
So =
Amk

The minimum energy is found from this result:

2
4mk k h
= -co,0)
8m \mk

where co appears in the final answer as the familiar angular frequency of the
classical oscillator. Our estimation of the minimum energy from the uncertainty
principle happens to agree with the exact formula obtained from quantum
mechanics. The result is called the quantum zero-point energy for the one-dimen-
sional oscillator.

Example

Consider the image cast on a screen by a beam of particles projected through a

The width of the image grows with
slit. the width of the slit,and also grows
when the slit is made very narrow owing to the diffraction of the beam. Hence,
there must exist an intermediate width for the slit that produces a minimum
width for the image. We can use the uncertainty principle to study this

beam-divergence effect since we expect some degree of uncertainty in the

components of coordinate and momentum transverse to the direction of the
beam. We suppose that a particle passing through the slit is localized within a
distance y of the beam axis, and we argue that the corresponding transverse
204 Matter Waves

Figure 4-12

Uncertain initial conditions for a particle

passing through a slit.

Slit
Screen

momentum can be as large as

h
Po = ir~
2 Jo

These uncertainties appear in Figure 4-12 as uncertain initial conditions for a

classical treatment of the subsequent motion of the particle. The indicated
off-axis displacement is given by

y = ya + — t= yo+ ~
n
— '<

where t is the time when the particle reaches the screen. The distance to the
screen is determined by the beam momentum P as

/'

x= -t,
m

and so the off-axis displacement becomes

h mx fix

y =y + ~7T = yo +
2my P 2Py

This expression has a minimum for a certain choice of y , as obtained from the
condition

— = 0=1
dy

dy
hx

2P7Z

The minimizing value of y and the corresponding minimum value of y are

2
hx j>

-fo
= /

VV tb
2P
and y
= yo + —
y
=
Q
2 yo-
 4-6 Waves and Wave Packets 205

We conclude that the image cast by the pa rticle be am has its smallest width
when the half-width of the slit is taken to be y/hx/2P Note that the result for y .

can be rewritten as

hx
J
Xx
2P " V 477 '

where A is the de Broglie wavelength of the particle.

4-6 Waves and Wave Packets

We begin our formal treatment of the quantum theory in Chapter 5. Our purpose in
this concluding section is to prepare a foundation for the wave picture of quantum
mechanics by reviewing the properties of waves. We are especially concerned with the
use of a wave to convey the idea of localization, since we know that a wave distribution
is supposed to represent a distribution of probability for locating a quantum particle.

This review deals only with waves described by a single spatial variable. We begin
with the properties of a monochromatic traveling wave and illustrate by means of the
wave function

^ = A COS 277 vi A cos( Aw — to/ ). 14-10)

Note that factors of 277 are eliminated by introducing the wave number k and the
angular frequency w as

k = —
277

A
and to = 2mv. (4-11)

The argument of ty is called the phase of the simple harmonic wave. This quantity
determines the cyclic behavior of the wave as the function ^ varies with the
independent variables x and t. Figure 4-13 shows how two configurations of a
traveling wave on a string are seen as snapshots of ^ versus x, taken at two different
times during a cycle.
Equation (4-10) is not necessarily restricted to waves in a one-dimensional medium,
even though the expression has only one spatial variable. We can also let ^ represent

Figure 4-13

Simple harmonic wave at times / = and

/ = 1/4 »». The wave propagates with phase
velocity v^ = vX.
206 Mailer Waves

a plane wave in three dimensions and visualize the wave as the propagation of a plane
surface of constant phase. This wave front is defined by setting the argument of ^
equal to a constant:
kx — co/ = <j) .

The resulting plane surface has a varying position along the x axis, given by

<J>
+ co/
x = at time t.
k

Hence, the surface of constant phase propagates in the positive x direction with phase
velocity

v, = — = v\. (4-12)
* k

A similar conclusion is drawn for the traveling wave in Figure 4-13. The alternative
wave function
^ = Asm(kx - co/)

Figure 4-14

Analogue model of phase propagation. Clocks are arrayed at 3 m intervals along an axis, and
each clock is set in sequence to run 3 h out of synchronism with its predecessor. The hour hands
simulate wave motion, with wavelength X = 12 m and frequency v = (12 h)~ '. The system of
clocks is read at times / = 0, / = 3 h, / = 6 h, . . . .In each instance special notice is taken of
the indicated 1 2-o'clock reading as a particular choice of phase. The selected orientation of the
hour hand is observed to propagate with phase velocity v^ = 1 m/h. Thus, the phase travels
along the axis while the clocks remain in place.

x =

t=

(= 6
 4-6 Wares and Wave Packets 207

describes a wave with the same properties as the original ^ in Equation (4-10), apart
from the obvious quarter-cycle difference in phase. Another entirely different example
of phase propagation is described in Figure 4-14.
A complex-number representation is often employed as a convenient mathematical
device for the handling of phase in an oscillating system. A brief summary of the
properties of complex numbers is given in Table 4- 1 The main result for our purposes .

Table 4-1 Properties of Complex Numbers

Imaginary number i = /— 1

Complex number z = x + iy (Cartesian form)

Real part = Rez
v

Imaginary part y = Im z
Complex conjugate z* = x — iy

2
Modulus \z\ where \z\ = zz* = x
2
+ y2 = r
2

Phase where tan 6 =

Imaginary axis

Real axis
Complex plane

Power series x = r cos 6 = r( 1 — — + • •

)
2!

y = r sin0 = r(8 1- • • •
)
3!

z = r(cos + i sin 6)

3
{idf (id)
= r[\ + id + +
2! 3!

Complex number z = re' (polar form)

6
Phase factors e' = cos 6 + i sin 6 and e
,e
= cos 9 - i sin 6
Real part Ree' = cos0 = {e'
e
+ e~ ,e )/2
Imaginary part Imf' 8 = sin0 = (e
iB
- e~ ,e )/2i
208 Mailer Waves

is the formula for the complex exponential function

e"*" = cos <p + i sin (£,

in which the cosine and sine functions appear as the real and imaginary parts. This
formula can be applied advantageously to represent a wave in the form

- at)
* = Ae* kx = A[co&(kx - at) + ism{kx -at)}. (4-13)

Notice that the expression describes both cosine and sine monochromatic traveling
waves at once. The complex form can be used to make calculations of wave behavior
in a physical medium, and then the real or imaginary part can be taken, as
appropriate, at the end of the analysis.
The foregoing illustrations and formulas pertain to waves traveling in the positive x
direction. The mathematical expressions are immediately adapted for propagation in
the opposite direction by changing the phase variable from (kx — at)to( — kx — at).
In either case the various forms of the wave function are easily seen to satisfy the
one-dimensional wave equation, written (with speed of propagation z;) in Equation
(2-1 1). Of course, we are not yet able to write the wave equation for use in the case of
matter waves.
Let us consider the possible adoption of Equation (4-13) as a matter wave for a
quantum particle. We see at once that the parametrization defines a unique de Broglie
wavelength A = 27i/k and a correspondingly unique momentum for the particle:

h
p = — = hk.
A

This assignment of momentum has no uncertainty, and so the uncertainty principle

implies no localization in the position of the particle. The given matter wave evidently
describes a particle whose likelihood of detection is uniform over all locations in space.
We begin to achieve a degree of localization when we superpose waves with slightly

differentwavelength and frequency. Let us illustrate this point by adding two such
wave functions, using the real-valued form in Equation (4-10):

* = Acos[(k + 8k)x - (a + 8a)t] + Acos[(k - 8k)x - {a - 8a)t].

The complex exponential representation provides an efficient way to perform the

addition:

ty = A Re (^'[^ + SA )*-(" + s ")'] + giHk-Sk)x-(a-6a)t]-\

= ARe{\e' <Skx ~ s " n + £-'(e**-*«0"L«(**-«0]

= 2Acos(8kx - 8at)Re[e' (kx -" n ]

= 2Acos(8kx - 8at)cos(kx -at). (4-14)

 4-6 Waves and Wave Packets 209

Figure 4-15

Composition of two monochromatic waves with different wave numbers and frequencies
(k + 8k, w + Su) and (k - 8k, u - Sto). The composite system propagates with group velocity

v
g
= Su/Sk.

^v e

This superposition of waves exhibits the familiar phenomenon of beats. Figure 4-15
shows a snapshot of ^ versus x in which the oscillations of the wave are contained in
an envelope defined by the first of the two wave factors in Equation (4-14). This factor
by itself describes a monochromatic wave with wavelength 2^ /8k and frequency
540/277-. The whole wave pattern in the figure travels in the x direction with a speed
determined by the propagation of the envelope. The speed of such a composite wave
system is known as the group velocity, given in this instance by the formula

8cj 2tt 5co

(4-15]
2tt 8k " 8k

Note that the group velocity is quite different from the phase velocities

and
k + 8k k - 8k

for the two monochromatic waves in the composition of ty.

A semblance of localization is apparent in Figure 4-15 since the resultant wave

clusters into a sequence of groups traveling together with a well-defined speed. This
formation of localized groups becomes a more marked effect with the superposition of
many different monochromatic waves. The resulting localization is still not satisfactory
as a representation of a quantum numbers of
particle because the addition of finite
differentmonochromatic waves always produces an infinite sequence of repeating
groups. This undesirable repetitive feature can be eliminated by summing an infinite
number of component waves according to the following prescription.
Figure 4-16 shows schematically how a wave packet displays the desired property of
localization. The composition produces oscillations confined to a single region of space
and thus provides an idealized picture of a localized matter wave. This structure may
be employed to derive a correspondingly localized probability distribution for a
210 Mailer Waves

Figure 4-16

Schematic wave packet representing the localization of a particle. The packet travels with
group velocity v .

quantum particle. We wave packet by superposing complex mono-

construct such a
chromatic waves of the Equation (4-13), where the superposition runs
sort given in
over a continuous range of wave numbers according to the integration formula

/oo
'- a,)
* A(k)e iik dk. (4-16)

An amplitude function A(k) is supplied to specify the contribution of each component

wave in the composition of V
P. Let us suppose that the distribution of wave numbers
assigns a maximum weight to a particular wave number k = k, as illustrated in Figure
4-17. The construction of the wave packet has the property that the angular
frequency to appears as a function of k in the integration of Equation (4-16). Hence,
the component waves are summed for infinitesimal increments dk in wave number
and do in angular frequency and are controlled by A(k) so that destructive inter-
ference of waves tends to occur outside the localized portion of the wave packet. The
resulting wave system propagates with a group velocity similar to the ratio given in
Equation (4-15). The formula reads

do)

Figure 4-17

Distribution of wave numbers in the

composition of a wave packet. The amplitudes

of thecomponent waves are heavily weighted
around wave number k = k and become
vanishingly small outside the interval
(k - ii, k + R).

A(k)
 4-6 Waves and Wave Packets 21 7

where the infinitesimal increments are taken at the value of the heavily weighted wave
number k = k in the figure.

We should note the important distinction between the group velocity v in

Equation (4-17) and the phase velocity v^ in Equation (4-12). A value of v^ is defined
for every wave number k in the integration of Equation (4-16), while a single value of
v is associated with the entire wave packet and the heavily weighted wave number
k = k. The two quantities can be connected by the relation

l'
s
=
du
lk
=
,1

-(K)
7k
»*
*
+ *
—
dvj,

dk
(4-18)

Thus, the group velocity and the phase velocity at k differ whenever v^ depends on k.

Phase velocity is independent of wave number for the special case of light waves in
vacuum. We see this from the simple formula

v+ = p\ = c,

and so we obtain the expected result v = c for the group velocity of any wave packet
(or pulse) of light in vacuum. A different result is found for the propagation of light in

a medium because of the effect of the index of refraction as a factor in the phase
velocity

The refractive index n has a dependence on k, and so the determination of the group
velocity for a light pulse in a medium calls for an identification of the wave number k
and a proper evaluation of Equation (4-17). This k dependence (or X dependence) of
the index of refraction causes the phenomenon of dispersion.
The dispersive property of a wave can also be described as the result of a nonlinear
relation between the wave parameters to and k. We see such an effect when we
compute the group velocity of a matter-wave packet for a localized free particle. Let
us introduce energy and momentum for this purposeand adapt the parameters in
Equations (4-11) accordingly, using the Planck-Einstein and de Broglie relations

E E p p
w = 2?:- = - and k = 2v- = -. (4-19)
h h h h

We can then regard the matter-wave packet as a superposition of matter waves with
definite momentum, summed over a continuous range of momenta and energies. In
this parametrization the formula for the group velocity of the wave packet becomes

dE
i--, (4-20)

where the heavily weighted momentum in the superposition is given as

p = hl. (4-21)

The effect of dispersion arises because the parameters satisfy the nonlinear relation

2m
212 Mailer Warn

for a free particle. The group velocity of the corresponding wave packet is then found
to be

v
g
=~ (4-22)
m

from Equations (4-20) and (4-21). We identify this result immediately as the velocity
of the localized free particle.
The mathematical properties of the wave packet in Equation (4-16) are not
difficult to analyze. Let us examine these details in the context of Figure 4-17
specifically so that we can visualize the idea of localization. We note that the equation
defines the wave packet as a sum over all wave numbers and that the range of
summation becomes finite when the amplitude A(k) has the shape indicated in the
figure. The formula for ^ therefore assumes the simpler form

~ ~
k+ K - ut k+ K
* = [ A{k)e* kx Uk - A(k) [ e
ikx
e-
iu
'dk.

The last step approximates the integral by taking the amplitude function to be
evaluated at k = k, where the distribution of wave numbers has its peak.
The remaining integrationis then performed via the following series of maneuvers.

We first define a new integration variable k by setting

k = k + k,

and we note the k dependence of the angular frequency:

co = -
E
h 2mh
p
2

- = —h

2m
k
2 =
h

2m
_
(k
2
+ 2kK + k
2
).

The resulting expression for the wave packet becomes

^"v-' (A /2m,(p 2 * K K
~'
+ +
* = A(k)e ,ix f ' ,
^c

= A(k)e ,l<e-'"'r f "V"" / ""V-" t/ -, '"" I

7K, (4-23)

in which the value of w at k = k is introduced as

2
hi
co = .

2m

We then make a further approximation and replace the third exponential factor in the
2
integrand by unity. Our treatment of this function of k is justified since k remains
small when the integration is restricted to such a small k interval as that shown in
Figure 4-17. These steps lead us to the result

- _
- Ul) rK hk
*= A{k)e ,(kx \ e'
{x -"*' )K
dK, where v=—,
J-k rn

in which Equations (4-21) and (4-22) are recalled to identify the group velocity v .
 4-6 Waves and Wave Packets 213

The elementary integral yields the desired formula for the wave packet:

*- S,)
* = A(k)e i(i r,
~ c

Ax v l
g )

= 2A{k)e* k *- z" ) —
sin( * - vj )k
^— (4-24)

The significant part of the final expression is the rightmost ratio of factors containing
the quantity (x — v t). The shape of this function of x at a given time / is just like the
behavior of the wave packet in Figure 4-16. We note that the oscillations are localized
within a region centered at x = v t and conclude that the wave system must be
traveling at group velocity v in the positive x direction.

Let us conclude our discussion of wave packets by offering a few additional

mathematical comments without proof. These remarks should appeal to our intuition
and are meant to apply quite generally for waves of any kind. We take a proper wave
packet t to be a system of waves whose structure is localized within a definable
spatial interval Ax. We construct such a system by choosing an amplitude function
A(k) whose distribution is confined to a wave-number range of width Ak. It can then
be proved that Ax and A/: satisfy a relation of the form

AxAk ~ 1 (4-25)

for any consistent definition of the two quantities. This result turns into a statement of
when the second of Equations (4-19) is employed to relate
the uncertainty principle
wave number k and momentum p. The range of k values in the construction of the
wave packet corresponds to an interval Aco in the angular frequency. This localized
system of waves travels past a given location in a time interval A/. It can be proved
that the intervals Aco and At satisfy the additional relation

Ace At ~ 1. (4-26)

If we again consult Equations (4-19) to relate angular frequency and energy, we find
that this second conclusion becomes an uncertainty principle involving energy and
time:

AEAt~h. (4-27)

The generality of Equations (4-25) and (4-26) should be emphasized as both are
applicable to any type of localized wave. We should also acknowledge the primitive
status of the uncertainty principle

h
Ax Ap
H >
-
2

since the inequality can be proved from the basic quantum mechanical properties of
the observables x and p. All the proofs cited in this paragraph fall outside the scope of
our mathematical presentation.
214 Mailer Waves

Figure 4-18

Diffraction of waves by a single slit. Each element of slit width dy emits a wave element d^.
The emitted waves are in phase at the plane of the slit and travel parallel paths to a distant
point of observation.

Example

The is an instructive exercise in the addition of

analysis of single-slit diffraction
waves and the use complex numbers. We refer to Figure 4-18 and consider
of
the superposition of waves arriving at a point located by the indicated distance
R and off-axis angle 0. Huygens' construction tells us that each element of slit
width dy m a. slit of width a acts as a source of waves assumed to emanate in
phase from the plane of the slit. We let R be large enough so that we can
assume parallel paths for all waves out to the point of observation. A wave
emitted at coordinate y in the slit travels a distance (R — y sin 6 ) to the remote
point. We express the contribution of the emitted wave element in complex form
as

dy
= Ae k R -y 3ine )- ul ]—
dty >l <.

and evaluate the sum of such waves as follows:

ffl/2
d '(*«-w')/ ,-'*>sintf_Z
Ae'/ />

•'slit
J

1 .(*« u>t)f/2 „„„/ t ..„:„flW.._?f..a«

cos( ky sin 6 )dy= e
i{kR <*»f
wt)
( cos(ky sin 6) dy
Jf-
-a/2
a/2 a J()

ka
|
— sin

Ae i(k*--)
ka

Oddness and evenness properties are employed in the integrand along the way
to the final result. The rightmost ratio of factors is the main part of the
expression since the square of this ratio describes the 8 dependence of the
distribution of intensity for single-slit diffraction.
 4-6 Waves and Wave Packets 215

Figure 4-19

Gaussian distributions for the amplitude

function A(k) and the wave packet ^ The .

widths Ax and Ak obey a reciprocal relation

in which the product Ax Ak is equal to a pure
number.
A(k)

A-

Example

The following construction of a wave packet illustrates the uncertainty relation

in Equation (4-25). We consider a superposition of complex waves at t = 0,
given by
X hx
* = \
A{k)e' dk,

and let the distribution of wave numbers be specified by the amplitude function

2
A (k) =*-<*/*> .

The shape of this gaussian distribution is shown in Figure 4-19. We note that the
peak of the function occurs at k = 0, and sowe can assume that we are
describing a wave packet ^ for a particle at rest. The integration becomes

*~ * /K) ik/K) '

(
"(cos kx + t sin kx) dk = / e~ cos kxdk
- oo ^ oo

since the sine portion of the integrand is odd and integrates to zero. A table of
definite integrals yields the result for the wave packet at t = 0:

* = ^TKe- (Rx/2f (Dwight 861.20).

This function is also shown in the figure to have the form of another gaussian
distribution. Each of the two shapes has a readily identifiable width, defined as
the indicated spread in the distribution evaluated at half the maximum value of
the function. These definitions of Ax and A£ can be shown to satisfy Equation
(4-25) for any choice of ic; the demonstration of this property is left as Problem
1 7 at the end of the chapter. Note the reciprocal sense in which the parameter ic
 .

216 Matter Waves

controls the widths of the two distributions. We see that A(k) is sharp and ^ is

broad if it is small, and we find that the reverse is true if k is large. This striking
feature makes the gaussian wave packet an especially appealing prototype to
illustrate the mathematical concept of localization.

Problems

1. Let the kinetic energy of a particle at room temperature be expressed as -,k B -^ eV. T=
Calculate the de Broglie wavelength for electrons and for neutrons at room temperature.
21
(Take the neutron mass to be 1.67 X 10" kg.)

2. Consider the de Broglie relation for a relativistic particle and show that wavelength and
kinetic energy are related by

he
X =
2
]JK(K+ 2mc )

This formula implies

he
X ~ - for K » me
1
,

K
and

h
X ~ , for K <s: mc
flmK

Obtain the leading correction to each of these approximations.

A potential difference of 1000 V accelerates a beam of electrons in an electron diffraction

experiment. The beam strikes a crystal whose interplanar spacing is 0.05 nm. Determine
the directions of the observed diffraction maxima in terms of the angle <p indicated in
Figure 4-2.

A beam of 1 eV neutrons strikes a crystal whose crystal planes are spaced by 0.025 nm.
Determine the angle <p for which the first diffraction maximum is observed. Are there
higher orders in the diffraction pattern?

Plane waves of 500 nm light are incident on a photocell whose receptor is 1 cm square.

Suppose that the cell records a counting rate of one photon per second with 100%
efficiency. Calculate the intensity of the light (in W/m 2
), and determine the amplitude of

oscillation of the propagating electric field.

An object is dropped from rest so that its subsequent vertical position is given by

This deterministic result becomes blurred if the initial position and velocity are not so

accurately known. Let ^(0) and v(0) lie somewhere in the intervals — Sy, Sy) and
(

( — Sv, Sv), respectively, and deduce the resulting behavior of the variable y(t). Draw a
graph of the deterministic result and show how the graph is modified by these considera-
tions.

A proton bound in a nucleus experiences the strong force of nuclear attraction when the
-15
particle is within about 10 m range of another nuclear particle. Estimate the kinetic
 Problems 217

energy of the proton for this sort of localization. What can then be said regarding the
potential energy?

8. Reevaluate the calculations of the previous problem for an electron localized in a region

of nuclear size.

9. A hydrogen atom has total energy

E^ 2m
».2

e
477e
2

'—,
r

neglecting the reduced-mass effect. Let r denote the radial distance within which the
bound electron is localized, and estimate the corresponding momentum p. Continue
the estimation procedure to obtain expressions for the minimum value of E and the
minimizing value of r. Compare the results with those found in the Bohr model.
10. A particle of mass m is confined to a one-dimensional region of length a. Use the
uncertainty principle to obtain an expression for the minimum energy of the particle.
Calculate the value of this energy for a 1 g bead on a 10 cm wire and for an electron in a
region of 0.1 nm length.

11. Let pellets be dropped onto a small spot on the floor. The uncertainty principle implies
that the pellets cannot be assumed to fall straight down from rest. Allow for uncertain
initial conditions, especially those transverse to the vertical, and deduce an expression for

the minimum range R on the floor at a distance H below the location of release.

Calculate the range for 1

g pellets dropped from a 2 m height.

12. Show that any function of the form f(kx + ut) is a solution of the one-dimensional wave
equation. Identify the speed of wave propagation in terms of the parameters in /.

13. Carry out the addition of the two waves

* = ,4sin[(* + 8k) x - (u + 8u)t] + Acos[(k - 8k)x - (to - 8u)t]

by means of the complex-number representation, and interpret the result.

14. Consider the interference of two waves ^, and *$?.,, emitted in phase from two very narrow
parallel slits. The waves have the same amplitude, wavelength, and frequency and are
observed as shown, at an angle 6 and at a large distance R. Construct the superposition
4', + ^2 using the complex wave format, and deduce the 6 dependence of the resulting
interference pattern.

15. Consider the addition of waves emitted in phase from two parallel slits with width a and
separation d. The resultant wave is observed as shown, at an angle 6 and at a large
distance R. Let the wave element emitted at the indicated location y be written as
218 Mailer Waves

Determine the resultant wave and deduce the 6 dependence of the observed diffraction
pattern. Evaluate the limit of these results as a —* 0.

16. The width of a wave packet and the width of the associated wave-number distribution are

connected by the "equality" Ax AA ~ 1. Use this result to construct a simple proof of the
analogous "equality" AwA< — 1 involving the related intervals of angular frequency and
time.

17. Refer to Figure 4-19 and consider the gaussian wave packet discussed in the second
example of Section 4-6. Express the widths Ax and Ak in terms of ic, the parameter

appearing in the amplitude function

hy
A(k) =e~ (h \

and show that the product Ax A k is equal to a pure number independent of k.

18. Determine the form of the complex wave packet ty at / = 0, given the amplitude
distribution

a( l\ — I ^o f° r ^ ' n tne interval (k — k, k + k)

\ otherwise

2
Obtain the squared modulus |^| and sketch a graph of this function.

19. Let the amplitude function for a complex wave packet ^ be given as

sin ka
A(k)=A ()
-

ka

and determine the form of ^ at / = 0.

 FIVE
QUANTUM
MECHANICS

/he formalism of the quantum theory was

substantially in place by 1926. Heisenberg's nonclassical treatment of observable
physical quantities constituted one of the two original versions of the theory. The other
alternative presentation of quantum mechanics was put forward around the same time
by E. Schrodinger. These formulations were offered from two different mathematical
points of view and were soon proved to be equivalent theories.
Schrodinger drew some of his inspiration from studies of the theory of light
undertaken by W R. Hamilton in the 19th century. Hamilton had investigated the
connection between the equations of geometrical optics and wave optics, and had
demonstrated mathematically how the one description could be regarded as an
approximation to the other. Schrodinger argued that classical particle dynamics
should bear a similar relation to a proposed wave theory for a quantum particle. De
Broglie's matter wave was in immediate harmony with this notion, and so Schrodinger
adopted the hypothesis as a main ingredient in his theory. The matter-wave approach
to quantum physics made wave equation, while Heisenberg's
use of solutions of a
picture gave a representation of measurable quantities by means of matrices.
Schrodinger's wave mechanics had more intuitive appeal than Heisenberg's matrix
mechanics because the wave picture was easier to visualize. The mathematics of waves
was also well understood, while the matrices in Heisenberg's formalism had infinite
dimension and were therefore rather unfamiliar.
A comprehensive interpretation was essential to the mathematical consistency and
physical content of this new theory. The solutions of Schrodinger's wave equation
were correctly interpreted by M. Born (over Schrodinger's objections) in 1926. The
probabilistic aspects of the theory were formalized through this important contribu-
tion.

Quantum physics became a quantitative science as a consequence of these dis-

coveries.The new theory was based on a coherent system and furnished a
of principles
predictive scheme by which the formalism could be tested. These goals had been
awaiting fulfillment for more than a decade and were at last achieved.
This chapter is intended as an introduction to the basic concepts of quantum
mechanics. We include all that we need, here and in Chapter 6, to conduct a

219
220 Quantum Mechanics

Erwin Schrodinger

satisfactory survey of modern physics. Schrodinger's wave equation is the keystone of

the entire presentation. The solutions of this differential equation enable us to describe
such phenomena as the occurrence of stationary states and the quantization of energy.
The probability interpretation of the wave function is also introduced in this chapter.
The probabilistic treatment then tells us how to define the physical observables for a
quantum particle. All these new ideas and methods are needed as we depart from
classical physics and proceed toward the quantum theory of the structure of matter.

5-1 The Schrodinger Equation

Most of our discussion in this chapter is devoted to the special case of a particle in
one -dimensional motion. Our intention is to introduce the new mathematical procedures
in certain familiar situations where the behavior of the particle is described by a single
linear degree of freedom. Figure 5-1 shows an oscillating mass on a spring and a freely
sliding bead on a wire as two such examples. Each situation involves constrained motion

in which the quantum particle is highly localized with respect to the two coordinates
transverse to the particle's one degree of freedom. This constraint allows us to ignore
two out of three coordinates in all stages of the treatment. We also assume that the
motion of the particle is governed by a conservative force so that we can define a
potential energy as a function of the remaining spatial variable.
Let us assume that the particle is able to move in the x direction and that the
motion is nonrelativistic. We let the potential energy be expressed by means of a
function V(x) so that the force on the particle is given as F = —dV/dx. Classical
mechanics would have us determine x(t), the position of the particle at time /. This
sort of result is not the objective of interest in quantum mechanics. Instead, we want to
find the wave function ^(x, t) for the matter wave and then use ^ to make
predictions about the probability of random detection of the particle. These goals
 5-1 The Schrodinger Equation 221

Figure 5-1

Particle motion constrained to one dimension.

Constraining

Constraining tube

cannot be addressed until the wave equation for ^ is specified. It is obvious that we
are looking for a partial differential equation in the independent variables x and t.
The equation is evidently supposed to contain the given potential energy V(x) in one
of its terms.
Let us turn for guidance to the problem of wave propagation in a one-dimensional
medium. We recall the appropriate wave equation as

2 2
d u 1 d u
(5-1
dr 2 ^Yi 2

where v is the speed of propagation and u(x, t) is the displacement of the vibrating
medium. Equation (5-1) is linear in u; therefore, the existence of independent solutions
u (x, t) and u 2 (x, t) implies the existence of another solution given by the sum of
{

waves

«,(*, /) + u 2 (x, t).

In general, the linearity of the equation allows us to take any set of solutions u k (x, t)
and construct arbitrary linear combinations in the form

to obtain other solutions. This property is known as the principle of superposition. The
concept is fundamental and the construction of wave
to the description of interference
packets, since both of these procedures involve the summing of waves. We want the
desired equation for the matter wave to be linear in the wave function ty(x, t) so that
matter waves can also enjoy these important consequences of superposition.
We observe that Equation (5-1) is a differential equation of second order in the time.
It follows that two pieces of initial data must be given to determine the subsequent
time dependence of the solution. Thus, we may take an initial specification of
displacement and velocity for all points in the medium as

du
.(x.O) and (-1)

and then predict a unique solution u(x, t) for any later value of /. The matter wave
222 Quantum Mechanics

ty(x, t) is subject to rather different considerations. We learn as follows that the

Schrodinger wave equation is of first order in the time so that the wave function is

uniquely determined from a single initial condition given by the behavior of ^{x, t)

at t = 0.

Let us examine this feature of the quantum theory by considering the case of a free
particle. We choose the arbitrary reference level in the definition of the potential
energy V(x) so that the constant value of V is equal to zero for a zero force. A
localized free particle is described by means of a wave packet of the form

*(x,t) = r A{k)e i{kx - Ut)

dk,

where ^ has properties as discussed in Section 4-6. The wave parameters satisfy the
relation

<o = —
M
2m
2

(5-2)

for a particle of mass m, and so the formula for the free-particle wave packet becomes

/oo
kx - (h/2m)k
.,

A(k)e-\ ~^dk. (5-3)

-oo

We note that the k dependence of the complex exponential function establishes a

correspondence between second-order differentiation with respect to x and first-order
differentiation with respect to t, whereby

<9
2
* ,oo
- (h / 2m
T =( A{k)(ik)
2
e'\
kx
»'Uk
dx 2 J-oo

and

d^ ,oo / in \
= A(k)\
V
k
2
\e'^-' h/2m)k ~'Uk.
dt J-*, '\ 2m J

2 2
These two results tell us that the quantities (ih/2m)d ^ /dx and d^/dt are
identical. We express this equality as

2 2
h d d
-V =
2
ih —* (5-4)
2m dx dt

and thus obtain the Schrodinger equation for the wave function of a free particle.
Note that the Equation (5-4) are of different order because
partial derivatives in
the wave parameters co and k appear with different powers in Equation (5-2). We are
again reminded of the Planck-Einstein and de Broglie formulas

E= h(x> and p = hk, (5-5)

and we recall that the relation between w and k expresses the nonrelativistic energy*
 5-t The Schrodinger Equation 223

relation for a free particle of mass m:

2
P
i~=E. (5-6)

This connection holds for each component wave in the matter-wave packet <f
i . Our
observations suggest a simple procedure that produces the Schrodinger equation
directly from the energy relation. We find that Equation (5-4) is obtained immediately
if the two sides of Equation (5-6) are interpreted as differential operators according to the
substitutions

r) -

p
2 -* -h 2 —-, and E^ifi —r)

,
(5-7)
ox at

where the operations are allowed to act on the wave function ^(.v, / ). This proposition
introduces a pair of representation rules for the new quantum treatment of the physical
2
quantities p and E.
It has already been noted in Section 4-6 that the monochromatic wave functions
— — £'(** _w wave
cos(kx u>t), s'm(kx co<), and are possible solutions of the ordinary
equation. We now observe that the cosine and sine wave functions cannot possibly
occur as solutions of Equation (5-4) because of the appearance of the first-order time
derivative. In fact, the presence of the imaginary number / in the time-derivative term
leads us to expect a complex-valued time dependence in ^( x, t ).

Let us not be tempted to regard our deduction of the Schrodinger equation as a

derivation. We should realize that Equation (5-3) is an assumed free-particle wave
packet whose chosen form is desirable as a matter wave for a localized particle.
Equation (5-4) is then shown to follow from this assumption. Such a heuristic
approach is quite proper since the Schrodinger equation is not to be considered as a
derivable result. Instead, the equation represents a hypothesis whose validity is to be
ascertained by examining the predicted consequences. Schrodinger's theory is intended
to describe a certain body of conceivable measurements and, like Newton's theory, is

supposed to work within a certain regime of applicability. Equation (5-4) is somewhat

akin to Newton's first law, since the principles refer to a free particle in both
situations. Our next concern is the analogue of Newton's second law, as we proceed to
Schrodinger's wave equation for the case of a nonfree particle.
As preparation, let us return to the free-particle case and include the potential
energy as a nonvamshing constant in the analysis. This tactic is not as contrived as it

may seem since the results are going to lead us to something new. A constant potential
energy V is incorporated in the energy relation for a particle of mass m by writing

—
p
Im
+ V=E, (5-8)

where both E and p are constant quantities for a free particle. We may use the simple
monochromatic wave function

- Ul)
*{x,t) = Ae ilkx (5-9)

and thereby assign a precise momentum hk, since we are not concerned with the
question of localization in this part of the discussion. The wave number k and the
224 Quantum Mechanics

angular frequency u; satisfy the equality

2 2
h k
+ V= ho> (5-10)
1m

by virtue of Equations (5-5) and (5-8). This relation between w and k tells us that the
wave function in Equation (5-9) must obey the differential equation

2 2
h

2m dx
d
^ + V* = —
2
ih
d

dt
*. (5-11)
V

Thus, we obtain another version of the Schrodinger equation for a free particle, and
we conclude that no real physical distinction exists between Equation (5-4) and
Equation (5-1 1).
The same comments hold for the alternative wave function

- kx ~ at
*(x,0 = Ae i( \ (5-12)

We observe that Equations (5-9) and (5-12) refer to waves traveling in opposite
directions, since the expressions differ only in the sign of A', and that Equation (5-10)
controls the wave parameters without regard for this sign. It is therefore obvious that
both wave functions are equally valid solutions of the free-particle Schrodinger
equation.
We see the purpose of using a nonzero constant potential energy for a free particle
when we turn to the situation of interest, where the particle is not free and the
corresponding potential energy is not constant. A typical varying potential energy
might resemble the function shown in Figure 5-2. The energy relation maintains the
form of Equation (5-8), although the momentum p can no longer be treated as a
constant. It wave number k cannot be employed to parame-
follows that a constant
trize the wave function as in Equations (5-9) and (5-12). We can still regard £ as a

constant in Equation (5-8) and retain a constant angular frequency co. (We should
also say that our discussion assumes a choice of constant E that exceeds V(x) for all
values of x. This stipulation is already built into Figure 5-2.) It would seem that
Equation (5-10) has no further use now that V enters as a function of x. Let us
suppose, however, that we approximate the potential energy function V{x) in the
manner illustrated in the figure, so that the x axis is divided into pieces and average
values of the potential energy are substituted for V(x) in all the intervals. The figure
shows a new potential energy function that approximates V(x) by a stepwise construc-
tion of constant potential energy segments. The particle acts like a free particle in
every interval, and so the conclusions of the preceding paragraphs are still applicable
on this basis. We therefore identify a different constant wave number k interval-by-in-
terval and again rely on Equation (5-10) with a correspondingly different constant V
in each of the intervals. Hence, Equations (5-9) and (5-12) become valid forms for
ty(x, t), as Equation (5-10) holds in every interval for either of these wave functions
or for any combination. This piecewise construction of ^ satisfies the Schrodinger
equation as given Equation (5-11) for the case of a stepwise potential energy. We
in

can approximate the original potential energy function V{ x ) to any desired accuracy
by this procedure. Therefore, we argue that the corresponding exact wave function
ty( x, t ) can be found as an exact solution of Equation (5-11) by allowing the equation
to contain a potential energy that varies with x.
 5-1 The Schrodinger Equation 225

Figure 5-2

Approximation to a potential energy function

V(x) by a sequence of constant potential

energy segments V ,V ,V2 ,.

l
. . .

E
1 1 1
1 1 1 1 1 1

Vj

\ —'V
1

We should look for plausibility instead of rigor in these arguments. The result

asserts that quantum mechanics in one dimension is expressed in terms of a wave

function ^(v, 0, where ^ satisfies the Schrodinger equation as written in Equation
(5-11) for any given potential energy V(x). We are supposed to accept this assertion
and become confident of its validity by using the procedures and examining the
consequences.

Example

kx ~ ut -««)
The functions e
'(-
)
ancJ ^'<~ are solutions of the Schrodinger equation
for a free particle, so any combination of the two functions is also a solution. Let
us gain some practice with the differential equation by considering the particular
combination

^( x, t) = A cos kxe
'<*>' _ \ gi(kx-ui) _|_
^i(-h-wl)]

We confirm directly that we have a solution by performing the following

differential operations:

1 2
h d h-
2
-\
k + V A \ cos kxe
2m ax- 2m
and

ih — ^ = huA
8t
cos kx
e~' ul
.
226 Quantum Mechanics

It is clear that the Schrodinger equation is satisfied by ^ if the wave parameters

co and k obey Equation (5-10). This free-particle wave function is a superposi-
tion of two component waves traveling in opposite directions.

5-2 Probability Interpretation

Schrodinger's wave equation is only one of the ingredients in the Schrodinger theory.
Attention must also be given immediately to the proper meaning of the solutions of
the new equation. Our remarks in Chapter 4 suggest that we adopt a probability
interpretation for these matter-wave solutions. We now wish to pursue this suggestion
so that we can learn how the matter wave is used to determine probabilities for the
random detection of a quantum particle. We continue with the one-dimensional
approach in order to introduce these important considerations while the theory is in its

simplest mathematical stage.

Schrodinger originally regarded the wave function ^ as a visualizable physical
wave. Born took ^ to be a mathematical wave function instead and identified |^|
2
as
the basic observable quality of the matter wave. Born's interpretation prevailed,
despite the fact that his proposal did not meet with Schrodinger's immediate approval.
An acceptable solution of the Schrodinger equation is supposed to provide a
complete description of a physical state for a given system. This statement means that all

observed properties of the system are obtainable from the solution, once the wave
function ty has been found. A given physical system is defined for a particle in one
dimension by a particular specification of the potential energy V(x). The resulting
differential equation for ^ is of first order in the time, and so a unique wave function
is determined if the initial behavior of the state is prescribed. This aspect of the wave
function is associated with the differential operator ih d/dt in the equation. The

Max Born
 5-2 Probability Interpretation 227

presence of the imaginary factor implies that the time dependence of ^ must be given
by a complex-valued solution. This general property of ^ suggests that the wave
function itself cannot be a measurable physical quantity, as in the case of solutions of

the ordinary wave equation. Instead, the wave function must be a purely mathemati-
cal device to furnish probabilistic information about the state of the system. The
Schrodinger theory is then supposed to include further rules that determine the
various observable properties of the particle when the system is in such a state.

The fundamental observable entity in this interpretation is the probability of

finding a particle at a certain location. Such a quantity must be real and positive,
mathematical properties not possessed by the complex function ^. Physical properties
of matterwaves have been proposed in Chapter 4, where distributions of probability
have been likened to distributions of wave intensity. The definition of the desired
probability is expressed accordingly in terms of the square of the modulus of ^,

because this (and only this) operation on the wave function conveys the meaning of an
intensity for a complex-valued wave.
Let us postpone the actual definition of the probability for a moment and call
immediate attention to an especially desirable feature of the quantity ^*^. We
suppose that we have a system in which particles are transmitted by a double slit, and
we assume that the wave function for a single particle is written as the sum of two
complex waves

* = ¥, + %.

The separate parts of ^ are identified as single-slit wave functions with modulus and
phase such that

^, = |¥,|*''*' and % = \%\e^.

We are allowed to superpose these waves because of the linear property of the
Schrodinger equation. The double-slit probability involves the square of the wave
modulus:

|*|2 = (¥* + **)(¥, + %)

= |^,|
2
+ ^2*^, + ¥f% + \%\ 2
= \%\ 2 + |^ 1
||^,|[f'
< *>-*-' )
+ *-«"<*|-*2)] + |¥2 2

The result contains the two single-slit quantities l^,!

2
and \^,)
2
, as well as the
additional interference term

2|* 1
||* 2 |cos(4> 1
- 4> 2 ).

We observe the effect of this phase-dependent contribution in the phenomenon of

double-slit interference. The phases <f>, and <J> 2
vary for different points of observation
and produce constructive and destructive interference in a pattern just like that found
for light in Figure 4-5. We note that the interference pattern results from the
superposed form of the wave function ^ for a single particle. The result determines
the distribution of probability for detection of any such particle in a beam of particles
228 Quantum Mechanics

Figure 5-3

Probability density for a localized particle in

one dimension.

Ax-

incident on the double slit. We now clarify these observations by expressing the
probabilistic properties of ^ in terms of a new defined quantity.
Born's interpretation identifies ty*^ as the probability density for a system in a state
with wave function ty. This quantity depends on the variables that specify the degrees
of freedom of the system. Thus, a single particle in one-dimensional motion has
probability density

P{x,t)=\*{x,t)\\ (5-13)

in which Sk * ^ may exhibit a variation with time. Figure 5-3 shows a sketch of a
possible shape for the x dependence of P at a particular time t. If a certain value of

the coordinate x is selected and an infinitesimal interval dx is taken, as in the figure,

then the probability of finding the particle in the given interval at time / is defined by
the expression

P(x, t) dx =\ty(x, t)\" dx.

The probability of finding the particle in the finite interval Ax between the indicated
points x x
and x 2 is determined by computing the integral

f \V(x, t)fdx.
The total probability of finding the particle somewhere in the entire one-dimensional
space is then found by extending the range of integration to get

2
\^{x, t)\ dx.
/

Note that ^(x, t) must be a suitably localized wave function to ensure the conver-
gence of this integral. Note also that the numerical magnitude of ^ is not fixed by
solving the Schrodinger equation, since any solution ^ may always be multiplied by
any constant and still serve as a solution. The probability integral is employed to
remove this arbitrariness and set the overall scale of ty. The wave function is said to
be normalized if the solution ^ satisfies the additional restriction

/oo n
\*(x,t)\~dx = 1. (5-14)
 5-2 Probability Interpretation 229

This normalization condition means that the particle has unit probability to be found
somewhere in all of one-dimensional space.
The probability density makes allowance for a possible time dependence in the

local behavior of the probability. This feature of the interpretation of ^ suggests the
introduction of another local quantity to represent the flow of probability. An
appropriate definition emerges from consideration of the free-particle equations
obeyed by ^(.v, t) and by <fr*(x, t):

2 2 2 2
h d d d 8

2m 3x
-V =
2
ih —*
dt
and
fi

2m dx
r^*
2
= -ih —
dt
¥*.

Note that the two equations are related by complex conjugation. These formulas may
be used to analyze the time dependence of the probability density for a free particle:

d 3* d**
dr ' dt dt

( h d
2
*\ l h d
2
**
\ lim ox J \
2im ox

h i d
2
* d
2 **
= \J/
* _ \W
2
2im 8x 3x 2
3
*
8* d**
\j/ >i/

~Yx 2im \ dx dx

The equality can be rewritten to read

— P(*,t) + —j(x,t) = 0. (5-15)

at ox

The result serves to introduce the probability current density

h ( 8* d-** \

j(x,t)-— \* m -
lim \
r T
ox
-
~
ox
-*
)
. (5-16)

This new quantity appears in the defining equation as a flux of probability. Thus,
Equation (5-15) has the form of a conservation law in which a time variation of the local
probability is compensated by a space variation of the flux across the local region.
It is possible to cast the probability conservation law in integral rather than
differential form by considering the probability of finding the particle in some finite
interval Ax = x 2 - x v The rate of change of this quantity is evaluated as follows:

-d fx 2
P{x,t)dx=
fx 2 d
P— P{x,t)dx
-

dt J X] f JXi at

2
= ~ ^-j(x,t)dx=j(x ,t)-j(x 2 ,t).
f
Jx, ax
i
(5-17)

The result represents the net flow of probability into the interval Ax. Equation (5-15)
carries over in the case of a nonfree particle, with the same definition for the
230 Quantum Mechanics

probability current density j{ x, t ). The details are left to be examined in Problem 2 at

the end of the chapter.
The probability interpretation of the wave function has an immediate extension
from one to three dimensions. Let us take a brief excursion into three-dimensional
space and identify some of the more self-evident facts for later reference. We let the
wave function ^ represent the state of a three-dimensional system, and we use the
notation ^(r, t) to indicate the dependence on the three coordinates (x, y, z) as well
as the time. The probability of finding the particle in an infinitesimal volume element
di at time / is then written as

2
\*(r,t)\ dT,

so that the corresponding probability in a finite volume At is given by the volume

integral

/ |*(r,0| ^.
•'At

The overall scale of the wave function is fixed by requiring ^ to obey the restriction

2
|^(r,/)| ^r = 1. (5-18)
fall space

This normalization condition generalizes the formula in Equation (5-14) for applica-
tion in three dimensions.
Section 4-6 has provided us with an intuitive picture of a matter wave for a
localized quantum particle. We have just learned that the property of localization is

described by the distribution in space of the real positive probability density ^*^.
Let us hasten to clarify our understanding of this quantity, since the notion certainly
does not mean that the particle itself is distributed over all space. Instead, the
probability of locating the particle is understood to have this interpretation. To
illustrate, let us appeal to the measurement process in a single-slit experiment and
recall that the location of the particle is not determined with certainty after passing
through the slit. We let the infinitesimal element dr represent the volume of a certain
cell in a particle detector, and we take the value of ^ * ^ dr to be the probability of
detecting the particle in the given cell. Note that the entire particle is either found or
not found in the cell at a particular instant. Hence, the process of measurement for a
random count somewhere in the detector system. If we make
single particle results in a
the same observations on a large number of similar particles in separate single-slit
experiments, we obtain a distribution of random counts that conforms to the distribu-
tion in space predicted by the probability density ^P*^. Thus, we find that the wave
function ^ for a single particle determines the single-slit diffraction pattern for a beam
of particles according to this probabilistic interpretation.

Example

We have glossed over a subtle point in the normalization of the wave function in
Equation (5-14). It is obvious that the element of probability <&* <}'dx may
<r
depend on t because of the t dependence of i . This dependence on / remains
after the integration over x, and yet the total probability is set equal to unity
 5-3 Stationary States 231

with no account taken of the apparent / dependence on the left side of the

equation. We can justify the result, specifically for the case of a free particle, if

we consult Equation (5-17) and rewrite the formula for the time derivative of
the probability as

d
- fx 2

dt J Xl
^**dx =
2im
h I

\
**-3*
dx
d**
—
dx

It is clear that the probability of finding the particle in the finite interval
Ax = x2 — x x
may vary with t, since the right side of this equality is not
necessarily required to vanish. Equation (5-14) pertains to the infinite interval,

however, and so the question concerns the behavior of the equality in the limits
at, —> — oo and x 2 -» +oo. A properly localized wave function must vanish
rapidly at infinity so that

8* 8**
<$r * _ \J/- as x, — —
> oo and x, -» oo.
dx dx

co 2
Itfollows that the normalization integral / 00 vI'(^, t)\ dx has no t dependence, |

and so Equation (5-14) can be introduced to set the resulting constant value of
the integral equal to unity.

5-3 Stationary States

The Schrodinger theory is based on a partial differential equation whose solution

determines the space dependence and time dependence of the wave function. The
relevant mathematics goes beyond that employed in Newtonian mechanics, where the
dynamics entails the solution of an ordinary differential equation. Fortunately, the
mathematical treatment of partial differential equations of the Schrodinger type is
well developed and straightforward. The most useful method of solution is provided
by the technique of separation of variables. This procedure leads us directly to one of the
central ideas in quantum physics — the concept of stationary states.

The wave function has independent variables x and / in the one-dimensional

version of quantum mechanics. We can separate the x dependence from the /
dependence if we seek solutions in which the wave function is written as a product of
functions of a single variable:

¥(*,*) =*(*)/(<) (5-19)

This expression is supposed to satisfy the Schrodinger equation, and so the product xpf
must obey a modified form of Equation (5-11):

2
h d 2xp df
-^—77/+
2m dx~
V4,f=ih)-
dt

Note that the partial derivatives acting on the wave function ^ turn into ordinary
derivatives acting on the factors \p and /. If we divide both sides of the equation by
 .

232 Quantum Mechanics

the product of factors \pf, we obtain the equality

*> j2
—
j

—^(x) + V(x)^{x) ih-f(t)

Zm dx dt
(5-20)
+ (*) f(t

This result has an interesting structure, inasmuch as the left side of the equation
depends only on x while the right side depends only on t. It is possible to have an
equality between a function of x and a function of t only if each function is a
constant. We therefore set each side of Equation (5-20) equal to a separation constant X
and obtain separate equations for \p and / in which X appears as a common
ingredient:

2
h d 2^
2
+ Vrp = Xxp (5-21)
2m dx

and

df
ih-=\f. (5-22)
dt

Note that V must occur as a function of x alone; the method of separation of variables
would not apply otherwise. We conclude from this procedure that the Schrodinger
equation has solutions in the form expressed in Equation (5-19), provided the two
ordinary differential equations have solutions for the factors \p and /.

Let us look first at the solution of Equation (5-22). The first-order differential
equation can be solved at once to yield

-i\i/h
f( t )= e t (
5 . 23 )

apart from an arbitrary multiplicative constant. This complex exponential solution

describes an oscillating function of time:

A X
f(t) = cos — — / i sin — t.
h h

The wave function constructed in Equation (5-19) is therefore characterized by a

unique angular frequency co, connected to the separation constant X through the
relation

X
(0 = —
h

A unique energy may also be associated with this type of wave function by virtue of
the Planck- Einstein formula:

E= hco = \. (5-24)

Thus, Equation (5-19) describes a system in which the quantum particle is found in a

state of precisely specified energy.

Equation (5-24) tells us that the separation constant is the same as the energy
parameter of the state. The actual value of the energy remains to be determined from
 5-3 Stationary States 233

Equation (5-21), the other of the two ordinary differential equations in the construc-

tion of the wave function. We substitute E for A and rewrite the equation as

2
h d2
~1TT1^ X ) + V(x)4,(x) = E^(x). (5-25)
Im dx~

The resulting differential equation for \p(x) with energy parameter E is called the
time-independent Schrodinger equation. It is obvious that we must be given the potential
energy V(x) before we can proceed to solve for the unknown function yp(x). We note
that we are able to establish the form of the t dependence of ^ in Equation (5-19)
without any knowledge of the form of V(x). Equation (5-25) then plays the main role
in the remaining construction of ^. The product expression in Equation (5-19) is
indeed a valid solution of the Schrodinger equation, provided the value of E corre-
sponds to a physically allowable solution 4 ( x ) from the time-independent equation.
/

An allowed value of E is called an energy eigenvalue. The associated physically allowed

solution \p(x) is called the corresponding eigenfunction. We
must learn how to solve
Equation (5-25) in order to find these last two ingredients and assemble the wave
function.
The method of separation of variables produces solutions of the Schrodinger
equation in the special form

*(.v,0 =ip{x)e-' E " h . (5-26)

There is certainly no reason to suppose that every wave function is necessarily of this
sort. Indeed, we know that any number of these allowed solutions can be superposed
to generate a valid wave function. We also know that the determination of X
P( x, t ) in

a particularproblem depends on given information regarding the initial wave

function ^(x,0). The point to emphasize in this section is that solutions of the type
expressed in Equation (5-26) are special wave functions whose mathematical proper-
ties describe the stationary states of the system. To appreciate the terminology let us
examine the probability density associated with the state in Equation (5-26). The
entire time dependence of ^ is contained in a single complex exponential factor of
unit modulus, and so the square of the modulus of ^ has no dependence in such a t

state:

2 2
\*(x,t)\ =\^(x)\ . (5-27)

Hence, the state is said to be stationary because the probabilistic aspects of the
corresponding wave function do not vary with time. We have already attached
additional significance to this wave function by noting above that the energy of the
state is a precisely defined quantity.
We expect to find a set of allowed £"s and i^'s as solutions of Equation (5-25) for
any given potential energy V(x). These solutions represent the energy levels and
stationary state eigenfunctions for the particular dynamical system. We elaborate on
this observation by turning to special cases of quantum systems in the next two
sections.

Example

Let us accept the fact that the Schrodinger theory always yields a set of energy
eigenvalues E ,E2 ,...,
{
corresponding to the set of stationary state wave
234 Quantum Mechanics

functions

*,(*)«-*•"*, M*)*-*"*,
A particle in one of these states has a stationary probability density, as noted in
Equation (5-27). Suppose, however, that the state is a superposition of two
stationary states described by the wave function

*(x,t) = a^ x
{x)e-' E ^ h
+ a,t 2 {x)e~'^ l/h .

We obtain this function as the unique solution of the Schrodinger equation if we

are given

*(x,0) =a l
xp
i
(x) + a.^ 2 (x)

as the initial condition for ^(x, t). We then find that ty*^ is not t independent:

2 E >' /h
|*(x,0| = (afWeW + a*^*e'^' /h )(a^^ lE ^ /h + a 2 ^ 2 e-' )

2 - Ei)l/h
= \a l \^ i
(x)\ + a*a 2 iP*(x)UxyiE>

+ a*a iP*(x)^
l l ( X )e-*
E >-W' + \a 2 \
2
\$ 2 (x)\
2
.

The expression contains two oscillating terms with angular frequency

|£, - E2 \

The state represented by the wave function ^(x, t) is not stationary, and so all
its probabilistic features can be expected to oscillate with the same angular
frequency w.

5-4 The One-Dimensional Box

Several first principles of quantum mechanics have already made their appearance in
this chapter. It is appropriate that we pause and reflect on the new ideas by
considering models like the ones shown in Figure 5-1. We devote this section to the
simpler of the two indicated systems.
The illustrated example of a sliding bead on a wire is known in quantum
mechanics as the problem of a particle in a one-dimensional box. The classical
particle travels freely between the two ends of its course and abruptly reverses
direction at either end with no loss of energy. We describe this model by means of the
potential energy shown in Figure 5-4. The classical motion is confined to an interval of
length a, and the origin is taken to be at the center of the interval. The potential
energy function is then defined as

,w _/°
v
'
\ oo for
;°7*/2
\x\ > a/2,:r'
/2
- (5-28)

so that a nonvanishing force acts only at x = ±a/2. An energy E is assigned to the

 5-4 The One-Dimensional Box 235

Figure 5-4

Potential energy function V(x) for a particle

in a one-dimensional box.
V(x)

system as in the figure; hence, the kinetic energy of the particle is equal to E in the
region of vanishing potential energy. Classical motion is forbidden outside this region
because the infinite value of V exceeds any possible choice of E. Thus, the given
potential energy function provides barriers to confine the particle in the interval
[
— a/2, a/2] for any assigned energy.
Let us now insert the function V{x) in the Schrodinger equation and find the
stationary-state wave functions for the quantum particle. We learn as follows that
only certain discrete values of the energy E are obtained from Equation (5-25), the
time-independent equation for the eigenfunction \p(x). The equation takes the form

h
2
d 2^

2m dx

when x is in the interval ( — a/2, a/2) where V = 0. We rewrite this differential

equation as

d 2^
~ + k^f = 0,
dx

where

2rnE
k = ' (5-29)
2
h

and recognize the immediate solutions

cos kx and sin kx.

The potential energy becomes infinite when x is not in the range [

— a/2, a/2], and so
Equation (5-25) makes sense only if \p(x) vanishes everywhere in this outside region.
We conclude that there is zero probability of finding the quantum particle anywhere
beyond the interval [ —a/2, a/2].
The probability density is physically observable and should therefore be continuous
in x for all problems. It follows that the wave function must always be a continuous
function of x. This requirement is supposed to hold for our particle-in-a-box eigen-
function \p(x). The piecewise behavior of the function can be described by the general
 ,

236 Quantum Mechanics

solution

/ A cos kx + B sin he for - a/2 < x < a/2

^ {X ' =
, s (

~
\
for |*| > a/2.

Continuity at x = +a/2 implies two conditions on the parameters:

ka ka
A cos V B sin — =
2 2

and
ka ka
A cos — — B sin — = 0.
2 2

(We use the evenness and oddness of the cosine and sine to write the second result.)
The two equalities can be combined to read

ka ka
A cos — =0 and B sin — =0.
2 2

We cannot allow both A and B to be zero, and we know that cos(ka/2) and sm(ka/2)
cannot both vanish for the same value of k. Only two other possibilities remain:

B = and cos
ka
—
2
= so that
ka
—
2
= —
tt

2
,
—
3v
2
. . .
.

or

ka ka
A = and sin — = so that — = 77 , 2 77 ... . .

2 2

Both options are permitted, and both make equivalent predictions for the parameter
k. The allowed values of this quantity are evidently restricted to the discrete set

kn =-n, (5-30)
a

where n is any integer, odd or even.

We observe that there are two classes of eigenfunctions in this model. Cosine
solutions are found for B = and odd n:

rnrx
\p n { x) = A cos for x in the interval [ —a/2, a/2].
a

Sine solutions are found for A = and even n:

nirx
xp
n
( x) = B sin for x in the interval [ —a/2, a/2].
a

The multiplicative constants A and B remain to be determined in these formulas.

Note that the integer n serves as a quantum number to index the allowed eigenfunctions
and the allowed values of k. The energy eigenvalues are obtained from Equations
 5-4 The One-Dimensional Box 237

(5-29) and (5-30) and are labeled in similar quantized fashion:

h h~ tt~
E„ = — k\ = rn" (5-31;
2m 2m a~

We note that the possibility of an n = state is ruled out because the corresponding
eigenfunction vanishes. The lowest allowed value of En occurs for n = 1 and gives the

energy of the ground state as

i.2 2
n it

E, = (5-32)
1
2 ma

The nonzero result is interpreted as quantum zero-point energy in the ground state of
the system. We have encountered this notion before in our comments on localization

in the context of the uncertainty principle.

Let us summarize our conclusions and express the stationary-state wave functions
in normalized form. We write the results as follows:

-iEj/h
cos e (odd n
a a a a
*„(*,') = for - - < x < - (5-33a)
2 mrx -' E r,'/ f
2 2
sin e
'
(even n)

and

%(x, t) = for |x| > a/2. (5-33b)

The factor \2/a ensures that each tyn satisfies the normalization condition

/°° , ,2 ra/2 , ,2
\%{x,t)\ dx= I \%{x,t)\ dx.
_M J- n /9

We verify this property of the wave functions in the first example below. The energy
eigenvalues E n
appear in the / dependence of Equations (5-33) as multiples of the
ground-state energy:

E„ = n E,
2
(5-34)

It is convenient to organize this information about the stationary states according to

the scheme of energy levels and normalized eigenfunctions shown in Figure 5-5.
Note that the zeroes, or nodes, of the eigenfunctions increase in number as the
energy E n and the quantum number n increase. This property is a general characteris-
tic of the stationary-state eigenfunctions for any problem. It is apparent from the

figure that the eigenfunction \p„(x) has n + 1 nodes in the interval [

— a/2, a/2]. In
fact, a comparison between Figure 5-5 and Figure 2-6 reveals how closely the various
functions resemble the standing waves on a vibrating string.
The two classes of wave functions in Equations (5-33) are distinguished by their
even and odd behavior under a change of sign in the variable x —* —x. We see from
Figure 5-5 that the states alternate in this respect as the energies increase. The
238 Quantum Mechanics

Figure 5-5

Energy levels and normalized eigenfunctions for a particle in a one-dimensional box.

= .12. cos 3jra

A3

a
/\ 7
VJ Vy

V=

evenness or oddness of a given particle-in-a-box eigenfunction is expressed by writing

$S-x) = + ^n( x ) for odd n (5-35a)

and

$ n ( — x) = — ^ n {x) for even n. (5-35b)

This symmetry or antisymmetry of a stationary-state wave function under the

substitution x —* — x is called the parity of the state. Equations (5-35) may be restated
to say that ^ (xld n
has even parity and ^ vcn (
. „ has odd parity. The parity is always
found to be a manifest property of the states whenever the potential energy of the
particle is an even, or symmetric, function of x. We should expect the observable
probability density in a stationary state to be symmetric under the replacement
x —» — x if the dynamics of the particle is governed by a symmetric potential energy
V( x ). We then conclude from the even behavior of ty* x f
i
n
that the wave function 4^
must be either an even or an odd function of x. The particle in a box is the simplest
such example in which the system has a symmetric potential energy and displays
stationary states of definite parity.
The eigenfunctions »^ n (^) illustrate another mathematical concept known as ortho-

gonality. The property of interest refers to integrals of pairs of eigenfunctions written as

a /2
cos
n 7TX
cos
n TTX
dx .
fa/2
/ sin —
"V
cos
n 7T.X

dx ,

/ a/2 a a J -a/2 a
 5-4 The One-Dimensional Box 239

and
a /2 rnrx nrnx
sin sin dx.
/ a/2 a a

These expressions occur frequently in applications of the model. The integrals are
found to vanish, and the functions are said to be orthogonal, whenever the quantum
numbers n and n' have different values. Orthogonality is a general result for families
of eigenfunctions appearing in all kinds of problems. It is obvious in the case at hand
that the second of the three integrations is equal to zero, because the integrand is odd
and the range of integration is symmetric about the origin. The other two integrals are
left to be examined in Problem 20 at the end of the chapter.

Example

The problem of the particle in a box has many illustrations and applications.
Let us look first at the normalization of the wave functions in Equations (5-33).
We note immediately that the range of the normalization integral shrinks from
/f oo to j- a2/2 since the wave functions vanish outside the interval —a/2, [
a/2].
The cosine eigenfunctions produce the following integration:

fa/22 2 nwrx
^TITTX 2
*
fa/2 ra /2 l
1 / 2ri7TX
f°° f"/
I
T
I^J" dx
2
= —cos"
2
dx = — f — 1 + cos dx
•'-oo
f
J -a/2a a aJ- a /22\

a znirx
x + sin-
a \ 2niT a
-
a/2

The sine eigenfunctions produce the same integration except for the sign of the
second term in the end result. This contribution vanishes at the two limits, and
so both calculations reduce to the same first term and give the value unity, as
announced.

Example

Let us turn next to the formula for the energy of the ground state in Equation
(5-32) and apply the expression to a neutron confined in a linear region of
~
nuclear size. We take a = 10
14
m for the length of the box and get

2 2 2
h 7T [(1.05 X 10" 34 J •
s)t7/10~
14
m]
-27
2ma 2
1

2(1.67 X 10 kg)(l.60 X 10~ 13 J/MeV)

This amount of zero-point energy is comparable with the scale of energies for
the constituents of nuclei.

Example

The quantization of states is the main nonclassical result of this model. Figure
5-5 reveals a separation between the discrete energy levels which increases with
the quantum number n. Let us interpret this observation in the light of Bohr's
240 Quantum Mechanics

correspondence principle and examine the limit of large quantum numbers. The
separation of adjacent levels is obtained from Equation (5-34):

A£„ = E n + l
-E n
= [(« + l)
2
- n-\E = x
(2n + 1)£,.

We note that the energy difference A£ n

grows linearly with n while the energy
En grows quadratically. Hence, the ratio of these quantities tends to zero for
large n:

A£„ (2n+ 1)£, 2

'

£„ " 2£ i
«

We recognize this as a sort of classical limit in which the discreteness of the levels
becomes increasingly difficult to establish, even as the levels grow farther apart.

Example

Let us investigate the classical limit from another angle by applying the
quantum formulas a macroscopic particle, such as a 5 g bead on a 40 cm wire.
to

We learn immediately that the nonzero ground-state energy of the particle is

extraordinarily small:

/zV [(1.05 X 10~ 34 •

s)ff/0.4ml"
= = LJ ~

= 6.80 X 65

X 10"-r-{
£, ;
2
-.
10 J
J.
1
3
2ma 2(5 kg)

It would be difficult to distinguish this quantum ground state from the classical
state of rest. Let us suppose instead that the bead is moving with speed 2 m/s.
We can try to associate a quantum number with this state of motion by
consulting Equation (5-31) and identifying the kinetic energy

2 2
m h ir
—v 2;
= n
y

'

2ma 2

The resulting value of the quantum number is enormous:

mva 2mva 2(5 X 10" 3 kg)(2 m/s)(0.4 m)

,4
= 1.21 X 10
31
.
'

~~h^
'

h 6.63 X 10 J •
s

It would be difficult to insist that such a particle is in a discrete quantum state

since the energy would have to be known with incredible accuracy to distinguish
the state from its immediate neighbors. Discreteness of energy can scarcely be
regarded as a detectable property of this macroscopic particle.

5-5 The Harmonic Oscillator

The other of the two illustrations in Figure 5-1 shows the example of an oscillating
mass on a spring. The classical oscillator is an important topic in physics, and so the
 5-5 The Harmonic Oscillator 241

quantum oscillator Is a natural model to study in our introduction to the Schrodinger

theory. We begin by recalling the following classical results as background for this

investigation.
The classical particle is subject to a restoring force proportional to the displacement
from equilibrium. The oscillator has potential energy

V{x)= -x\ (5-36)

so that the particle experiences a force

dV
F= = — kx
dx

where k is the force constant of the spring. Newton's law then provides the differential
equation for the displacement of the particle:

m —— =
d x
2
— kx.
dt

The solution determines the displacement and velocity as

x(t) = A cos(w < + <f>)

and
dx
v( t ) = — = —u A sin( co / + <£)
dt

and thus parametrizes the motion in terms of amplitude A, phase angle <£>, and
angular frequency

wo =
V m

These expressions for x and v appear in the formula for the total energy and produce
a constant of the motion:

m k
E= K+ V = -v 2 + -x 2
2 2

m k
= (0
o^ 2sin2 ( wo' + <M + -^ 2 cos 2 (« + Z 4>)
Y
k
= -A 2
.

This result can be rearranged to give » as a function of x:

-(e-^
m\ 2
2
)
/
=J-(A
m
-x
V
2 2
)
242 Quantum Mechanics

Figure 5-6 Figure 5-7

Potential energy V(x) for a harmonic Classical probability density for a harmonic
oscillator. Classical motion with total energy oscillator.
E is not allowed in the region |*| > A, where P cl (x)
V exceeds E.
V(x)

Y////////A V/////////<
Forbidden Allowed Forbidden

It is obvious that x~ must not exceed A" if v is to be a physical velocity for a classical
particle.
The classical picture can be visualized with the aid of Figure 5-6, which shows the
potential energy V(x) along with a chosen value for the constant total energy E. We
note that any choice of energy is permitted in the classical treatment of the problem.
The figure indicates that

2E
V(x) = E = +A
at x
T
and that classical motion is forbidden if \x\ > A. If x is in the allowed region
— A, A], a classical probability density can be defined to express the likelihood of
finding the classical particle in a specified interval dx. The corresponding probability
Pd ( x) dx must be proportional to co dt, the portion of the cycle of oscillation that the
particle spends in the given interval. We find that the probability density is given by
the formula

/'.>(*) = (5-37)
n{£~-

The proof of this result is left to Problem 1 1 at the end of the chapter. Figure 5-7
shows how the function P c] (
x ) describes an increasing probability for intervals near
the turning points x = +A, where the oscillating particle reverses its motion.
We can use the harmonic-oscillator potential energy in a variety of physical
applications that do not actually contain a mass-arid-spring system. The interaction of
the two atoms in a diatomic molecule is a case in point. Figure 5-8 shows a graph in
which the potential energy V varies with the separation r between the two atoms to
simulate the main dynamical properties of the molecule. The function V has an
equilibrium position at separation rQ where dV/dr is equal to zero. We can place the
,

origin of the x axis at this point by defining x = r — r and expand V in a power

 5-5 The Harmonic Oscillator 243

Figure 5-8

Model of the potential energy of a diatomic

molecule. The harmonic-oscillator potential
energy V( x ) serves as an adequate
approximation if the separation of the two
atoms stays close to the equilibrium value r .

V(x)

series about the equilibrium position:

1 / d 2V
V= V(r ) + 2
x
i
+
2 dr

Note that no term linear in .v is present since the coefficient (dV/dr) r vanishes. We
may neglect the higher powers of x if we confine our attention to bounded motion in
the neighborhood of the point r = r . The choice of reference level is immaterial and
can be shifted to eliminate the constant V(r ) and leave only the term quadratic in x.
The resulting potential energy is just like the harmonic-oscillator function in Equation
(5-36), as suggested in the figure. Any diatomic system is adequately described in

terms of harmonic-oscillator behavior as long as the energy stays near the minimum
value of V. The same conclusion holds whenever the physical problem of interest
involves a similar stable-equilibrium configuration.
The quantum description of the harmonic oscillator is based on the eigenfunction
solutions of the time-independent Schrodinger equation. These solutions determine the
quantum particle. We define this problem in terms
stationary states of the oscillating
ofEquation (5-25) by taking V(x) to be the potential energy given in Equation (5-36).
We then proceed to find a solution in the form of an eigenfunction 4'( x ) with energy
eigenvalue E. The differential equation for i// contains several bothersome constant
factors. Let us rearrange these constants so that the equation reads

d% 2m ink 2E\
Hx1
-£U = t*
and then manipulate the result to obtain the awkward-looking equality

ft d 2^ IE [W
mk dx
2
tVt
244 Quantum Mechanics

Our purpose in these steps is to construct a streamlined version of the differential

equation in which all the cluttering constants are out of the way. We accomplish this
in one more step by introducing a dimensionless variable £ and a dimensionless
parameter X according to the definitions

vmk
e = —-x 2
(5-38)

and

2E [W 2E
x=
TV7 =
w (5 " 39)

These maneuvers result in the compact equation

d'xb
—1 = (£2 -\H (5-40)
a?

in which the eigenfunction xp is regarded as a function of the new variable £. Note

that X assumes the role of an eigenvalue analogous to E in the original equation for
\p. The quantum oscillator presents a challenging mathematical problem since Equa-
tion (5-40) is a rather unfamiliar second-order differential equation.
Let us make some classical observations to illuminate the structure of this equation.
We recall that the classical particle is confined to the region \x\ < A, and we note
from Equation (5-38) that the corresponding maximum value of |£| is given by

ymk
-.2
max
= 1 A2 •
' ,

This expression simplifies when we use the classical connection between the amplitude
A and the energy E:

)/mk 2E
=
£Lx=-r-T
n k
X (classical). (5-41)

Our final result tells us how the dimensionless quantities £ and X are related in
classical physics. The relation has a special significance in the quantum problem
because of the presence of the factor (£ — X) in Equation (5-40). We observe from
2

2
the differential equation that the factors d \}//dt-' and \p have unlike signs for £-' < X
and like signs for £ 2 > X. We also realize <//(£) must have smooth behavior at the
that
matching points £ = ± vX (Recall that •must always be continuous, and note that
\p

dip/di; must also be continuous since d \p/di;~ exists at every point.) The two domains
2
£ < X and > X correspond to the allowed and forbidden regions of Figure 5-6.
!""'

Thus, it becomes apparent that the quantum problem has a nonvanishing solution in
the forbidden region, in sharp contrast to the classical situation. It follows that there
are nonzero probabilities of finding the quantum particle in locations where the
classical particle is never found.

We expect small probabilities for intervals in the region £" > X. This expectation
suggests the necessity for a suppression of the eigenfunction \p at large values of £". It
 5-5 The Harmonic Oscillator 245

is easy to show that a possible \p is provided by the gaussian function

The derivatives of ^ are

and

d 2yb 2
= t2 -f-'/2 _ ,-| 2 /2 = (* 2 _ 1^-S
f
/2

Thus, we see that the given function satisfies the differential equation provided A has
the special value

A = 1.

Equation (5-39) gives the energy eigenvalue for this solution as

hco (l fico,,

E --y\ --T' (5-42)

The eigenfunction e
~^ /2 corresponds to a normalized stationary -state wave function
of the form

•/»
/ mk \
2
%(x,t)= -j-2 ^-v^* /2A,-<£o'/*. (5.43)

This simplest solution of Equation (5-40) produces the smallest possible result for the

parameter A and the energy eigenvalue E. Hence, the wave function ^„ and the
energy EQ refer to the ground state of the oscillator, and the quantity ^w /2 represents
the quantum zero-point energy of the system. The normalization and other features of
the ground-state wave function are discussed in the example below.
If we continue the analysis we learn that all other possible solutions of Equation
(5-40) are suppressed in the forbidden region by the same gaussian factor e~* ^ 2 The .

solutions have the form

*(«) = #(0«- |,/2 ,

(5-44)

where the factor H( £ ) denotes a polynomial. This function is obtained first by deducing

the differential equation satisfied by H and then by solving the equation. We

elaborate on these mathematical details at the end of the section.
The main conclusion of the analysis is the fact that the parameter A is allowed to
have only the following discrete values:

\„ = 2n+ 1. (5-45)

We designate these special values by an integer n and thereby introduce a quantum

number to label the stationary states of the system. If we insert the expression for An in
the defining relation, Equation (5-39), we obtain the formula for the nth energy
246 Quantum Mechanics

Figure 5-9

Energy levels and eigenfunctions for the first four stationary states of the harmonic oscillator.
Shaded areas represent the penetration of the wave function into regions where classical motion
is forbidden.

7fitup

eigenvalue:

nu
En =
~Y
X» = W" + (5-46)

The corresponding eigenfunction y\/

n
is sketched along with its energy level for each of
the lowest values of n in Figure 5-9. We observe, from Equation (5-46) and from the
figure, that the discrete energies obey the equal-spacing rule

/?co„

The spacing is equal to the quantum oscillator energy hypothesized by Planck in his
treatment of the radiating blackbody cavity. The figure also shows how the eigenfunc-
tions "leak" into the classically forbidden region and how the nodes of \p n increase in
number with the energy E n
. This behavior is a general feature of any solution of
Schrodinger's wave equation.

Detail

The solutions of Equation (5-40) are found by a standard procedure in the

treatment of differential equations. We begin by assuming an eigenfunction \p of
the form given by Equation (5-44), and we proceed to deduce the differential
 5-5 The Harmonic Oscillator 247

equation obeyed by H. The derivatives of \p are

?/2 _ Hit -IV2

and

*± = %-?" - 2-£e-^ - He-?" + H&-**

We insert these results in Equation (5-40) and find

d~H dH
-2£— +
,
(|
,
2
- 1)//
rfl
2
^
Therefore, our construction of >// produces a valid solution of Equation (5-40) if

the unknown function H(£) satisfies the equation

—H
d2
.-
n - + (X-l)H-
dH
. (5-47;

The analysis of the quantum oscillator thus reduces to the problem of solving
this differential equation for every possible function H and parameter X. We see
that there is an immediate solution of the form

H= any constant with A = 1

corresponding to the ground-state wave function in Equation (5-43). The

physically acceptable solutions of Equation (5-47) are restricted to polynomials
for //(|), since any other type of function fails to produce the desired suppres-
sion of \p for large values of £ . Let us accept this fact without proof and
introduce the integer n to denote the order of these polynomials. We observe
that the potential energy V(x) is a symmetric function of x, and so we expect to
find stationary-state eigenf unctions of definite parity. Since the factor e~^ ^ in
Equation (5-44) is an even function of x, it follows that each polynomial //(£
must be either even or odd in its dependence on £ and must therefore consist of
either all-even or all-odd powers of the variable. We express the acceptable even
and odd solutions of Equation (5-47) as

k
2^ a k i- for even n
even £=

"M) = (5-48)

£ a £
k
f° r °dd n.
odd k = 1

The differential equation is then solved by finding the coefficients a k . Our main
goal is to secure the important result in Equation (5-45) for the allowed values of
 —
248 Quantum Mechanics

X. It is sufficient to examine the case of the even-order polynomial

H n
= a + a2i
2
+ a4£
4
+ • • •
+aj" where an * 0.

The derivatives of H n
are

H,: = 2a.£ + Aa,e + • +naj n

~ l

and

H" = n
2a 2 + 12a 4 £
2
+ • • •
+n(n - l)^!"" 2 -

We insert these expressions in Equation (5-47) and obtain

[2a, + 12a 4 £
2
+•••+«(«- l)a„r~ 2 ]

-2€[2a 2 €+ •••
+™„r-']
2
+ (A- l)[a + fl
2|
+ ••• + „r] =0.
fl

The sum of the coefficients of each power of £ must vanish, power by power, if

this equality is to hold for all values of £. The coefficient of £" produces the
condition

-2na n + (X- l)fl„ = 0.

We note that a n cannot be zero, and so we arrive at our main conclusion:

X = In + 1.

At the other end of the polynomial we find

2a 2 + (X — \)a = from the coefficient of £°,

12a 4 — 4a 2 + (X — \)a 2 = from the coefficient of £ ,

These conditions determine each coefficient a k+2 in terms of its predecessor a k :

a2 = —-X—
1

a = -na ,

5 - X
-a,
-'9 =
— —-
2
:

6
n
u
a.9
2 !

The results can be generalized to read

2(k-n)
'A + 2
a,.
(k + l)(k+ 2)

The derivation of this general recursion relation between successive coefficients in

the polynomial is left to be proved in Problem 17 at the end of the chapter.
 5-5 The Harmonic Oscillator 249

Equation (5-45) can be combined with Equation (5-47) to giv< : the Hermite
differential equation:

d2 H n
dH n

-TT ~ 2£—7^ + 2nHn = 0. (5-49)

The first few Hermite polynomials may be listed as follows:

ff (O-l,
#,(£) = 2£,

H {i) 2
= ±e-2,
H,u) = %e- m,

Both the equation and its polynomial solutions are named after C. Hermite, a
French mathematician of the 19th century.

Example

Much can be said about the ground-state wave function ty () in Equation (5-43).
Let us begin by verifying the normalization. The probability density is given by
the time-independent quantity

1/4 1/4
mk mk
P( x ) = %*%=\—\ / \
,-«,
.

where £ =
/

I—
\

)
x,

and so the normalization integral f™ P(x)dx becomes

(Xi

1/4
/oo mk
/
-— \
e-tdx=-
1

rj
,oo 2
,-*#=-— j
., /-0C

e-tdl
..

The last step can be taken because the integrand is an even function. The final
result is equal to the value at oo of a tabulated function known as the error
integral

erf(a) = -j^ /
e~f dl-.

The normalization of ^ is confirmed if we can prove that erf(oo) = 1. To

demonstrate this we define the numerical quantity

x
J= /
e~ dx

and evaluate the square of J as an area integral:

e~ r
(x ~
J =/J
2 x +r)
e~ dx- dy= dxdye~ .

J () JJ \ st quadrant
 .

250 Quantum Mechanics

We then transform the integration variables to polar coordinates and obtain

2
' dd
J =
2
[ ( rdre-' =
2 -2

The result is
J= \ir /2, and so the calculation finally gives the desired value

erf(oo) = ^J=
V7T
1.

The probability density ^* ^ is shown as a function of the convenient variable

£ in Figure 5-10. The indicated points £ = + 1 are significant for this state
because these values of the variable correspond to the extreme displacements of
the classical particle at energy E = ho) /2, as implied by Equation (5-41). It is

apparent from the figure that there is a nonnegligible probability of finding the
particle in the classically foi bidden region. The probability in the allowed region
is found in two steps, by computing

A
f P(x)dx = -j= Ce-P d£ = ' erf(l)
J -A vV ->q

and by consulting a table of the error integral to get erf(l) = 0.84. Hence, we
see that in the ground state the particle has 16% likelihood to be found outside
the range of classical motion. The n = state (or any other low-lying quantum
state) is not expected to exhibit classical behavior. We recall that the classical
probability density is given by the quantity P c]
(x) in Figure 5-7, and we note
that this distribution looks nothing like the behavior of ^^^ . Figure 5-11
shows a graph of ^o^io to illustrate the fact that the distributions begin to
compare with Pd when the quantum numbers become sufficiently large. Ob-

Figure 5-11

Probability density for the n = 10 state of the

harmonic oscillator. The average of the
Figure 5-10
distribution agrees with the classical
Ground-state probability density as a function
probability density in Figure 5-7.
of the variable £ = (mk/h 2 ) l
' 4
x. Classical

motion with energy Aw /2 is forbidden outside

the interval - 1 < | < 1

*o**o

-Classical domain-
 5-6 Eigen functions and Eigenvalues 251

serve that all the wiggles in this n = 10 probability density occur in the
classically allowed region, and note that the average value of the distribution
approximates the shape of the classical function Pd .

5-6 Eigenfunclions and Eigenvalues

The models in the last two sections provide insight into the workings of the
Schrodinger equation. These studies illustrate the properties of quantization, since the

stationary states of the two systems occur in discrete sets where only certain values of
the energy are allowed. We are now in position to examine the generality of this

all-important aspect of quantum physics.

Let us continue to focus on stationary states and wave functions with the elemen-
tary time dependence

E h
*(*,/) =^{x)e-' >/ .

The eigenfunction \p(x) and the energy eigenvalue E are obtained together by solving
the time-independent Schrodinger equation

- —h

2m
— + V(x)t =
2
d 2>L

dx~
E*.

Our goal is to explain the general circumstances behind the discrete occurrence of i/>

and E. We take the potential energy to be some given function V(x) and base our
claim of generality on the arbitrariness of this function. A representative potential
energy is provided in Figure 5-12 for use throughout the following discussion. The
graph also includes a chosen value for the total energy E, to be considered as a
candidate for an allowed energy eigenvalue in the Schrodinger equation. Note that
the selected energy satisfies the equality

V(x) = E at .v = .v, and x 2 .

These values of the coordinate play a significant role in the dynamics of the classical
and the quantum particle.
We begin with some classical observations regarding the kinetic energy
m
'
2

Rearrangement yields a formula for the velocity as a function of .v:

2
v
2
= -(£- V(x)). (5-50)
m

A real value of v is obtained from this formula only if the value of x is such that
E > V(x). We visualize this condition in Figure 5-12 by noting that one-dimensional
classical motion is bounded between the indicated points ,v, and .v., for the given energy
E. These special values of x are called the classical turning points. The figure shows that
the two points approach or recede from each other as E decreases or increases. We
observe that no turning points exist, and so no configuration of the system is possible.
252 Quantum Mechanics

Figure 5-12

Potential energy function V(x) and total energy E for classical motion with two turning points.
The classical particle is not allowed in the regions to the left of x, and to the right of x 2 The
.

eigenfunction ip( x) 1S constructed so that the curvature-to-value ratio is positive in the

forbidden region and negative in the allowed region.

if E falls below the minimum of V(x). We also note that the left turning point *,
remains finite recedes to infinity when E reaches a
while the right turning point x,,

certain critical value. The motion is unbounded in the positive x direction for any
larger choice of the energy. Our two models in the preceding sections can be seen from
Figures 5-4 and 5-6 to have the property that bounded motion persists, no matter how
large E becomes. The main thrust of our discussion in this section pertains to bounded
motion in the system described by Figure 5-12.
The conclusions drawn from Equation (5-50) are classical and do not apply to the
quantum particle. It is clear that the equation itself is in conflict with the uncertainty
principle since the formula defines an exact value for the momentum of a particle,
given an exact value for the coordinate. The classical turning points a:, and x 2 are
nevertheless important in the determination of quantum behavior. We can appreciate
their importance immediately if we rewrite the time-independent Schrodinger equa-
tion as

d 2^ 2m
~^(V(x) £)*, (5-51)
~~dx<

V'{x) 2m
= -T (V(x)-E). (5-52)
*(
The right side of the second equation represents given information with regard to the
variable x and indicates a change of sign at the turning points like that observed for
2
the quantity v in Equation (5-50). The quantum problem deviates from its classical
 5-6 Eigenfunctions and Eigenvalues 253

Figure 5-13

Eigenfunction behavior on either side of a classical turning point.

counterpart, however, and offers a solution for all .v, in the form of the eigenfunction
ipi*), with nonzero probability density in the forbidden as well as the allowed regions of
classical motion.
Equation (5-52) prescribes a change of sign at a turning point as a property of the

ratio of unknowns \p"/ip. The equation expresses the ratio of the curvature of \p to the

value of \p at each point x and hence determines the shape of the eigenfunction on a
point-by-point basis. It is evident that the curvature of \p vanishes, so that \p has a
point of inflection, at each of the turning points. Thus, there is a one-to-one
correspondence between regions in which the curvature-to-value ratio is positive or
negative, and regions in which the classical motion is forbidden or allowed. This
observation is summarized in the lower part of Figure 5-12. Figure 5-13 goes on to
show the qualitative shapes of possible eigenfunctions deduced from Equation (5-52).
Note that \p may change its sign away from a turning point as long as \p" has a
coincident change of sign. The eigenfunction then has a node and a point of inflection
at the same point. The eigenfunction may even oscillate and produce a succession of
nodes, provided the region is one in which ip"'/\p is negative.
Equation (5-52) is not the only ingredient in the determination of i//. Appeal must
also be made to additional physical considerations beyond those expressed by the
differential equation. We recall that the probability density is a measurable quantity,
and so we be a continuous function of x with a unique and finite
require that ty * ty

value at every point, including the limits x -» + oo. The behavior at + oo is especially
important, since ^ *^ is supposed to be integrable over — oo < x < oo if ^ is to be a
normalizable wave function. The properties of continuity and finiteness must hold for
the eigenfunction \p(x) if they hold for '&*'&. These requirements on the behavior of
\p usually include one more condition. Equation (5-51) implies that d^/dx 1 is unique
and finite wherever the given potential energy V{x) is unique and finite. It then
follows that dip/dx must also be a continuous function of x. (An exceptional case is

the problem of the eigenfunctions in a one-dimensional box. Continuity of dip/dx is

not imposed in that problem because the value of V becomes infinite at the ends of
the box.) The additional conditions on ^(x) are to be incorporated in the procedure
for selecting a physically allowable solution. Some of the shapes drawn in Figure 5-13
can be eliminated from consideration on these grounds.
We can now assemble our new mathematical ideas and draw our main conclusions
about quantization. First, let us realize that we are concerned with an ordinary
254 Quantum Mechanics

Figure 5-14

Construction of an allowable eigenfunction. The slope of i// at x can be adjusted to make

xp —* as x —» oo. For this selection it is possible to have \p
—» as x — — oo
> only if a suitable
choice has been made for the eigenvalue E.

0(X)

differential equation of second order, whose solution 4'( x ) iS uniquely determined if

we specify values for ip(x ) ar>d ^'(x ), where x is any chosen point. Let us take x

to be in the classically allowed region between the points x and x 2 in Figure 5-12.
l

We assign ^(x ) an arbitrary positive value and then examine different choices for
\p'(x () ) to see how the shape of \p develops for x > x . The upper part of Figure 5-14
illustrates some of the possibilities. Note that each possible \p turns downward to the
left of x., and fits smoothly onto another piece of \p that turns upward to the right of
x,y. Only one of the three indicated curves remains finite everywhere on the right; the
prospective solution has the property that \p
— > as x —> oo. We can tune \p'(x ) so
that i^( at ) assumes this particular shape for the given value of E. Ifwe then follow the
selected *p(x) to the left of x , as in the lower part of the figure, we are likely to find
that \p has unsatisfactory behavior as x —* — oo. We cannot expect i// to tend
asymptotically to zero on the left as well as the right unless we also tune a second
parameter in addition to i//(x ). The only remaining adjustable quantity is the energy
E. A properly behaved eigenfunction results when a suitable choice of E is made. If

we let E depart even slightly from its determined value we damage the asymptotic
behavior of the solution by forcing \p to diverge either above or below the x axis. This
argument rules out the occurrence of nodes in any classically forbidden region
extending to infinity, since \p must diverge once it crosses the axis in such a region.
Let us recall that the entire discussion pertains to values of E for which the
corresponding classical motion is bounded between turning points, as in Figure 5-12.
Our arguments imply that the energy E is quantized because only certain discrete

choices of E are found to have allowable solutions for ^(x). These discretely
determined stationary states are called bound states since the probability of finding the
quantum particle vanishes at asymptotically large distance.
It is also possible to have an eigenfunction for a value of E such that only a single

turning point exists. For instance, Figure 5-12 shows that x, becomes a lone turning
point when E is chosen large enough. The classically allowed region then has infinite

extent to the right, and so vanishing asymptotic behavior cannot be required as

x —» oo since \p is supposed to oscillate instead. We see that any such value of E is

allowed above a certain threshold, once this constraint on \p is removed. The resulting
 5-6 Eigenfunclions and Eigenvalues 255

Figure 5-15

Two eigenfunctions with different numbers of nodes. At x \p and ip\ have equal values, but
,

\p l has more negative curvature than ^ . Equation (5-51) then implies that £, must be larger
than En
2m
4/'
q
(xq) = -T2(V(Xq) -E ) O (*O>

<l>o(x)

<I/[(X )=^T(.V(X )-E 1 ) 0!(X O )

<M*

stationary states are called continuum states. The associated wave functions have the
property that the probability of finding the quantum particle at large distance does
not approach zero.
We introduce a quantum number n to enumerate the discrete energy eigenvalues
En and eigenfunctions 4 „( x
/ The wave functions have the form
)-

%(x,t) = ^ n (x)e-' E ^ h

for the corresponding stationary states. We have devoted Sections 5-4 and 5-5 to
circumstances in which only this discrete category of stationary states can arise. These

models exemplify the general situation, where an eigenfunction $ n (x) has certain
nodes, all occurring at points in the classically allowed region, and where the quantum
number n denotes an ordering of the number of nodes with increasing energy E n The .

fact that the nodes of \p n increase in number as the energy E n increases can be
established by means of a rather technical proof. Let us summarize the content of the
proof qualitatively by noting that the chain of argument takes the following steps:

more more more larger

nodes oscillation curvature energy

The link between the curvature and the energy eigenvalue is supplied by Equation
(5-51). Figure 5-15 illustrates this part of the reasoning with the aid of a simple
construction.
The potential energies in Figures 5-4 and 5-6 have the special property of
symmetry under the parity replacement x -» — x. The resulting stationary states are
therefore found to have definite even or odd parity. Our arbitrarily chosen function
V(x) in Figure 5-12 lacks this special symmetry feature. Hence, the eigenfunctions in
the general discussion do not necessarily have any predictable behavior relating
positive and negative values of x.
It is clear that the time-independent Schrodinger equation can have a collection of
distinct eigenfunctions 4' n ( x ) with energy eigenvalues En The. members of this set of
256 Quantum Mechanics

Figure 5-16

Qualitative forms of the lowest eigenfunctions

for a V-shaped potential energy.

solutions obey the orthogonality property

f%:.(x)t n ( x )dx = o (5-53)

for any two different quantum numbers n and n' . We have already seen orthogonality
in the context of the particle-in-a-box problem at the end of Section 5-4. The proof of
the general formula in Equation (5-53) is demonstrated example below.
in the last
Our description of the eigenvalue problem is taken from an area of mathematics
known as Sturm-Liouville theory. This general analysis of the solutions of second-order
ordinary differential equations is named after the 19th century mathematicians C.-F.
Sturm and J. Liouville.

Example

Consider the V-shaped potential energy shown in Figure 5-16. The associated
differential equation has unfamiliar analytical solutions; however, there is no
mathematical obstacle to deter us from making the following qualitative re-

marks. Each choice of energy corresponds to bound classical motion with two
turning points, and so the sign of the curvature of \p varies according to
Equation (5-51) in three regions of the x axis. The shape of V(x) tells us at once
that all the stationary states are discrete and that the eigenfunctions \p n have
definite parity. We expect the nodes of \p n to increase in number with E n , so
that a given eigenfunction must have one more node than its predecessor. It
follows that the parities alternate with increasing n and ascending energy. These
observations on the curvature, nodes, and parity of the eigenfunctions are
displayed qualitatively in the figure.
 5-6 Eigenlunclions and Eigenvalues 257

Figure 5-17

Square-well potential energy and ground-state

energy E. The eigenfunction for the ground
state must be symmetric with no finite nodes.

vn -

Mx)

Example

Next, we examine an eigenvalue problem that we can solve in more detail. Let
the potential energy be given by the square-well function in Figure 5-17, where

for -a/2 < x < a/2

V(x) =
V for |*| > a/2,

and consider the determination of the energy and the eigenfunction for the
ground state. We note that V is a symmetric function of x and conclude that
4>(x) must be an even function with no finite nodes. (The eigenfunction has to
be either even or odd. An odd function would have at least the one node at
-v = 0; however, the even function with no nodes would have the least energy.)

The definite parity of tp( x implies that the solution can be found by con-
)

centrating on the behavior of \p for positive values of x. In the region

< x < a/2 where V = 0, Equation (5-51) has the form

2mE
= -kfy with k x
=

The general solution in this interval is

4>(x) = A cos k x ,

since the other possible solution sin£,x is an odd function. In the region
x > a/2 where V = V , the differential equation becomes

—
d'^ , „
2m(VQ -E)
-
2
= k;\b
2Y with kl2 = 7,
2
.

dx h

The general solution in this interval is

$(x) = Be~ k * x
258 Quantum Mechanics

since the other possible solution e z*

diverges as x —* go. The two expressions for
i// are required to match smoothly at x = a/2. Continuity of \p implies

k a l
-k,a/2
A cos

and continuity of d\p/dx implies

k.a
-k.Asm
.
= -k„Be'^ a/2 .

We divide the second of these equations by the first and make several cancella-
tions to find

k a
{

k, tan = k .

The defining relations for k l

and k 2 are then used to convert this result into a
formula for E in terms of the parameters of the model:

ma 2 V -E
~^E =

The formula has an interesting limit as V — > oo. We see that the argument of

Figure 5-18

Determination of the ground-state energy in

a square well. The left and right curves refer

to the two sides of the equality

I'

tan

and the intersection of the two curves gives

the solution. The limit V —»
(l
oo results in the
solution E= E t
, corresponding to the ground
state of a particle in a one-dimensional box.

Solution
 5-6 Eigenfunclions and Eigenvalues 259

the tangent approaches 77/2, and we find that the ground-state energy becomes
equal to E x
, the energy obtained in Equation (5-32) for the problem of the
one-dimensional box:

t2 1
ma m n 77
E = E, =
2
~V? 2 2 ma

Note also that k — > oo as V — » oo, and so ^(x) no longer penetrates the
classically forbidden region in this limit. The original formula for E assumes a
tidier form when we introduce E x
as a parameter:

77

tan —
2 /•:,

The most useful way to solve this transcendental equation for the ground-state
energy is to plot both sides of the relation versus E and look for an intersection
of the two graphs. The procedure is employed in Figure 5-18 to provide a
solution below the limiting energy £",.

Example

Finally, we undertake a proof of the orthogonality relation in Equation (5-53).

We let \p n and ip
n
, be different eigenfunctions with different discrete energy
eigenvalues E n
and En ,. Thus, 4> n (x) satisfies the equation
2
h d 2>p n
T + V(x)\L = E iL ,

m ax

while ip*(x) satisfies the conjugated equation

—
h

Im
d*M
-— + V
ax
( X )W E n
.xb*.
T n

(We assume that V(x) is real, and we use the fact that En , is also real.) If we
multiply the equation by \p* and the second by ^„, and then subtract the
first

second equation from the first, we obtain

d'w
im dx
2 r ^i =(E
2 n
-E ,u:4 n n
.

dx

The left side of this equality can be rewritten and then integrated as follows:

h~ re
dJZ
2m 4>n\ ^ Yn *,
J dx\ dx dx 2m dx dx

The result of the integration is zero, since properly behaved discrete eigenfunc-
tions tend to zero at + oo. The right side of the equality must therefore vanish
upon integration:
/oo
4>:4„dx = o.
-oo

Our hypotheses rule out the possibility that E n

might be equal to En ,. It then
follows that the integral factor must be equal to zero as in Equation (5-53).
260 Quantum Mechanics

5-7 Expectation Values

The wave function and the probability density are fundamental to the analysis of any
quantum system. We use the wave function ^ to specify a physical state, and we then
suppose that the probability interpretation of ^ determines all observable aspects of
the system in a manner consistent with the constraints of the uncertainty principle.
The probability density is only the first of a list of measurable quantities to be
associated with the given state. The list goes on to include position, momentum,
energy, and all the other observables of a quantum particle. We may regard the
values of these physical variables as information encoded in the wave function. Our
next objective is to learn how this information is extracted for any specified state of the
system.
Classical mechanics treats the position of the particle at time t as the primitive
observable quantity. The momentum p(t) is then found from the coordinate x{ t ) by
computing
dx
K,)-m-.

Quantum mechanics takes a different approach beginning with the description of the
state at time /. The normalized wave function ^(x, t) is then employed to construct
the probability density

P(x, t) = y*{x, t)^(x, t).

We know that the concept of localization is embodied in P(x, /); hence, we expect the
probabilistic definition for the position of a quantum particle to reside in the
interpretation of this quantity. Let us visualize our localized particle in terms of Figure
5-3 and recall that such a distribution at time / assigns a likelihood P(x,t)dx for

finding the particle in an interval dx at location x. We cannot determine the position

of the particle with certainty, and so we turn to a statistical treatment of the observed
coordinate instead. A number of experiments performed on similarly prepared systems
would result in a variety of values for the measured position of the particle. The
average of sufficiently many such measurements would provide the logical operative
specification of the value expected for that observable. We therefore define the position
of a quantum particle by means of an average, which reflects the statistical information
contained in the state. Every other observable is likewise defined in terms of an
average, or expectation value, whose determination depends on the wave function.
Uncertainties in these observables are also to be defined as averages over the
particular state.
Let us digress briefly to recollect the procedure for averaging over a sample
discrete

of objects. We assume that there are N objects of several different types and that the
ah type of object occurs «, times in the sample. We wish to evaluate a quantity A
whose value is equal to A }
for every object of type i. The fraction n t
/N denotes the
likelihood that a given object is of this type, and so the average value of A is

computed by weighting the value A with

t
the iih likelihood factor and by summing
over all the different types:

W = E^--W-. (5-54)

J
 5-7 Expectation Values 261

Note the use of the relation £ n

]
= TV in the last step. We have calculated averages
based on this familiar method in Section 2-4.

The wave function ^(.v, /) describes an analogous sample of probable positions for
a particle at time t. Figure 5-3 shows an example in which the coordinate x serves as a
continuous index and the probability P(x, t ) dx acts as a likelihood factor for each value
of x. Any x-dependent quantity A has an average value defined as in Equation (5-54),
except that the summation over the discrete index is replaced by an integration over
the continuous variable:

/oo
A{x)P(x,t)dx. (5-55)
-oo

This formula may be recast to exhibit the explicit wave function in the form

(A) = C **{x,t)A{x)-*{x,t)dx.
J- 00
(5-56)

Note that the quantity of interest A{x) enters multiplicatively and may therefore
appear anywhere in the integrand. We discover the motive for inserting A(x) between
ty* and ^ as we proceed with further related developments.
The average value of the coordinate has a special significance in this formalism.
We write

=
<*) f* **(x,t)x*(x,t)dx, (5-57)

and refer to (*) as the expectation value of the position of the particle at time t. The
terminology is linked to our earlier remarks regarding the value expected for the

measured quantity. It is clear from Equation (5-57) that (x) may depend on /. Thus,
the role of x(t) in classical physics is transferred to the expectation value ( x ) in
quantum mechanics. Consequently, we anticipate a definition for (p), the expectation
value of the momentum at time t, which satisfies the relation

d
(P)=m-(x) (5-58)

for a nonrelativistic particle. In fact, this formula tells us how to define (p) when we
return to that question below.
A good example of an .v-dependent observable is provided by the potential energy
function V(x). Equation (5-56) expresses the corresponding expectation value as

/oo
**V(x)*dx. (5-59)
oc

Another useful expectation value of a function of x is given by the expression

/oo
2
-**x *dx.
-oo

We note that (jt) and (x) 2 are determined by evaluating integrals, and we
different

therefore realize that there is no necessary reason to expect an equality between the
two quantities. It is apparent that a special type of state ^ must be involved if (x 2 )
and (x)- are to have equal values.
262 Quantum Mechanics

The definition of the uncertainty Ax assumes that the average value (x) has
already been computed, as in Equation (5-57), for a particle in the state ^. We then
imagine that we conduct a large number of experiments on particles in the same state
and observe the departure of the position of each particle from the expected value, as
measured by the behavior of the variable x — (*). The root-mean-square of this
deviation is defined according to Equation (3-4) as

to give the desired formula for the uncertainty in the position of the particle. We can
simplify the resulting expression for Ax by the following manipulations:

2 2
(A*) = ((, - (x)) ) = (x 2 - 2x(x) + (x) 2 )
= (x 2 ) - 2(x)(x) + (X y
2 2
= (x ) - <*> - (5-60)

We know that the integration over x, denoted by the symbol ( ), always results in a
quantity independent of x. We
use this observation above to factor (x) out of the
integral expression (*(*)) in the second of the three terms obtained from ((x —
We (x — (x))
2
(x)) ). also note that is always equal to zero and therefore cannot be
used to represent the uncertainty in x. The final formula in Equation (5-60) tells us
2
that (x ) and (x) 2 are equal only for special states in which the variable x has no
uncertainty.
We turn next to the momentum of a quantum particle and consider our first

instance of a dynamical variable that is not expressible as a function of x. Equation

(5-58) provides the requisite guidance as we subject the quantity md(x}/dt to the
following series of maneuvers:

d d rC
™-(x) m— I ty*x'i'dx
dtJ-
/SO O
— (y*xy) dx = m
/-00

/
/

xy + y* x .
dx.
~d~7

The potential energy V(x) is taken to be real valued, and the Schrodinger equations
for ty and for ty* are consulted, to obtain the relations

ih d
2
* V ih d
2 ** V
+ —^ and \p1
17 2m d; ih ~d7 2m dx 2
ih

We insert these formulas in the expression for md(x)/dt and continue to manipulate
the resulting integral:

ih d
2
** V ih d
2
* v
in
I
+ * dx
2m dx' ih 2m dx' ih

ih d
2
* d
2
^*
-x^ dx
I dx 2
ih re d d* 3** d*
~2
I
** x^ + ^*^ 24" dx
J- dx dx dx

ih d** /.oo dty

x% + ^*^ ih / ** dx.
~Jx~ ./_„ dx
 5-7 Expectation Values 263

The endpoint contributions vanish because ^ approaches zero rapidly at +00, and
the integral term remains as the desired result for md(x)/dt. We return to Equation
(5-58) and write this important conclusion in the form

/oo ho
**(x,t)-—*{x,t)dx. (5-61)
-00 1 ox

Note that the differential operation {h/i)d/dx must appear between ty* and ^ in this

formula.
An important procedural result emerges when the expression for (p) is compared
with our previous formulas for (a) and (A). Whenever a wave function ^(x, t) is
used to describe the state of the system, it is correct to represent the momentum
variable by means of the differential operator (h/i)d/dx, where the operator acts on
the x dependence of the wave function. We write this representation rule symbolically
as
h d

l ox

and we then represent the square of the momentum by setting

2 2
h 3 \
d
= -h (5 " 63)
~Y~
1ox \
/
*T*
ox

as another operator acting on ^(.v, t). These rules can be invoked to compute the
momentum uncertainty A/? according to the formula

2
{^pf=(p )-(p)\ (5-64)

since the development of Equation (5-60) for Ax is equally valid for A/? or any other
uncertainty. With these definitions of the uncertainties in v and p it is possible to
prove the uncertainty principle as stated in Equation (4-6).
The energy of a quantum particle is another primary observable to be identified by
these means. Let us proceed by regarding the classical nonrelativistic energy relation
as an equality of expectation values:

<*> = + <">.
(£)
We use Equations (5-59) and (5-63) to write the equality in terms of an integral:

2 2
/c h d
iH <f+ V(x)* <h
Im ox'1
/oo u

,
^*ih — ^dx.
,)

ot
dt
(5-65)

The final formula holds because the wave function ^ obeys the Schrodinger equation.
The evaluation of (E) employs a time derivative inside an integral, just as the
evaluation of (p) employs a space derivative. The above result for (E) is the basis
for a second representation rule

d
E -* ih—, (5-66)
ot
264 Quantum Mechanics

whereby the energy variable is represented by letting the differential operator ih d/dt
act on the wave function ^(x, t). We have entertained the possibility that p and E
are expressed by means of derivatives in Section 5-1, and now we see the underlying
reasons for the proposition. The operator assignments for p and E are general and
apply beyond the context of our one-dimensional treatment. We should be prepared
to use these representation rules, and others yet to come, whenever we wish to pass
from classical physics to Schrodinger's quantum theory.
It is obvious from Equation (5-57) that (*) is a real-valued quantity, as must be

the case since the value of (*) is measurable. The same must be true of (p) and (E),
despite appearances in Equations (5-61) and (5-65). The real-valued property of these
quantities is left to be examined in Problem 26 at the end of the chapter.
We can give a further interpretation to the stationary states of a system if we look
at the expectation value of the energy in such a state. We let the system be described
by a wave function with energy eigenvalue £„,

and obtain

ih — % = ^ {x)E e" E^
3
n n
h
= En % (5-67)

under application of the energy operator. The expectation value of the energy then
becomes

/oo O /-oo

%*ih—%dx = En \ %*%dx = E n
-oo ut •'-oo

since 4^ is a normalized wave function. In similar fashion we also find

2
d \
ih—\ *., = E 2 ^„

and

< £
W>*K)'*- a = £ --

The fact that (E 2 ) and (E) 2 have the same value tells us that the energy of any
stationary state is equal to the energy eigenvalue for that state with zero uncertainty.

We recall from Equation (5-27) that the probability density is independent of time
in a stationary state:

2 2
!*«(*» 1
= I
^.(*) I
-

Time independence implies a sort of nonlocalization of the particle with respect to the
time, since the probability of finding the particle has no time variation. We know that
localization in time and uncertainty in energy obey an uncertainty relation, and we
associate this observation directly with the vanishing of the energy uncertainty A.E in
the given state. Equation (5-67) formalizes the observation by stating that the energy
operator ih d/dt acts on a stationary state to produce the same state multiplied by its

energy eigenvalue. This kind of eigenvalue equation does not hold necessarily for a
 5-7 Expectation Values 265

more general type of wave function. We stress the importance of the special property
conveyed by Equation (5-67) by letting the stationary states be known as eigenf unc-
tions of the energy operator, or energy eigenfunctions

Example

We learn more about the special nature of the stationary states when we
consider a superposition of two such wave functions:

^ = c% + c'%,, where E„ ¥= E n
,.

Application of the energy operator yields the result

3
ih — * = cE % +
ot
n
c'E„,%,

by virtue of the eigenvalue property in Equation (5-67). The expression on the

right does not contain the state f as a specific factor; hence, the given wave
function does not satisfy the eigenvalue equation, even though ^ is certainly a
solution of the Schrodinger equation. To interpret the state we begin with the
normalization condition:

/OO /-00

ty*ydx = / (c*%* + c'*%? )(c^ n + c'ty n )dx = \c\- + \c'\\

- OO ^ OO

We and
recall that ^ ^
are normalized and orthogonal, as in Equations
n

(5-14) andand we use these properties to obtain this simple conclusion.

(5-53),
Note that no cross-term contributions arise from the two stationary states. The
expectation value of the energy also follows at once with the aid of the same
properties:

/OO d

/OO
(
c **r* + c >*y* )(cE ^ n
+ c 'E n ,%,)dx = \c\
2
E„ + \cfEn ,.

- oo

These two results imply that the energy (E) lies between the eigenvalues E n
and
E n
,. We interpret the quantities |c|"' and \c'\
2
as probabilities of finding the
system in the stationary states with energies E n
and E n
,. It is obvious that the
state ^ is not stationary and that the corresponding energy uncertainty is not
zero.

Example

There is no simpler illustration of the ideas in this section than the problem of a
particle in a box. Let us take the particle to be in its ground state so that, for x
in the interval [
— a/2, a/2], the wave function is

h 27T~
/2-cos — "7TX

e
-' E ^' /h
with£,
2ma~
266 Quantum Mechanics

The expectation value of x is given by the integral

/OO /"a/ 9 2 77\

^*x^dx = / " -xcos 2 dx.
- 00
J - a/2 &

This integral vanishes on inspection, because the integrand is odd and the range
of integration is symmetric. The expectation value of p has the form

/oo
**-—*dx
h

l (IX
d 2 h
f /2 _ _ _ _
a

J- a/2d I
I
I

\
TT

a
\
cos — —
TTX

a
sin
77

a
X
dx

and vanishes for the same reason. The evaluation of (x 2 ) produces a nonvanish-
ing result, with the aid of a table of integrals:

3
2 a
<*
2
> = r - oo
^*x 2 ^dx= ["' -x 2cos 2
J -a/2 a
TTX
dx
a 77
J
I 77

24

2
1277^ T (* -6).
2
The calculation of (p ) is easier to perform because the Schrodinger equation
can be used:

(p
2
) =
f H-A^ *A
2
=
J
r A> ¥*[ 2mi'A— Wd* = 2m£, f'
J. l
***dx = 2mE,.
a/2 \
dt) a/2

To obtain the uncertainties in x and p we compute

(Axf=(x')-(xf 2
77 12
and

(A/,)' = (p 2 ) - (p) 2 = 2mE l

The product of the uncertainties is then given by

/t7
2
-6

a result slightly larger than Heisenberg's lower bound #/2.

Example

We now combine the main features of the previous two examples and assume
that our particle in a box is described by the wave function

*(*,«) cos — e
- ,E
>'/* + sin
277*
-4i£,//A

fa
 5-7 Expectation Values 267

We recognize the state to be a superposition of the two lowest-energy eigenfunc-

tions,

in a normalized equal-parts admixture. The expectation value of x is given by a

rather lengthy expression:

(,v> = **x<lrdx
f°°

ra/2
/•a/2

J - a/2
n /'» a
-
x
cos
2
77 .V

a
h cos —
77 .V

a
sin
2tt.v

a
(e
3,E,l/
!/n
<

+ e
3iE,t/h
-f sin
o
2
27TX

a
\
dx.

The first and last terms in the integrand are odd and do not survive the
integration. Only the middle contribution remains to be computed with the help
of a table of integrals:

<*>
C
1
,3<£,</A
= -(^'
a
''
f e
-3i£,f/«) f
'
a/2

-n/:>
:os —
77.V

a
sin
2tTX

a
dx

2
— cos
a
3E
h
i
t

•
— =—
8a 2

9tt~
t
16a
rcos
977"
?>E

h
x
t

This result describes an interesting time dependence for the average position of
the particle whereby (x) oscillates with amplitude I6a/9v 2 and angular
frequency ?>E /h. The behavior of (*)
x
is sketched in Figure 5-19, along with the
shape of the initial wave function ty( x, 0). The expectation value of p calls for a

Figure 5-19

Oscillation of the expectation value (at) for a

superposition of particle-in-a-box states. The
initial wave function is

2nx
ty(x,0) =
1

-j=\ cos
/
—
77 x
+ sin
—

and the angular frequency of oscillation of

(x) is 3E^/h, where E is ]
the ground-state
energy.

V(x, 0)
 —

268 Quantum Mechanics

more laborious calculation:

/oo h d
**-—*dx
-oo I OX

fa/2
'
-a/2ia
h_l

/2 ia \
\
—
77*

a
e'
E ^ h
+ sin
2tTX

a
e
4i W
77

-sin
a
—
TTX

a
e-'
E ^ h
277
+ —cos
a
277AT

a
,-«*.'/*

Nonvanishing contributions arise solely from the even terms in the integrand:

A'
hTT I 277 77*
<P)=--\e hE l/h f /
flit

ia \
_
'
..

J
ra/2
ra /2

a/2
-a/2
sin
s
a
sin —a
dx

, „ ,,.
_ le -i,E,i/h fa/2
/
cos _
VX
cos
2-TTX
dx
\
\

J-a/2 a a
J

tin ( \a 2a \
= e
3iE t/k t .
2e~ 3!Et
' /fl
2
ia \ 3t7 3t7 /

= — — /?77

ia
-
\a

3tt
2i sin
3E
h
x
t

=
8h

3a
sin
3E
h
l
t

Let us finally make a test of the correctness of the / dependence in (*) and (/>):

d 16a / 3£, \ 3E t

m — (x)/ = m -\
x

sin
dr 9t7
2
\ h ) h

\bma h\ 2
3E,t 8k 3E,t
sin = sin
2 2 "
3t7 £ 2ma h 3a'

The result is equal to (/>) as required by Equation (5-58).

5-8 Radiative Transitions

The framework of quantum physics supports the theory of quantized energy levels as
originally proposed by Bohr. Features of Bohr's picture can already be seen in the
assembled formalism, even though the presentation has been limited to one dimension.
It is actually quite instructive to look at the picture in this context because the
one-dimensional models are useful sources of insight for the more realistic situations

that lie ahead.

Bohr's quantum theory postulates the existence of stationary states and the occur-
rence of radiative transitions. The quantization of states has found its place in the
Schrodinger theory, but the mechanism for transitions has been left unmentioned.
Thus, the states of the quantum particle are presented in a kind of isolation, as no
provision has yet been made for the particle to change its energy', and so no means has
been provided for the states to reveal their existence.
We are concerned with radiative transitions, brought on by the presence of
electromagnetic fields in interaction with the quantum particle. Fortunately, we are
 5-8 Radiative Transitions 269

able to adopt an approximation procedure for the treatment of this complex problem.
We continue to use the familiar quantized states that arise from the internal dynamics
of the quantum particle system. We then let the resulting levels experience the small
effect of a perturbing interactionbetween the system and the electromagnetic fields.
The most natural way to admit the added influence of electromagnetism is to assign a
charge to the quantum particle and let the accelerated motion of the particle produce
classical radiation. This hybrid semiclassical approximation takes the energy levels
from the Schrodinger theory and includes the excitation and deexcitation of the levels
by appealing to classical radiation theory.
The procedure immediately accommodates Bohr's hypotheses. In fact, the desired
stationary states and radiative transitions are easily recognized, just by inspecting the
time dependence of the probability density \^(x, t)\
2
We let e denote the assumed .

charge of the particle so that we can use the expression for the expectation value of the
coordinate x to introduce the electric dipole moment

e(x) = e r
J- 00
x\*(x,t)\
2
dx. (5-68)

We are especially interested in circumstances where this quantity oscillates with time,
because we know that an oscillating dipole emits classical electromagnetic radiation.
No time dependence can appear in the dipole moment, and so no radiation is

observed, if ^ represents a stationary state. We are led directly to this conclusion

when we combine Equations (5-27) and (5-68) to find

/oo 2
*| \p{ X) |
dx.

Thus, Bohr's hypothesis of nonradiating energy levels is automatically realized in the

behavior of the stationary states.
A radiating system corresponds to a situation where ^ is given as a superposition of
stationary states. Any two energy eigenfunctions may be added together to illustrate
this property, as long as the two energy eigenvalues are not equal. Let us choose
quantum numbers n and n' to construct the combination

iE iE„l/h
*(*,/) = c+ n ( X )e- -'/ k + c'yf, H .(x)e-

and let us assume for definiteness that E n

exceeds En We .. call this sort of superposi-
tion a transition state because the wave function describes simultaneous probabilities for
finding the system in states of different energy. The probability density in Equation
(5-68) consists of time-independent and time-dependent pieces, and the electric dipole
moment takes the form

/oo
i{E "- E » )t/h
x{\c^f + c*c'$$y\> n >e
-oo

+ c'*c4i*4 n e- iiE-- B "

),/h
+ kVvl 2 ) dx. (5-69)

The integrals containing the two stationary terms are equal to zero for eigenfunctions
of definite parityand are not associated with radiation in any case. The other two
contributions have an oscillating time dependence, as desired, with frequency

E ~ E.
n n
v= 1 •
 .

2 70 Quantum Mechanics

This one-dimensional oscillation of a charge-bearing particle is just like the behavior

of a radiating linear antenna, where charge is driven at a certain frequency and is

able to emit electromagnetic radiation of the same frequency. The associated quantum
system has a determinable probability of transition from a higher to a lower energy
level, resulting in the emission of a discrete spectral line. Thus, the transition states
automatically offer the means by which Bohr's hypothesized radiative transitions are
to be understood.
The wave function is supposed to contain the answer to every possible question
pertaining to a given quantum system. Transition states are equipped especially with
the information needed to predict intensities for the observed spectral lines. Informa-
tion of this sort appears specifically in the complex-valued coefficients, or amplitudes,
which accompany the oscillating time-dependent terms in Equation (5-69). We know
from classical physics that the radiation intensity is proportional to the square of the
amplitude of oscillation of the electric dipole moment, because the electric and
magnetic fields are directly proportional to that quantity. The complex amplitudes in
Equation (5-69) are called quantum mechanical transition amplitudes since the
corresponding squared moduli determine the probabilities for the transitions n —* n'

and ri —* n. We introduce the dipole transition amplitude for the transition n —* n' by
choosing the third term in the equation and selecting the particular integral factor

[%J(xK(x)A. (5-70)

This integral specifies uniquely the mutual contribution of the two states involved in
the transition. Indeed, the strength of the transition by the is largely determined
magnitude of &„„, as the predicted intensity of the spectral line depends on the square
of the modulus of this amplitude. Note that Equation (5-69) also contains a similar
quantity, with n and n' interchanged, pertaining to the other transition n —* n. This
second integral is not independent of the first, since the two amplitudes are clearly
connected by the relation x*n = &„'„. .

It may happen that the integral in Equation (5-70) vanishes for some pair of

quantum numbers n and n' The transition n —* n' is then not allowed to occur with
'.

the emission of radiation characteristic of an oscillating electric dipole. We say that

the electric dipole transition is forbidden in this circumstance. The conditions of a
given problem produce a rule, called an electric dipole selection rule, to tell how the
quantum numbers must be related in order that the transition from n to n is allowed.
An illustration of such a selection rule in one-dimensional quantum mechanics is given
as follows.

Example

Let the quantum system be the harmonic oscillator of Section 5-5, and consider
the possibility of electric dipole transitions between the energy levels. We wish to

show that the amplitude x n n is equal to zero unless the quantum numbers n
.

and n' are linked in a very selective way. Recall that the eigenfunctions ^„(x)
for this model are written in terms of Hermite polynomials as

rnk >/ 4
\

H {$)e~ e/\
n
where £ = | -^ \
 5-9 Barrier Penetration 271

Hence, the amplitude defined by Equation (5-70) is proportional to the integral

We consult Problem 16 at the end of the chapter to find the recursion relation

Hn+l -2£H n
+ 2nHn _ ]
0,

and we substitute for £Hn in the integral to obtain

\
(" H (i)[H M)
n n + 2nHn _ (0]*- e H.
l
•'-oo

The resulting two integrals can be rewritten as

/OO /-OO

-oo '-oo

apart from an overall multiplicative constant. Our last step is to invoke

Equation (5-53), the general orthogonality property of eigenfunctions. (Note
that complex conjugation is immaterial here since these eigenfunctions are real.)
We conclude that the integrals must vanish whenever the labels on the »//'s do
not match. This conclusion applies to the first term when n' ¥= n + 1, and it

applies to the second term when ri =£ n — 1. Thus, we find that dipole transi-
tions are allowed between states n and n' if and only if the quantum numbers
are related by the selection rule

n' = n ± 1.

It follows that the excitation and deexcitation of oscillator states by this

mechanism can only take place between adjacent levels. Since the energy levels
of the oscillator are equally spaced, the energy of the photon absorbed or
emitted must be equal to the spacing hu in all electric dipole transitions. We
recognize the substance of Planck's quantum hypothesis in this result.

5-9 Barrier Penetration

We have had little opportunity to discuss continuum states since almost all our attention
has been devoted to systems with quantized energy. Recall that stationary states may
exist in the continuum, where the energy eigenvalues vary continuously in excess of
some threshold energy. Figure 5-20 indicates how such a state might occur and shows
the general behavior of a typical eigenfunction. We observe that any energy in the
continuum range corresponds to classical motion that is not bounded by a pair of
turning points. Consequently, the associated eigenfunction is able to oscillate inde-
finitely at large distance, like the example shown in the figure. We wish to study this

type of wave function in terms of an elementary model whose analytical solution is

immediately recognizable. The quantum phenomenon of barrier penetration can then

be treated in detail via this simplified approach.
Let us first review the properties of the continuum states of a free particle. This
simplest of all quantum systems has been employed in the beginning of the chapter,
 '

272 Quantum Mechanics

Figure 5-20

Eigenfunction for an energy level in the continuum. There is only one turning point on the left

forany energy E above the threshold. The eigenfunction oscillates in the region of classical
motion, which extends to infinity on the right.

V(x)

Threshold

where the monochromatic traveling waves

,i(kx-wt) ,i(-b-ul)
and

are introduced as elementary wave functions. We can obtain standing waves instead
by constructing the combinations

i(kx-ul) l „i( — kx—ut) _ 2 cos kx e

and

e
i(kx- u i) _ e
n-kx-ut) = 2ismkxe-' ul

All these functions are stationary-state solutions of the free-particle Schrodinger

equation, with the same unrestricted energy eigenvalue

¥k
2 1.2

E= hu> =
2m

We note that the two traveling forms are distinguished by their respective behavior as
eigenfunctions of the momentum operator:

h d

i dx

The momentum eigenvalues +hk refer to an unlocalized particle moving in the

positive and negative x directions. The standing waves do not have this unique-
momentum property because the expressions are formed by superposing the two
 5-9 Barrier Penetration 273

Figure 5-21

Reflection and transmission of a classical particle by a rectangular potential energy barrier.

V(x) V(x)

Reflection if E<V Transmission if E> Vn

momentum eigenfunctions. We note instead that the two standing waves have their
own distinctive attributes of definite positive and negative parity. We are going to use the
relations among these free-particle eigenfunctions as we proceed with our main topic.
Barrier penetration is a process that enables a quantum particle to leak through a
classically forbidden region where V(x) is greater than E. We simplify the mathe-
matics of this problem by assuming that V( x ) consists of piecewise-constant segments
in the shape of a rectangular obstacle to the motion of the particle. Figure 5-21
illustrates the encounter of a classical particle with a potential energy barrier of height
V Both classical and quantum versions of the problem require that we specify
.

whether or not the energy of the particle exceeds the height of the barrier. The figure
shows that the classical particle experiences either reflection or transmission in the two
instances. These cleanly separated alternatives do not apply to the quantum particle,

as some transmission occurs for E < V and some reflection occurs for E > V . We are
especially concerned with the first situation since the case E < V pertains to barrier
penetration.
As preparation, letus solve for the wave function in the presence of a single-step
potential energy. We employ the function

x <
V{x)
V x>0
and consider a stationary state with E < VQ , as indicated in Figure 5-22. It is clear
that the point x = divides the axis into two regions such that classical motion is

Figure 5-22

Eigenfunction describing reflection by a single-step potential energy.

V(x)

V —
</.(*)
274 Quantum Mechanics

allowed on the left and forbidden on the right. We wish to find the eigenfunction
solutions in each region and then match the functions smoothly at the turning point.
For x < 0, the eigenfunction satisfies

2
d 2m
- T=
xp

-*ft with k\= —E. (5-71)

dx n

Both cosk x and l

sin k x are x
needed as solutions, so that- the general form of the
eigenfunction may be written as

\p = A cos k x x
+ B sin k x x
in the region x < 0.

(The complex exponential functions e' k{X and e~' k <" are alternative solutions to be
employed below.) For x > 0, the differential equation becomes

/-'»// 2m
-rj=k& with k\=--(V -E). (5-72)
dx h'

Both e 2*
and e~ k2 * are possible solutions, but only the latter choice remains finite as
x —» oo. We therefore write the eigenfunction as

\p = Ce~ 2"
in the region x > 0.

Continuity requirements are imposed on \p and dxp/dx at x = to yield the following

two conditions on the three unknown coefficients:

continuity of \p(0) => A = C

continuity of \p'(0) => k x
B = —k 2C.

We choose to write A and B in terms of C, and leave C undetermined in the final

expression for the eigenfunction:

*o \

x <

x > 0.

A sketch of this result in Figure 5-22 shows a standing-wave configuration, with nodes
at fixed locations along the negative x axis.
It is instructive to recast our solution in terms of the complex exponential
representation. The eigenfunction for negative x takes the form

i// = C
1
-('''*'* + <?~' v )
- —
k9
(e'''
,x
~ e~'
k'x
)

c
'
+ i— \e'
k
<* +1-1— \e- ,k >

2 *. *i

and so the stationary-state wave function becomes

CI k,\ CI k.A
^ 1 + i-t ^i(*,*-«0 +_!_,_ ^i(-*,x-«0
in the region * < 0.
2 \
a:. / 2 \ A:, /
 5-9 Barrier Penetration 275

This expression is a superposition of right- and left-propagating momentum eigen-

f unctions with momentum eigenvalues + hk l
. The complex coefficients have equal
moduli because of the equality

2
k
1 + i
— 2
= 1 - -
1
k
—2

*i *l

Consequently, the incident and reflected traveling waves are able to combine and
produce the standing wave shown in the figure. The wave function becomes

^= Ce~ k2 "e' iut in the region x > 0.

This expression exhibits penetration and attenuation into the forbidden region in the
manner discussed in Section 5-6.
Our stationary-state wave function describes the reflection of a quantum particle
with definite wave number kv The momentum uncertainty is zero and so the
description is not that of a localized particle. To achieve localization we should make
a wave packet by superposing a continuous range of k x
values as in the construction
of Equation (5-3).
The comparison between real- and complex-valued solutions completes our pre-
paration for the problem of barrier penetration. We parametrize the barrier prob-
lem according to the model on the left in Figure 5-21. The barrier height V exceeds E
and is defined by the potential energy

x <
f
V(x) = lv < x < a
'

x > a.

The solution is more involved in this case because there are three regions and hence
three pieces to the eigenf unction. For x < and for x > a, the differential equation
for 4*( x ) is

d 2^
TT
lx-
= -W
k,x k,x
as in Equation (5-71). The complex exponential solutions e' and e~' are chosen
this time, for reasons that become clear below. If x is in the interval (0, a), the
eigenfunction satisfies

d 2xb

dx~

klX
as in Equation and the real exponential
(5-72), solutions e and e~ k -
x
are again
obtained. The variable is bounded in this case, so can that neither of the exponentials
be discarded because of unacceptable behavior at large distance. It would therefore
appear that our eigenfunction should contain all possible terms in the general form

( Ae"*' + Be~ ik '* x<0

H*) = I Ce~ k* x
+ De k x *
Q<x<a (5-73)
k x k <*
\Ae' '
+ Be-' x > a.
276 Quantum Mechanics

In fact, we can remove a term from one of the pieces of ip if we appeal as follows to
the physical conditions of the problem.
Let us refer again to the classical picture, and let us choose to consider a quantum
particle incident on the barrier from the left as in Figure 5-21. This choice eliminates
lk x
the term Be~ '

from the eigenfunction in the region x > a because the correspond-

~ ~ w!)
ing wave function Be' { k x
'

describes incidence from the right. We build our choice

of incident direction into Equations (5-73) by setting B = 0. The five remaining
unknown coefficients satisfy the following four conditions of continuity on the func-
tions \p and d\p/dx at the points x = and x = a:

A + B = C + D from ^(0),

ik {
(A - B) = -k 2 (C - D) from i//'(0),

Ce'
k'a
+ De k* a
= Ae ,k a '
from xP(a),

- k {Ce~ k '"
2
- De k * a
)
= ik^Ae ^"
1
from xp'(a). (5-74)

A solution can be extracted from these equations by finding four of the unknowns in
terms of a fifth arbitrarily chosen coefficient. The algebra is rather lengthy and is
relegated to the second example at the end of the section. We quote the main results
as ratios of squared moduli for two of the coefficients:

k, k,
,1

= 1 + -
1 /
—+— I sinh A,a
2
(5-75)
A 4 I k k ] 2

and

B k k
— + — |
sinh
2
yt
2
a. (5-76)
A 4 \ k l
k2

The unknown A is left undetermined in these formulas. (We choose A instead of A, a

more natural physical choice, in order to simplify the algebra.)
Our findings are interpreted by examining the nature of the wave function on
either side of the barrier:

= {Ae>«>-°' +
*'< *.'-0 x<0
n }
\ Ae ,(k,*-uo
>

x>a
(5 _ 7?)

We observe that ^ consists of incident, reflected, and transmitted waves by noting the
directions of propagation in the two regions:

( ^,nc + ^ref, * <

^=

2 2
Equations (5-75) and (5-76) imply that \A\ exceeds \B\ ; hence, the incident and
reflected waves cannot combine to produce nodes as in the case of the single-step

standing wave in Figure 5-22. It is a straightforward matter to calculate the probabil-

ity density and prove that ^*^ has no zeros in any of the three regions. The
qualitative behavior of the probability density is sketched in Figure 5-23.
We 2 2
note that l^l = \A\ in the region x > a. The fact that there is a nonzero
probability of finding the particle in the region to the right tells us that there is a
 5-9 Barrier Penetration 277

Figure 5-23

Probability density in a model of barrier penetration.

nonzero probability for the particle to tunnel through the barrier. This remarkable
quantum result is attributable to the wave nature of the particle. Such wave behavior
is readily demonstrated in the case of light, using optical devices like the ones
illustrated in Figure 5-24. We should expect the quantum tunneling to be
effect of

undetectable for macroscopic particles. On we find numerous mani-

the other hand,
festations of the effect in such atomic and subatomic phenomena as the behavior of
electrons in metals and the emission of a particles from nuclei. We reserve these
examples of tunneling for discussion in their proper context later on.
It should be obvious from Figure 5-23 that our wave function is not normalizable.
This should come as no surprise, as we have already acknowledged the need for a
wave packet The wave packet would have the form of
to describe a localized particle.
an wave number k in which the coefficients A to D would be
integral over the x
,

expressed in terms of A for each value of h as in Equations (5-75) and (5-76). Such a
l
,

construction would involve an excessive amount of mathematics. Let us turn instead to

another method of extracting measurable information from the unnormalizable state.
The technique makes use of the probability current density

h ( 3* 8**
*
lim \ ox ox

Recall that we have introduced this quantity in Equation (5-16) to define a flow of
probability in the x direction. A current of probability provides a natural way to
compare the incident, reflected, and transmitted components of the wave function for
barrier penetration.

Figure 5-24

Transmission of light through an optical barrier. Total internal reflection takes place at a
prism-to-air interface ifthe angle of incidence exceeds the critical angle. Partial transmission
through a two-prism combination occurs when the intervening air gap is sufficiently small.

>-
—

W V
278 Quantum Mechanics

The piecewise form of the wave function ty( x, t ) generates a similar structure in the
current density j(x, t). The two regions on either
pieces of interest pertain to the side
of the barrier, where ^ has terms as given in Equations (5-77). The calculation of j
appears to have several contributions in the region x < 0:

j = —
2im
{(A*e-
,k x *
+ B*e'
k x '
)(ik l
)(Ae
!k ' x
- Be' ,k ^
x
)

-(-ik l
)(A*e~'
k x
'
- B*e ik x )(Ae ik * *
x '+
Be- ,k >")}.

All the cross-terms cancel, however, so that only the incident and reflected pieces
remain:
h
j= —ik x
{2\A\
2
- 2\B\
2
)
2im
Ilk ,
hk,
\A\< \B\'=jinc +j (5-78)
in in

Note that a one-to-one correspondence holds between j mc and ty-mc and between j refl
and ^.efl, because of the disappearance of the cross-terms. The calculation of j yields
a transmitted contribution alone in the region x > a:

hk,
2
J \A\ =ju (5-79)

Each of the current densities jmc j ref{ and j trans represents a flux of probability in the
, ,

direction of the associated traveling wave. recognize at once that the factor hk x /m We
denotes the speed of the particle. Let us take special note of the fact that this speed is

common to the results in Equations (5-78) and (5-79) because the height of the barrier
is the same from either side. It should be apparent that a different step height on the
right side of the barrier in Figure 5-21 would imply a different speed for x > a and a
correspondingly different factor in the transmitted flux.

The main conclusions of the barrier problem are found in the form of ratios
representing the transmission and reflection of probability relative to the incident flux.

The relevant defined quantities are the transmission and reflection coefficients

Jx Jref]
T= and R = (5-80)
J\

We use Equations (5-75), (5-76), (5-78), and (5-79) to obtain

7 2
A 1

T= (5-81)
A 1

1 + - sinh
2
A:
2
a
4 [t, *.J
and

2 sinh"£,fl
B />'
i 4 \
k \
k1
R (5-82)
A \lk 2 A,
1 + +
_

— sinh
2
A: 9a
\ A, k2
 5-9 Barrier Penetration 279

Note that the speeds always cancel in the calculation of R and that the speeds also
cancel in the calculation of T because of the symmetrical height of the barrier. We
see immediately that Equations (5-81) and (5-82) obey a sort of conservation law:

T+ R = I.

Thus, the coefficients T and R are able to give well-defined physical information
about probabilities and reflection, even though the
for particle transmission results are
deduced from an unnormalizable wave function.
The transmission coefficient is especially interesting because it measures the prob-
phenomenon. We may recall the defining relations for
ability for a truly nonclassical
kx
and k 2 in Equations (5-71) and (5-72) and derive an approximation to this
quantity for use whenever a is substantially larger than \/k 2 :

r=16 <5 - 83)

"l( '"I;)'"'"-"

The proof of this formula is offered as Problem 37 at the end of the chapter. It should
2k2 "
be clear that the exponential in Equation (5-83) is the dominating factor since e~
becomes a very small number for k 2 a » 1.

Example

Let us apply Equations (5-81) and (5-83) to a numerical illustration in which a 2

eV electron encounters a 10 eV potential energy barrier of 0.1 nm thickness. We
wish to try both formulas for T in order to test the approximation, and we also
want to assess the smallness of the quantum tunneling effect. The wave number
for the incident electron is

nmE /2(9.11 X 10- 31 kg)(2eV)(l.60 X 10" 19 J/eV)

1 ~ 34
h 1.05 X 10 J •
s

= 7.27 X 10
9
m-' = 7.27 nm" 1
.

The similarly defined quantity inside the barrier is given by

pm(V -E) rV~^E

k2 = = \l - -k t .

We have V = 10 eV, and so we find (V - E)/E= 4 and k 2 = 2k v It follows

that k 2 a is larger than unity, but not by much:

k2a = 2(7.27 nm~')(0.1 nm) = 1.45.

We use this number to compute

k2 a
= -k 2 a = ^ = k2a _ -k 2 aj =
e 4 26j g q 235^ and sinh k ^ £ g g qj

The transmission coefficient can now be calculated according to each formula.

280 Quantum Mechanics

Equation (5-81) gives

1 1

Texact
1
- /
2 2 2
= 0.137,
k2 kx \ 1 + i(2 5) (2.01)
1 + - smh 2
k2a
4 k k2
\ \
)

while Equation (5-83) gives -

Tapprox = 16 —Ey (
1 .-^-16(^)|
8
(0.235)
2
= 0.141.
To

The agreement indicates that k 2 a is large enough after all for the approximate
formula to be reliable with this choice of parameters. The answer itself tells us
that the electron has ; i remarkable 14% chance to tunnel through the potential
energy barrier.

Example

The continuity conditions for the rectangular barrier are straightforward to

apply, although the algebra is somewhat tiresome. Let us outline an efficient

algebraic strategy that determines four of the unknowns in terms of a fifth

undetermined coefficient. The algebra simplifies if we define

k,
a = — and T = Ae'
k a
'

as shorthand notation, and if we choose A to be the undetermined quantity. The

last two of Equations (5-74) are

+ De k >" = T ia(Ce~^' - De k a
=
k >"
Ce- and >
) T.

We can solve these easily to get

1 + la 1 — ia
Ce-
k* a
= T—. and De k *"=-T-
2ia 2ia

The first two of Equations (5-74) then become

A+B = C + D= —
2ia
[** 2fl (l + ia) - f
_ * 2fl
(l - ia)]

= r cosh k 2 a — — sinh k.,a

\ «

and

A - B = ia(C - D) = - [e k *a
(\ + ia) + ^"(l - ia)]

= r(cosh k 2 a + iasm\\ k 2 a).

 5-9 Barrier Penetration 281

We can also solve these easily to obtain

A = T cosh k 2 a + — a — — I
sinh k a
2 \ a

and
i
( 1 \
+ —
.

B = \ a sinh k 2 a.

The moduli of these complex-valued quantities are needed in the interpretation

of the wave function. We note that \Y\

2
= \A\~, and so we find

cosh
2
k. y a
/
1

+ —\ a — —\
M 2
.

sinh
2
/r, 7 a = 1
1

+ —1a + —
\
2
sinh A,a
'
4 a 4 a '

and
2
1 l

= —\/ a + — \
\
.

sinh~X>a.
4 \ a

These results are cited above as Equations (5-75) and (5-76).

Example

The investigation of barriers and tunneling is also applicable to bound states.

Consider the double-well potential energy for a particle in Figure 5-25 as a case
in point. The symmetry of V(x) implies the existence of eigenfunctions with
We can use these symmetry properties along with the curvature
definite parity.
arguments of Section 5-6 to deduce shapes for some of the solutions. The figure
shows the bound-state eigenfunctions \p and \p.> for the two lowest energy levels {

is, and E Let us suppose that the wave function of the particle is given by
.
2
some combination of these states, such as

We know that this superposition of stationary states produces an oscillating

expectation value for the position of the particle, with frequency of oscillation

E2 - E x

The qualitative shape of ^ at t = is shown in the figure, along with the

oscillations of (*) as a function of time. We can think of the oscillatory motion
as a periodic tunneling with frequency v , in which the particle starts in the well
on the right and tunnels to a symmetrical location in the well on the left in a
time \/2v. The two symmetrical positions of stable equilibrium for
particle has
the given potential energy V(x). These locations are separated classically by a
barrier; however, the tunneling process enables the quantum particle to pass
282 Quantum Mechanics

Figure 5-25

Double-well potential energy and two bound-

state eigenfunctions. A superposition of the
two states describes a tunneling oscillation of
the particle from one well to the other. This
behavior is analogous to the periodic inversion
of the NH , molecule.

V(x)

<l>i(x)

*(x,
 5-/0 Two-Particle Systems in One Dimension 283

from a neighborhood of one stable point to a corresponding neighborhood of the

other. This type of oscillation provides a simple model for the inversion behavior

of the ammonia molecule NH 3

. The molecule has a tetrahedral structure in
which the three hydrogen atoms define a plane at the base of a pyramid, while
the nitrogen atom has a position of stable equilibrium at one of two symmetrical
locations on either side of the plane. The nitrogen atom acts like the particle in

the double-well model, as the periodic inversion of the molecule corresponds to

an oscillation between the two stable configurations. The 3
inversion NH
frequency v = 23870 MHz is accurately known and has been employed as a

precise standard of time in one of the earliest atomic clocks.

5-10 Two-Particle Systems in One Dimension

Many of the important problems in quantum physics are concerned with assemblies of
several particles. The two-body system is already rich enough to generate a number of
new ideas for consideration in the Schrodinger theory. Our attention turns now to the
description of such systems, while the treatment continues to focus on behavior in one
dimension. This investigation leads us directly to a profound new concept when we
consider the symmetry of two identical particles in quantum mechanics.
Let us begin with some general remarks about the analysis of two quantum
particles in one dimension. We assume that the particles can be distinguished, at least
by their masses, for the first at, and
part of our discussion. There are two coordinates,
x 2 so that the state of the system
, wave function ^(x u x 2 t), which
is described by a ,

depends on these two independent variables. Note that we do not introduce separate
wave functions for each particle because, in general, we do not want the constituents
of the system to be isolated from each other.
The classical energy relation contains the kinetic energy of each particle and the
potential energy of the system:

P~ + £- + V{x ,x 2 )=E. x

We return to the representation rules in Equations (5-62) and (5-66) and write

h d h d d
Pi -* - t— , A> -» - T~ '
and E ~* lh
T~
i ox x
i ox 2 at t

as differential operators acting on ty( *,, x2 , t ). We then use these operators to convert
the energy relation into the two-particle Schrodinger equation:

2 2 2 2
h d h d d
2 2 V 2 '
2m dx l
2m 2 dx '
8t

The probability interpretation of the wave function makes a joint statement regarding
the detection of the two particles. We define the probability density in terms of the
normalized wave function as

P(x„x 2 ,t) = ^*(x l

,x 2 ,t)^(x ,x 2 ,t), l
284 Quantum Mechanics

and then we specify

2
P(x l
,
x2 , t) dx l dx 2 = \^(x l ,
x2 , t) |
dx l dx 2 (5-85)

as the probability at time t for finding particle 1 in the interval dx x

at location x x
and
particle 2 in the interval dx 2 at location x 2 . The wave function is normalized to give
unit probability of finding both particles somewhere, according to the condition

/OO /-00

dxA dx 2 \^ = 1

We assume that V has no dependence on the time so that we can find stationary-state
Each of these states has an energy eigenvalue E
solutions of the Schrodinger equation.
appearing as a parameter in the t dependence of the wave function

¥(*,,* 2 ,0=*(*i,* 2 )«- ,w *.

The spatial eigenf unction i>{x x ,

x2) and the energy E are found by solving an
eigenvalue problem defined by the time-independent partial differential equation

2 2 2 2
h d h d
2*~ T~ + V(x Xl x 2 )) = E*. (5-86)
2w, dx 2 2m T^^
dx 2 2

Our general discussion concludes at this point. We can proceed further if we are told
how V depends on its two variables. Only one special type of dependence on x and x 2 x

is of interest to us in the remainder of this section.

We suppose that the potential energy has an additive structure in the two
coordinates, of the form

V= V (x )+ V2 {x 2 ).
l l
(5-87)

Hence, the two particles may be subject to some external force but are not influenced
by each other since V includes no contribution linking the coordinates x, and x 2 The .

two particles are dynamically isolated from one another in this special situation, and
the solution for \p(x u x 2 ) simplifies as a consequence.
We construct \p by identifying separate eigenfunctions for each particle. The
eigenfunctions are defined as v//(x,) and \p(x 2 ), with energy eigenvalues E and £,
according to the one-particle equations

2
h d 24*
2
+ V (x )+ = E+ 1 i

2m l
dx

and
2 2
h d ^
,
+ V2 {x 2 )) = E).
lm 2 dx 2

We then find that, if we multiply the first of these equations by «K* 2 ) an<^ tne secon<^
 5- 10 Two-Particle Systems in One Dimension 285

by i//( at, ), and add the two results, we produce the equality

2
h
2
dS> ~ h ~d 2$
2m x
dx\ lm 2 dx 2

using Equation (5-87) to write the third term on the left side. The result may be
compared with Equation (5-86) to reveal that a solution for \^(x x
,
x2 ) has been found.
The two-particle eigenfunction is evidently of product form,

*(*„* 2 ) =+{ Xl )$(x 2 ), (5-88)

while the energy eigenvalue is given as a sum of energies:

E= E+ E. (5-89)

The particles share the total energy E as independent entities because the dynamics of
the system is based on a potential energy of additive form in the two coordinates.
Thus, the stationary state of the two independent particles is represented by a multiplica-
tive energy eigenfunction with an additive energy eigenvalue. It is apparent that this

construction would not hold in the absence of the hypothesis in Equation (5-87).
Our problem takes an entirely new and surprising turn when we consider particles
that cannot be distinguished. The constituents of such a system must have the same
mass and also the same value for every other identifying characteristic. We find that
the probability interpretation forces the probability density to have a certain unique
property in any state of such a system. The issue becomes clear if we return to
Equation (5-85) and realize that we cannot always say which particle is in dx and ]

which is in dx 2 if the two particles are indistinguishable. We do not encounter this

problem in classical physics because we are able to follow the trajectories of classical
particles precisely and are therefore able to tag identical particles visually in order to
tell them apart. The uncertainty principle precludes these possibilities for quantum
particles. Figure 5-26 shows schematically two distinct pairs of classical orbits whose
outgoing particles are detected indistinguishably in the quantum mechanical treat-
ment. These which-is-which considerations imply the existence, and indeed the
necessity, of anew type of symmetry property in a system of identical particles.
measurements cannot determine which of the two particles is which, it follows
If

that predictions of observable quantities must be unaffected by the replacement of one

particle by the other. This identical-particle symmetry is built into the probability density
by requiring that quantity to be symmetric under the interchange of particle coordi-

Figure 5-26

Distinguishable classical orbits in a collision of

two identical particles.

O—--ZD C

< O
286 Quantum Mechanics

nates in the wave function. Thus, the probability density in Equation (5-85) is

supposed to obey the condition

2 2
|¥(*„* 2 ,0I =|*(*2»*i»0l ( 5 " 9 °)

in a system of two identical particles. The wave function can realize this symmetry in
one of two ways. It must be the case that ^ is a symmetric wave function satisfying

¥(*„* 2 ,0 = +*(* 2 ,x,,0, (5-91)

or it must be the case that ^ is an antisymmetric wave function satisfying

¥(x„* 2 ,0 = -*(x 2 ,x lt t). (5-92)

We observe that the symmetry of |^| is dictated by familiar quantum arguments

and that no new principle is involved in Equation (5-90). On the other hand, it is a
deeper question to ask whether ^ itself should choose symmetry or antisymmetry. The
actual choice between Equations (5-91) and (5-92) turns out to be ordained as an
intrinsic property of the particles in question.
The independent-particle eigenfunction in Equation (5-88) is not correct for
identical particles because the expression does not satisfy identical-particle symmetry'.
We can easily adapt the solution, however, and generate either a symmetric or an
antisymmetric eigenfunction. Equation (5-88) is symmetrized by defining

1 . - „ -

or antisymmetnzed by defining

We observe that both }p(x )Tp(x 2 ) andl

\}/(x
l
)\p(x 2 ) are solutions of Equation (5-86)
with energy E=E+ E. We symmetry or antisymmetry is also
then insist that
s A
required for a proper eigenfunction, and we construct p and \p by superposing
equal parts of the two solutions with the appropriate signs. The factor l/v2 is
included to ensure the normalization of the wave functions. The resulting expressions
assign each particle an equal share in the occupation of the given single-particle states
described by ip and \p. Hence, the symmetry has the remarkable effect that each of the
two particles is "aware" of the configuration of the other, even in the absence of an
interaction between particles.
We should note that it is possible to use the solution 4>( X \)*P( X 2) as a symmetric
eigenfunction in the special circumstance where ^ an d ^ are identical functions. Let
us also note that the antisymmetric eigenfunction becomes

A =
\p when ip and \p are identical functions.

This interesting observation means that no antisymmetric state can exist for particles
whose single-particle quantum states are labeled by the same quantum number.
 5- 10 Two-Particle Systems in One Dimension 287

Identical-particle symmetry has far-reaching implications in the structure of atoms

and nuclei, and in the theory of other systems of identical constituents. We take up the
investigation of these matters in due course.

Example

A simple nontrivial illustration of an independent-particle system is provided by

two noninteracting particles in a one-dimensional box. This rather hypothetical
problem is defined by adapting the potential energy in Section 5-4 to the
two-body expression

nv _ J

\ oo
when both
otherwise.
.v, and x 2 are in (
— a/2, a/2)

Equation (5-86) tells us that the eigenfunction \^(x u x 2 ) satisfies

2 2 2 2
h d h d
- ~ —
2m yr^
ax\
~ o
2m 2 T~2
{
ox 2
^
= E^ —
if both x {
and x 2 are in the interval (
— a/2, a/2) and that the eigenfunction
vanishes if either coordinate is outside this region. We appeal to our indepen-
dent-particle result in Equation (5-88) and write the solutions for «//(*,, x 2 ) as
products of particle-in-a-box eigenfunctions taken from Section 5-4. Each of
these single-particle states has a single quantum number, and so every two-par-
ticle eigenfunction has two such quantum numbers, one for each factor in the
product

The corresponding energy eigenvalues are labeled in similar fashion. Equation

(5-89) gives these energies as sums of single-particle eigenvalues taken from
Equation (5-31):

hV h
2
m2 1 I hit \
2
1 »? n\\
E "^ =
W" 2
1
+
2^a~ 2
"2
2
" 2 l T) UT +
Z "

The stationary-state wave functions have the form

*ni „ 2 " +. (*l)*. 1(*2)'""-"'

1
/ *,

and so the two-particle probability in Equation (5-85) becomes a simple product

of separate probabilities for each independent particle:

|2 i2
P(x ,x 2 ,t)dx
l l
dx 2 =\\P ni (x 1 )\
dx r \^ n2
(x 2 )\ dx 2 .

It is instructive to list a few of the eigenfunctions and energies for some of the
288 Quantum Mechanics

lowest values of the quantum numbers n i

and n 9 :

^i,
= —cos cos
a a a 2 \ a I \ m, m2
77,, 277* 2
i//,2 = —cos sin-
a a a 2 \ a j \ m l
m2
2
2 277.x, 7r;t \ ( h7T\ l 4 1

4> 2 \
= — sin cos
2

a a a 2 a

We can apply these results to the case of identical particles if we set m = m 2 = m x

and either symmetrize or antisymmetrize the eigenfunctions. The stationary-state

wave functions become

V 1

/here

2
1 t hTT\ ,

lm\ a )

A list of the eigenfunctions and energies includes the following entries:

«|/'
n
2
= —cos
77* ,

cos
77X 2
£,, = —
2m
— I
fl7T

a
\

^12 =
.,
¥'21 = ~1k
12/
~
a
C°S
77,,

a
Sm_
.
277,2

a
+ sin
277,,

a
cos —
77,,;

a
\J2 \

1 / Hit
E„ •
5.
2m \ a

^12 = ~^2\ = -!=-

1 2

a
/

cos
77,,

a
sin-
277, 2

a
277,,

a
cos —
77, 2

a
V2 \

Observe that \p n n
is automatically symmetric, while \j/*
n
is nonexistent,
whenever «, and « 2 are equal.

5-1 1 The Three-Dimensional Box

The final topic in this chapter is intended as an introduction to quantum mechanics in

three dimensions. Our purpose is to let the new three-dimensional formalism begin in
a limited context where the familiar mathematics of one dimension can still be used.
We return to the investigation of a single particle in this section and continue the
problem into the next three chapters.
We describe a quantum particle in three-dimensional Cartesian coordinates by a
straightforward extension of the one-dimensional Schrodinger theory. A state of the
 5-// The Three-Dimensional Box 289

particle has a wave function ^(x, y, z, t ). The dependence on the three coordinates is
determined by solving a three-dimensional version of the Schrodinger equation. We
deduce the form of the equation by referring to the classical energy relation

—
P
2m
+ V(x,y,z)=E

and noting that the momentum p is a vector with three components. The kinetic
energy therefore consists of three terms:

f_ = p*+p; + p;
2m 2m

The customary rule for representing the momentum by a differential operator applies
to each Cartesian component of the vector p. We employ this technique to introduce
the set of differential operators

h d h d h d d
~* ~ — — E ~~
& ~T~
Px
i
~^~
ox
> Py ~*
i
T~
dy
> A "~*
i
~T~
dz
>
an d *
at
>

all acting on the wave function ^(x, y, z, t ). The energy relation is thereby converted
directly into the equality

~^~\
2m \
T^*
dx"
+ Tl*
dy
+ Tl*)
dz~ /
+ V(x,y,z)* = ih — *.
dt

We abbreviate the combination of spatial derivatives by adopting the convenient

symbol
2 2
d- d d
'

dx dy 2 dz 2

and we then rewrite the equality as

2
h
-—V
2m
,
2
*+V(x,y,z)<l' = ih —d y. (5-93)
dt

The result expresses the Cartesian form of the Schrodinger equation in three dimen-
sions.

The probability interpretation of ^ has already been described in the discussion

leading to Equation (5-18). We identify an infinitesimal neighborhood of the point
(x, y, z) by means of the volume element

di = dxdydz
and define the expression

2
\^(x, y, z, t)\ dxdydz

as the probability of finding the particle in dr at time t. The wave function is

290 Quantum Mechanics

supposed to satisfy the normalization condition

/oo /-oo /-oo o

dxj dyj dz\*(x,y,z,t)\ = 1,
oo — 00

so that the particle has unit probability to be found somewhere in all space.
A stationary state of the particle is an energy eigenfunction with energy eigenvalue
E. The corresponding wave function is written as

*{x,y,z,t) =i {x,y,z)e- lEt / h

l .

The spatial eigenfunction \p(x, y, z) and energy E are found by solving the eigen-
value problem conveyed by the time-independent partial differential equation

—
2m
V'^+ V(x,y,z)rP = E^. (5-94)

The dependence of V on its three coordinates has to be specified before any more
progress can be made.
A simple but instructive illustration is provided by the free motion of a particle in a
three-dimensional box. We confine the particle by means of an infinite exterior
potential energy:

x[n - /2, a/2], y in [-b/2, b/2], z in -c/2, c/2]

V( Xt y tt )-l°
fl
i [

I oo otherwise.

Thus, the region of motion is bounded by a rectangular parallelepiped with dimen-

sions (a, b, c), and the center of the region is chosen to be the origin as in Figure 5-27.

Figure 5-27

Rectangular boxes for the confinement of a particle. The energy levels are indicated below by
the quantum numbers n^n.,n i
. The states pass through different stages of degeneracy as the box
assumes higher degrees of symmetry.

y :/
c/ y / a / y

,/
/
a ./ a /
222
222 222

212 212, 122

122 221 221, 212, 122
221

112 112
211 211, 121 211. 121, 112
121

111
111 111
 5- 7 / The Three-Dimensional Box 291

The allowed solutions of Equation (5-94) must vanish outside the box and satisfy

continuity at the six walls

c
x = + —
H
~ 2
, and + -
~ 2

We can assemble such functions of (x, y, z) by using our solutions \p n ( x) from Section
5-4 in each of the three variables. We denote the one-dimensional particle-in-a-box
eigenfunctions as

^ ni (*), *P„ 2 (y), and tn 3 ( Z )

in the regions defined by

a a b b c c
.v in y in and z in
2> 2 2' 2 2' 2

We then take products of these solutions to form the desired eigenfunctions in three

dimensions:

t n] n nS X > y> Z )
= ^n (
X )^n {y)^n,( Z )- (5-95)
2 l 2

(A similar argument has led us to the expressions for the standing electromagnetic
modes in Equations (2-17).) Each factor on the right side of Equation (5-95) is
independently indexed by its own quantum number, and so a set of three quantum
numbers is needed to label all the requisite functions of the three Cartesian coordi-
nates. We can write an explicit formula for these eigenfunctions inside the box as

cos 2 I cos )l n 2 n y j cos n-,TTZ

Tn n n -,
(5-96)
\ sin \ sin
,
i
v sin b c

where the notation { } ( ) tells us to choose the cosine or sine function of the indicated
variable when the relevant quantum number is odd or even.
The energy eigenvalues are labeled by the same three quantum numbers. We
determine the allowed energies by direct use of Equation (5-94) inside the box:

2m

If we insert Equation (5-96) in this differential equation, we obtain the following

result

2 2 2
h* 1 d d d \

2 2
2m\ dx dy az J
'
3

=
h

2m
2

-
I
I

—
n TT'
x

a ,
,

1
2

Yn x
tt
2n3
/

1
n 2 ir\
^ 1
2

T n| n 2 n 3 f n.n 2 n.

2 2 2
tl TT
(
n \
V +
(
n 2\
+
/"3\ 2

T n n n
2m (7) (7) (7). ^ »
t
292 Quantum Mechanics

It follows that the energy eigenvalues are given in terms of the three quantum
numbers by the formula
2 2
/n 2
— -"^7 \2 « 3 N2
h 2
ir [/ n, \
£ +
7 \ (5-97]

The corresponding normalized stationary-state wave functions are expressed in terms

of the eigenfunctions in Equation (5-96) as

=J, - iE-
^ ( X y 2)e l -2'3 t / h .

These few steps produce a complete set of solutions to the problem and do so without
the need for any new mathematical machinery.
An interesting new feature appears in our results when the box has two or more
dimensions of equal length. Figure 5-27 includes the special case of a second box with
lengths (a, a, c), in which the energies are found from Equation (5-97) to be

2
2
m2 +
1m —
h I n nl n\
r^ + -
\
£ WJ
'
2 J =^H \ a c
• (5-98)

The significance of this case resides in the fact that the formula for the energy levels is

not affected by an interchange of the two quantum numbers n, and n2 . We therefore

have a situation in which the wave functions 4',, „ „ and i, „ „ „ represent different y

states whose energies E„ „ „ and E„ „ „ are the same. These states are indeed distinct
because the two wave functions ^„ „ „ (x, y, z.t) and ^ „ „ „ (x, y, 2, t) differ in their
dependence on x and y. This set of circumstances exemplifies a general quantum
phenomenon of far-reaching importance. The situation is called degeneracy, and the
states are said to be degenerate, whenever a quantum system has two or more distinct
energy eigenfunctions with the same energy eigenvalue. In the case at hand, we
associate the degeneracy of the states Sk n „ and ^n n n with the symmetry of the box „

under an interchange and y. The figure shows that this symmetry

of the coordinates x
distinguishes the second box from the first, where the assignment of unequal lengths
(a, b,c) precludes such an interchange.
The problem takes on a higher degree of symmetry in the further special case of a
cube with dimensions (a, a, a). This third box is also shown in the figure, along with
the energy levels obtained from the formula:

E„ in
1
,
-
ni
'
=—
lm\
nv\
— 1 /

a j
',
» +«| + »i). (5-99)

The complete symmetry of the box causes the expression for the energy to be
completely symmetric under any interchange of the three quantum numbers. The
resulting degeneracy of the states is maximal since all the different states

,^„
ty„ „ „ have the same energy, regardless of the order in which the
„ „ ,-
quantum numbers occur in the eigenfunctions. A numerical example is given below to
illustrate how successive degrees of symmetry of the box result in sequential stages of
degeneracy.
We have encountered degeneracy before, and not taken note, in our discussions of a
free particle. It is clear that the monochromatic wave functions

Hkx «o *«'<-**-«0
e and
represent distinct degenerate states. These right- and left-propagating waves have
different momentum eigenvalues +M, but the same energy hu.
 511 The Three-Dimensional Box 293

A degeneracy always reflects the existence of some symmetry in a given problem.

Degeneracy occurs more frequently in the chapters that lie ahead. The interpretation
in terms of symmetry always provides a deeper understanding of the particular
physical phenomenon.

Example

The following calculations demonstrate the evolution of degeneracy for the three
systems indicated in Figure 5-27. First, we let the dimensions of the box have
different, nearly equal lengths (a, -^a, jffl)- Equation (5-97) determines the
energies as

ftV I 81 121 A
2 =
lOOnf + 81«1 + 121«|
n: + n.,
2
+ ;

2ma' 100 100 100

in terms of the energy parameter E defined in Equation {

(5-32). Next, we let

two of the lengths be equal by choosing dimensions (a, a, jytf), and we use
Equation (5-98) to find

100n? + 100n| + \2\n\

^n,n.,n, ^ 1

100

Finally, we let the box be a cube with lengths (a, a, a) and use Equation (5-99)
to obtain

£„,„,„., = £i(»i + A + n\).

We observe a developing simplicity in the energy formula as we pass toward

maximal degeneracy. The lowest energies are tabulated in multiples of E X
/\QQ
to display this behavior as follows:

100
n, n2 n3
£ ri,n 2 n 3 Q Tn,n 2 n 3

1 1 1 302 -» 321 -» 300 cos — — —

tt mz
a
x
cos
try

a
cos
a

1 1 2 665 684 600 cos — —y

1TX

a
cos
77

a
sin
'Ittz

1 2 1 545 -> 621 -> 600 cos — 1my —

77

a
X
sin
a
cos
7TZ

a
my
2 1 1 602 621 600 sin —
Ittx
—
mz
cos cos
a a a

2my 2m
1 2 2 908 984 900 cos —
77 x

a
sin
_

a
sin
a
2mz
2 1 2 965 -» 984 -» 900 sin
277X

a
cos —
77^

a
sin
a
2my
2 2 1 845 921 900 sin
2 77 x
sin cos —
mz
a a a

277AT 277^ 2772

2 2 2 1208 -» 1284 -» 1200 sin sin sin
a a a
294 Quantum Mechanics

(We include in the rightmost column a listing of the eigenfunctions from

Equation (5-96) for the case where the particle is confined to a cube.) The
passage to maximal degeneracy is clearly seen in the energy levels, as listed in
the table and as drawn in the lower portion of the figure.

Problems

1. Suppose that the functions %(*, t), ^(x, l),

<
^ 3 (x, I), . . . are solutions of the Schrodin-
ger equation in one dimension. Let these functions be superposed by constructing

* = a,^, + a2 % + a3 * + 3
• •
,

in which the a's are constants, and show that ^ is also a solution. What mathematical
step needs to be justified when the construction of ^ involves an infinite series of

functions?

2. The probability current density is defined as

j(x,t) = —
2im
ft (

\
**~idx
<9* d**
^*
d>

Use the Schrbdinger equation to deduce the probability conservation law

n
(9

ox at

What condition must the potential energy V(x) satisfy in the derivation of this result?

3. Suppose that the state of a particle is described by the monochromatic wave function

Calculate the probability current density for this state and interpret the result. Replace ^
by the wave function in the example of Section 5-1 and repeat the calculation.
2
4. Show that the normalization integral /? oc >^(-«, 0| dx is time independent |
for the case of

a nonfree particle. What condition must V(x) satisfy to ensure this result?
~' E /h ~' E *'/ h
be two stationary-state wave functions with real-
{
5. Let )p l
(x)e \
and \p 2 (x)e

valued eigenfunctions \p i
and i//
2 - Suppose that the state of a particle is described by the
wave function

*(,, t) = «,*,(*),-*«'/' + « 2 * 2 (*),-'*'/*.

Show that the probability density is given by

2 2 2
|*(x,0| = KI 2 (^,(x)) + KI 2 (^(*))

+ 2|a,||fl 2 |^ I
(x)^ 2 (x)cosl - t - $, +<#> 2 I,

where </>, and (f>2

are the phases of the complex constants a, and a2 .

6. A particle in a one-dimensional box is confined to the interval [ —a/2, a/2] and is in its

first excited state. Calculate the probability of finding the particle in the subinterval
(a/8,3a/8).
 Problems 295

Show that the particle-in-a-box wave functions can be expressed as combinations of

traveling waves that propagate in opposite directions inside the box. Obtain the phase
velocity of these traveling waves.

Prove the orthogonality properties

a n nirx n ttx r a /2 mrx n mx

cos cos dx = and I sin sin
-a/2 a a •'-a/2 a a

for unequal quantum numbers n and «'.

9. Suppose that the wave function for a particle in a one-dimensional box is given by the
superposition

ty = c% + c'%,,

where ^„ and ^„. represent any two of the normalized stationary states of the particle.

What condition must the complex constants c and c' satisfy in order for ^ to be a
normalized wave function? Interpret this result.

10. Suppose that the wave function at / = for a particle in a one-dimensional box is given
by
1 / 2irx 3nx
*(x,0) = -f=\ sin + cos
\Ja \
a a

What is the subsequent form of the wave function ^(.v, ()? Use this form to compute the
probability density, and interpret the time dependence of the result.

11. Show that the probability of finding a classical oscillator in an interval dx between —A
and +A is given by

dx

TT\ A' - X
i

where A is the amplitude of oscillation. What is the probability of finding the oscillating

particle somewhere in the finite interval [0, A/2]?

12. Apply direct differentiation to the ground-state wave function for the harmonic oscillator,

2
* = e -fi^* /2h e -,u </2
unnorma ii zed),
(

and show that ^ has points of inflection at the extreme positions of the particle's classical
motion.

13. For an oscillator in its ground state, calculate the probability of finding the particle
between x = and x = A/2, where A is the classical amplitude of oscillation. Obtain a
numerical result and compare with the answer to Problem 1 1

14. Assume that an atom in a metallic crystal behaves like a mass on a spring. Let the spring
constant for a copper atom correspond to angular frequency con = 10' 3
rad/s, and
calculate the atom's amplitude of zero-point motion. Take the Cu mass to be equal to 63

H masses.

15. Prove that the Hermite polynomials //„(£) satisfy

H„^2iH„--
by showing that (2£//„ — //„') obeys the differential equation for H n +
296 Quantum Mechanics

16. Prove that the Hermite polynomials //„(£) satisfy

Hn+I -2iH„ + 2nHn _, =

by showing that (2£//„ - 2nHn _ ) obeys the l

differential equation for H„ +l . (The result
from Problem 15 might be helpful.)
17. Construct a general proof of the recursion relation

2(k- n)

(k+ l)(A + 2)

for the coefficients in the nth-order Hermite polynomial //„(£).

18. Let the potential energy of a particle be given by the function

where V and x
(j (j
are positive constants. Sketch a graph of the function and determine the
equilibrium position of the particle. Deduce the form of the harmonic-oscillator ap-
proximation for this potential energy.

19. Let E be the total energy of the particle in the previous problem, and obtain a formula
for the turning points of the classical motion. Consider the results for E < and for E>
as separate cases.

20 Consult a table of integrals to demonstrate the orthogonality relation

/oo
* 2*(*)*o(*)*-0,

where \p n and ip., are harmonic-oscillator eigenfunctions for n = and 2.

A W-shaped potential energy function V(x) produces a set of bound states, the three
lowest of which are arranged as shown in the figure. Sketch the qualitative behavior of the
three corresponding eigenfunctions.

V(x)

22. An eigenfunction in a square-well penetrates the classically forbidden region as indicated

in the drawing. Define the penetration depth d to be the distance into the region over

V(x)

N Mx)
 Problems 297

which the probability density falls by the factor \/e. Deduce the formula for d and

calculate the penetration depth for an electron with V — E= 3 eV.

23. Assume that the indicated square-well potential energy is capable of producing at least a

ground state and a first excited state, as shown. Sketch the behavior of the eigenfunction

for the first excited state.

V(x)

First excited state

Ground state

24. Show analytically how to determine the energy eigenvalue for the first excited state in

Problem 23.

25. Write out the proof of the formula for the square of the uncertainty in x,

2
(A,) = (, 2 >-<,>2 ,

using explicit integral expressions for all the relevant expectation values.

26. Prove that (p) and (E) are real by showing that (/>)* = (p) and (£>* = (E).
27. Let the wave function ^(x, I) be expressed as the superposition of two stationary states
having different energy eigenvalues,

¥ = c% + c'%.,

and obtain a formula for the energy uncertainty AE in this state. As a special case let ^
be an equal-parts admixture of ^ n
and ^ n , and interpret the corresponding result for

AE.
28. Assume that a particle in a one-dimensional box is in its first excited state, and calculate
the expectation values (at), (x ), (p), and (/>'). Evaluate the uncertainties Ax and A/>,

and compute the product of these quantities.

29. Use the wave function ^(x, t) for the superposition of states in Problem 10, and evaluate
the expectation values (x) and (p). Verify that these quantities satisfy the relation

(p) = md(x)/dl.
30. Write down a suitable transition state for a particle in a box describing transitions from
the n = 2 level to the n = 1 level. Evaluate the corresponding dipole transition ampli-
tude.

31. Repeat the steps of Problem 30 for the case of particle-in-a-box transitions from n = 3 to

n = 2.

32. Generalize the considerations of Problems 30 and 31 to allow for transitions between
arbitrary pairs of levels, and deduce the appropriate selection rule for electric dipole
transitions. Obtain a general formula for the nonvanishing dipole transition amplitude,
and compare with the results of Problems 30 and 31.
298 Quantum Mechanics

33. Refer to Figure 5-22 and solve for the nodes of the single-step eigenfunction

\p(x) = C\ cos k\X — — sin k x

{ |
in the region x < 0,

where k x
= \J2mE /h and k 2 = \J2m(V — E) /h. What happens to this solution in the

limit E -> V ?

34. A particle with energy E is incident on a single-step potential energy barrier with step
height V Incidence
{)
. is from the left and E exceeds V , as indicated. Determine the form of

the eigenfunction that describes this situation, and interpret the various contributions to
the wave function.

V(x)

O^ V

35. Use the results of Problem 34 to derive expressions for the transmission and reflection

coefficients T and R, and show that T+ R = 1.

36. A particle with energy E is incident on a rectangular potential energy barrier with height
V ()
. Assume E< V as indicated, and let the particle be incident from the left. The
transmitted wave function has the form

_
= AMk,x-ut)
Ae in the region x > a.
*. ran s

Show that the probability density in the region of the barrier < x < a is given by

*** = \A\<
2
cosh £ 2 (a - x) + { M
—
2
2
sinh*A,(a - x)
k 2)
\

where k {
and k, are defined in Problem 33.

V(x)
 Problems 299

37. The transmission coefficient for the particle in Problem 36 is given by

'
/ k2 k \

T= 1
1

+ — — + —x

smh'k.,a
4 \ ft, k,
J

Derive the approximate version of this formula,

T= 16—
M 1

^o

which holds when a is substantially larger than l/k 2 .

38. A 50 g particle slides with speed 20 cm/s toward a bump 1 cm high and 2 cm wide.

Adopt a rectangular-barrier model to estimate the probability of finding the particle on

the other side of the bump.
39. Let the rectangular-barrier problem be defined by the symmetric potential energy in the
figure, and assume the condition E< V . Use the symmetry to construct eigenf unctions of

definite parity.

V(x)

40. A particle is free to move inside a pizza box with dimensions (a, a, a/10). Determine the
six lowest energy levels, and identify the quantum numbers of the degenerate states at

each level.

41. A particle moves freely inside a cookie box with dimensions (a/5, a/5, a). Determine the
ten lowest energy levels, and tabulate the results according to the quantum numbers of the

corresponding states. What degeneracies occur among these states?

 S I X

QUANTIZATION
OF
ANGULAR
MOMENTUM

many important features of quantum me-

chanics are revealed when the Schrodinger theory is extended to three dimensions. We
find again, as we have found already in one dimension, that the Schrodinger equation
and wave function lead directly to stationary
the probability interpretation of the
states, quantized energy and expectation values. We also discover a powerful
levels,

new quantum concept that does not arise in the restrictive framework of one
dimension. The entire chapter is given over to the development of this fundamental
topic.
A limited version of three-dimensional quantum mechanics has already been
introduced at the end of Chapter 5. The Cartesian coordinate system of Section 5-11
must be set aside, however, because such a choice of coordinates would be very ill

advised for the situation of interest here. We are concerned in this chapter with the
behavior of a system under the influence of a central force. We know from our
experience with classical physics that the general central-force problem exhibits
conservation of angular momentum and that the solution of the problem is expedited when

we build this property into the analysis. Our objective is to learn how the concept of
angular momentum appears in quantum mechanics and how the conservation law-
takes effect as a quantum principle.
It would seem that the central force embraces a rather restricted class of dynamical
problems. In fact, the ideas associated with angular momentum prove to be surpris-
ingly general and make their appearance on many different occasions throughout
modern physics. The topic is a vital ingredient in the theory of atoms, since the
Coulomb interaction between an electron and the nucleus of an atom is a prime
example of a central force. We treat the problem of central forces in generality so that
our can be regarded as comprehensive. We can then apply our conclusions
results
any other appropriate quantum problem.
specifically to the atom, or to
Our treatment is based on the Schrodinger equation in three-dimensional polar
coordinates. We are faced with certain complications when we adopt this coordinate

300
 61 Centra! Forces 301

system and proceed to solve the resulting differential equations. We give these
equations serious consideration so that we can appreciate the interpretation of the
solutions. Our efforts are rewarded in the end as several very important principles
emerge from this investigation.

6-1 Central Forces

Let us begin by recalling the classical treatment of the two-body central force. We
suppose that the two masses m and M are separated by a variable distance and that
r

the center of mass is at rest, as in Figure 6-1. The force on each particle is assumed to
be oriented along the line defined by the separation vector r. We have learned in

Section 3-6 that this two-body problem is completely equivalent to a one-body problem
in which a reduced mass ju. is attracted or repelled by a fixed center of force located at
the origin. We recall that the reduced mass is given by

mM
M+ m

and that the separation vector r is the coordinate vector for the mass /x.

It is also assumed that the force on ju. is conservative and hence derivable from a
potential energy V. The central nature of the force implies that the potential energy
depends on the magnitude, but not the direction, of the vector r. We therefore
introduce a unit vector r and write the central force as

dV(r
F = (6-1)
dr

This expression tells us that F points away from the origin if dV/dr is negative and
toward the origin if dV/dr is positive. We take the function V( r ) to be completely
arbitrary to ensure the generality of our conclusions.
The force law in Equation (6-1) allows us to identify a constant of the motion. We
know from classical mechanics that insights are always gained whenever a conserved
quantity is revealed, and we expect the same experience to carry over in quantum
physics. It is evident that the angular momentum L is conserved since the force F

Figure 6-2

Classical orbit in the plane perpendicular to

Figure 6-1
the angular momentum L. The momentum p
has polar components p and p±
Two interacting particles and the r
.

corresponding reduced-mass particle. Pi.

~~IP.
302 Quantization of Angular Momentum

produces no torque on the particle:

dr
p = ju — and L = r X p
dt

dh dp
=>
dt
=
dr
—
dt
Xp + rX —
dt
=rXF = 0.

Since L is a constant vector, it follows that the classical orbit of the particle lies in a
fixed plane through the origin, perpendicular to the direction of L. In that plane the
momentum p has components along r and normal to r, as shown in Figure 6-2. These
components are expressed in terms of the radial distance r and angle x as

dr dX
Pr
= V- and Px =,r-,

so that the constant magnitude of the angular momentum is given by

L = rp ± .

We use this result to rewrite the expression for the kinetic energy,

2
P Pr + P\ Pr
+
2ju 2n 2n 2jur~

and we find that the classical energy relation becomes

2
L
Pr
%- + -— + 2
V(r)=E. (6-2)
2jU 2jur'

This equation is our starting point for an examination of the Schrodinger equation in

a coordinate system appropriate to the central-force problem.

Equation (6-2) is an interesting formula in classical mechanics. The equality is a
statement about radial variables alone, in which L and E are constants parametrizing
the classical orbit. It is instructive to call the second term on the left a centrifugal

potential energy and identify an effective potential energy function as

Ku(r)= P(r) + — L2
j. (6-3)

The equality becomes

K + Vcll (r) = E (6-4)

and thus assumes a form just like the energy relation for one-dimensional motion. We
can use this result to find the radial turning points for the orbit of a particle, as in the
following illustration.
 6-2 The Schrodinger Equation in Spherical Coordinates 303

Figure 6-3

Effective potential energy for an attractive Coulomb force. The two shaded regions indicate
allowed ranges of r for classical motion with total energies £, and E,. A bound orbit results for

energy Eu and an open orbit results for energy E2 .

Example

Let V be an attractive potential energy of Coulomb form:

b L
V(, (b>0) so VM {r)= - - +
r 2jur

Figure 6-3 shows a sketch of the effective potential energy for some chosen value
of the constant L, along with two selected values of the constant E. Observe that
the centrifugal part of Feff is always a repulsive contribution. The figure tells us
that this term dominates V(r) at small r and prevents the particle from
approaching the point r = 0. The quantity E— V eff
cannot be negative because
of Equation (6-4), and so the equality E= V efr
(r) defines as turning points the
minimum and maximum radial distances for the given energy E. The shaded
domains in the figure indicate the allowed physical regions for classical motion
in the variable r. For E < x
we have a bound orbit with two turning points,
and for E2 > we have an open orbit with one turning point. Pictures of these
two orbits are also shown in the figure.

6-2 The Schrodinger Equation in Spherical Coordinates

We have made the transition from classical to quantum mechanics on several previous
occasions. This time the appropriate form of Schrodinger's wave equation is to be
found from the classical energy relation in Equation (6-2). It is expected that the
terms in this equation should turn into derivative and multiplicative operations acting
on the wave function ty. We know in advance that E becomes the differential
operator ih d/dt and that the Schrodinger equation has the general three-dimensional
structure

V 2^ + V<V = ih —
dt
*, (6-5)
-V

where V = 2
d
2
/dx 2 + d
2
/dy 2 + d
2
/dz 2 The
. central nature of the potential en-
ergy function V is our main consideration.
 .

304 Quantization oi Angular Momentum

Figure 64
Cartesian and spherical coordinate systems.

We are concerned with a general situation where V depends only on r. The radial
variable is a rather complicated function of the Cartesian coordinates:

2
lx +y 2 + z
2
(6-6)

Hence, it is obvious that the Cartesian variables (x, y, z) are not suitable and that
spherical polar coordinates (r, 0, </>) should be adopted instead. Figure 6-4 shows how

the two coordinate systems are related through the formulas

x = r sin v cos

y = r sin 6 sin <

z = r cos 6 (6-7)

We want the wave function to appear as ty(r, 0, <fi,

t ), and so we must reexpress the
differential operator V in terms of the transformed coordinates (r, 0, $). It would be
a simple matter to find a reference book and look up the desired formula for the
transformed operator. We gain considerable insight if, instead, we return to our
starting point and look separately at each of the contributions to Equation (6-2).
We know that momentum components are supposed to be written as differential
operators, as in the representation rules px —> (h/i)d/dx and p —* (h/i)v~. It is
tempting to suppose that p 2 becomes the square of the radial operator (h/i)d/dr;
however, this supposition is not correct. On the other hand, it is not wrong to presume
instead that Equation (6-2) can be implemented by substituting purely radial and
purely angular differential operators for p and L We appeal to this equation for
2
.
r

guidance because the terms indicate a clear separation of radial and angular compo-
nents according to the classical construction in Figure 6-2.
We determine the form of p 2 by considering the special case of a wave
differential

function ^(r, / ), which has no dependence on and <p. The derivation begins with the
derivatives

d^ dty dr 3*
dx 8r 3;

and

d
2
* 1 3* 2
d* x- d
2
*
+
17 r dr "~d~7 ?- Ih 2
 6-2 The Schrodinger Equation in Spherical Coordinates 305

Substitution of y for x and z for x then yields the other two derivatives:

d
2
* 1 3* y
2
d* y
2
d
2
*
1 3
dy r dr r dr r dr~

and

d
2
* 1 8* z
2
d<P z
2
d
2
*
+ -x
dz r dr r dr r dr

Thus, the special form of V ^ 2

is found by adding the three results and using
Equation (6-6):

2d*
—*y.
2
d
V 2
*(r,t) = -—- +
r dr or

We may express this formula in two equally useful alternative ways:

V z*(r,t) = - —d [r
\

r~ or
l

\
2 —
d*
dr
2
1 d
= -—^(r<k). (6-8)
r dr"

The rule p~ -» (h/i)"V " can now be used along with the first of these expressions to
write
2
/ h \
l d d

as the radial differential operator that acts on the wave function *{r,t) in the
Schrodinger equation. We is correct to express L" with no radial
then argue that, if it
2
derivatives and p with no angular derivatives, it must therefore be correct to express
2
p by the purely radial differential operator in Equation (6-9), acting on any wave
function ^(r, 8, (/>, t).

We expect the formula for L2 to contain no radial derivatives because the classical

construction in Equation (6-2) and Figure 6-2 has the effect of separating changes in
angle from changes in r. Let us clarify this point, and secure an important formula for
later use, by examining a specific component of the angular momentum. We choose
the z component
Lz = xPy ~ yP*

and consult Equations (6-7) to manipulate the corresponding differential operator:

hid
— —
d \ hi
——
d
—
d
L z —* — x y = — \
r sin 8 cos <j> r sin 8 sin </>

i
\ dy dx J
t
\
if
y dx

We also invoke the chain rule to find

d dx d dy d dz d d d
= 7~ + 77 T~ + 77 7~ = ~ r sin e sin ^7~ + sin e cos -
77
09 77
d<p dx d<p dy d<p dz dx
r
^Tdy »
 -

306 Quantization of Angular Momentum

and we then compare the two differential expressions. The result is an important new
representation rule:

Lz -- —
d h
• (6-10)
; o<f>

The z component of L is distinguished because the z direction has been selected as the
polar axis in Figure 6-4. The other two components of L also become purely angular
differential operators. We quote the relevant formulas as

7
h
\
— sind>—
r —
dd
d
--
cot cos <f>
— d

and

L -»
hid
- cos<f>—- - cot 0sin<J>—
d
\
(6-11)
/ \ OV <l() I

and relegate the details to the end of the section.

Equations (6-10) and (6-11) can be used to construct the three terms in the square
of the magnitude of L:

L2 = L\ + L; + L\.

The derivation is a straightforward task, which we leave to Problem 3 at the end of

the chapter. The result is another important new representation rule:

2 2 2
/ h\ i h\ l l d d l d \

Note that a special symbol A"' is introduced in this formula to denote the differential
portion of the operator. We explore the detailed structure of A later on, when we
examine the form of the wave function.
The two rules in Equations (6-9) and (6-12) can now by employed to convert
Equation (6-2). The operators act on the wave function ^(r, 6,<f>, t) to generate the
Schrodinger equation in spherical coordinates:

2
h d d d
-^r~A
2\lt -T
or
r
i

\
V or
,
* r
+ A *
\

}
+ V{r)^ = ih—^f.
ot
(6-13)

It is interesting that the kinetic energy term in Equation (6-5) has turned into such a
complicated differential expression. The complications arise because the choice of
coordinate system has been tailored to the behavior of the potential energy term. We
pay this price willingly in order to take advantage of the fact that V depends only on
r. The mathematical strategy pays enormous dividends when we turn to the problem
of solving Equation (6-13).
Our next step is to seek solutions for wave functions of the form

^= ^(r,6,$)e-' E,/h ,
(6-14)

where the time dependence is parametrized by an energy eigenvalue E. Such a wave

 6-2 The Schrodinger Equation in Spherical Coordinates 307

function satisfies the eigenvalue equation

ih —
dt
Sk = E* (6-15)

and therefore has the properties of an energy eigenfunction. Thus, the proposed state
^ is a stationary whose wave function gives a time-independent probability
state,

density l^l
2
=
and whose energy occurs with zero uncertainty. The spatial
|i|/|
2
,

eigenfunction \p(r,9,<f>) and the energy eigenvalue E are determined jointly by

solving an eigenvalue problem based on the time-independent partial differential
equation

2
h
— — r
2
xp + Afy] + V(r)4> = Exp. (6-16)
2jur

Our previous experience in one dimension has taught us to expect a set of allowed
solutions for the eigenvalues and eigenfunctions.
It should be noted that the passage from Equation (6-5) to Equation (6-13) by way
of the classical energy relation has led to a derivation of V " in polar form, and a
great deal more. Our goal is to understand the concept of angular momentum in

quantum mechanics, and our approach has kept that quantity in view throughout.
The main conclusions are embodied in Equations (6-10) and (6-12), along with
Equation (6-13). We should regard the operator formulas for L. and L~ as essential
adjuncts to the Schrodinger equation. The eventual interpretation of the angular
momentum stems from this association.

Detail

Let us sketch the algebra involved in the derivation of the operator expressions
for L x and L . We begin by using Equations (6-7) to derive relations between
the sets of operators (d/dx, d/dy, d/dz) and (d/dr, d/dd, d/d§). The chain
rule has already been used to compute d/d<j>, and may be used again to find

Tr
8 dx
— —— + ——— + ——— =
d dy d dz d
sin 9 cos
d
§ —— + sin 6 sin
d
$ —— + cos 6 —
d

or ox or oy or oz ox oy oz

and

d dx d dy d dz d
~ + +
He JoTx YeYy YeYz
d
= r cos 9 cos 4>
—- + r cos 9 sin <p
—d
dx dy dz

The results for the operators (d/dr, d/dd, d/d<j>) can be assembled in matrix
 — —

308 Quantization of Angular Momentum

form as

8 3
sin 6 cos (p sin sin <p cos
Tr
d
—r
T r cos 6 cos $ r cos # sin </> si
Ty
d d
—r sin # sin </> r sin # cos (j>

8$

The square matrix can then be inverted to obtain expressions for the operators
(8/8x, d/dy, d/dz):

d cos 6 cos 4> sin i

8
sin 6 cos $
Tx r sin# Tr
8 cos o sin ( cos <p 8
sin sin $
Ty r r sin i
~dl

d sin 6 d
cos
Tz T$>

(It is a straightforward matter to multiply the two square matrices and get the
unit matrix as the expected result.) We proceed next to the calculation of the
desired components of L:

hid d \

•"*•-*'"'
7
1
'IT
z
Ty )

h d sin0 d
( n \
t sin u sin <b\ cos u
1
\ dr r dd)
1 d cos 6 sin <j> d cos <p 8 \

rcos 6 sin # sin <b + +

\ dr r 89 rsm6 8(}>)

and

Lv = */>, ~ *fc
5 jt dz
d cos # cos
r cos 9\ sin cos <i) — +
4>
—d —
sin <£>

—
<9

dr r d6 rsind 8<p

8 sin 8
r sin 9 cos $ cos 9 —
|

dr ~TTe
These expressions reduce in one more step to the formulas quoted in Equations
(6-11).

6-3 Rotational Motion

Angular momentum takes on several curious properties in the passage from classical
to quantum mechanics. The peculiarities are fundamental to the new quantum
interpretation of this important physical quantity. We encounter some of these
 6-3 Rotational Motion 309

Figure 6-5

Particle motion constrained to a circle.

features immediately when we look at simple quantum systems in purely rotational

forms of motion.
The simplest rotational problem concerns the free motion of a particle of mass /x

constrained to a circle of radius R. We can visualize the particle as a bead sliding

freely on a circular wire and compare the system to a particle in a one-dimensional
box. Figure 6-5 shows that the problem has only one coordinate variable, the
azimuthal angle <J>.
The particle is free, apart from the constraint, and so the kinetic
energy is the sole contributor to the classical energy relation:

P\
(6-17!
2n 2ixR-

We have introduced the angular momentum, noting that L, is the only nonzero
component of L.
The quantum particle has a wave function ty{<t>, t) and a probability density
P(<p, t) =
1^(0, 01 We obtain the Schrodinger equation from Equation (6-17) by
2
-

letting the operator substitutions E -* ih d/dt and L, -» (h/i)d/d<p act on ty;

2 2
d
h

2jU,r?
r
2
r
2
^= ih —8 ^
dt
d<f>

A stationary state with energy E is described by the wave function

where \p obeys the equation

2
d 2^ 2fiR

This familiar differential equation has complex exponential solutions of the form

^ = Ae
±,x *
with A2 = ——
2ixR
2

E.

We choose these functions instead of cos \<$> and sin \<j> to prepare the way for a
further property of the stationary states.
310 Quantization of Angular Momentum

At this point we bring forward the essential distinction between the circular system
and the particle in a box. The coordinate in <J>
the problem at hand is a cyclic variable
that repeats itself periodically after the basic interval [0,277]. Therefore, if we want
the stationary-state wave function ^ to be single valued, we must impose a periodicity
condition on the eigenf unction:

,/,(<*> + 2tt) = >//(<*>). (6-18)

This requirement applies to our complex exponential solutions with the following
implication:

£g ±iA(<f> + 2w) = £g ±«A4> ^ g

±2iriX = ^

Thus, the requirement tells us that the parameter X must satisfy

cos27rX + z sin 277 A = 1,

so that the values of A are restricted by the condition

A = m, an integer.

The energy eigenvalue is directly related to A:

2 2
h h
-X 2
2
so Em = -m 2 . (6-19)
2fxR 2iiR'

The resulting quantized energy Em defines a set of discrete energy levels in which the
integer m appears as an azimulhal quantum number.
These remarkable stationary states have an additional property with regard to the
angular momentum L,. We note that the complex exponential solutions are eigenfunc-
twns of the angular momentum operator:

h d
-—Ae ± m *=±hmAe ±,m '
*. (6-20)
i o<j>

Consequently, the angular momentum L, is also quantized in these states, with

eigenvalues given by integer multiples of h. The signs of the eigenvalues ±hm
correspond directly to counterclockwise and clockwise directions of motion. We
recognize the Bohr quantization condition of Figure 4-1 in these observations. We also
observe that the alternative solutions cos m<j> and sin m<$> do not possess this angular

momentum interpretation and have therefore not been employed to describe the
stationary states of the particle. Finally, note that the allowed values of Em in
Equation (6-19) are insensitive to the sign of m, so that every energy above the m =
level has a two-fold degeneracy. In other words, clockwise and counterclockwise
motions have the same energy.
The multiplicative constant in the solution is determined by normalizing ^ to unit
probability. The probability of finding the particle in the azimuthal interval d<p is

given by \^\ 2 d§, and so the normalization condition becomes

1 = / |^|
2
^= /
\A\
2
d<f> = 2w\A\'
 6-3 Rotational Motion 311

Therefore, we take A = 1/ v/2tt and write the normalized wave function as

,im<p

* = ''*-'/*
with m = 0, ±1, ±2, (6-21:
/277

Each member of this set is simultaneously an energy eigenfunction and an angular

momentum eigenfunction, with energy eigenvalue E m and angular momentum eigen-
value hm. Consequently, both of the observables E and L. are known with zero
uncertainty in any state ^m .

Equation (6-18) has played the key role in these arguments. We have deduced
quantization of energy and quantization of angular momentum from the single-val-

ued property of the wave function. Let us reconsider this condition and acknowledge
that the property is not as self-evident as it may seem. We realize that the wave

function ^ is not observable and that single-valuedness should be imposed on the

2
probability density |^| . For a stationary state we have
iEl/h 2
v|'
Ae iX +e SO 1*1 \A\ , a constant.

2
Thus, we see that |^| is already single valued and continuous, whether or not A is
equal to an integer. Of course, this assertion is restricted to situations where * is a
stationary state. Let us reapply the requirement of single-valuedness in the context of
a localized particle and write the wave function as a superposition of stationary states.

To make our point we consider a simple combination of two states,

^ = A e O#e -iEt/h + A ,
e
i\'$
e
-iE'l/h^

and examine the <j> dependence of the probability density:

2
= \A\
2
+ 4*4',-«-(X-X')V(*-*')//»
|*|

+ A >* Ae i(\-\')*e -i(E-E')t/h + |^|2_

We replace <J>
by <f>
+ 277 and find that |*|
2
becomes

<A " x (£_£" / *

+ /j*^v^' (A_x ^" 2,7
'
1 ) ' ) '
\A\ 'V'

+ A '* Ae i(.\-\')<l>e 2iri(\-\')e -i(.E-E')t/h _|_ M'|2

Thus, single-valuedness of the probability density implies

e
2v,(\-\') _ j Qr x _ X' = an integer.

We can implement this conclusion by taking every A to be integer valued and thereby
recover the results of the preceding paragraphs.
This entire illustration of rotational motion is flawed from the outset by the
presence of the constraint. Our assumption of a precisely circular path for the particle
violates the uncertainty principle and causes the fixed direction of L to be a violation
of basic quantum principles. These difficulties are handled properly in the full
three-dimensional quantum treatment of rotational motion.

Example

Let us introduce rotation in three dimensions by considering the rotating rigid

body in Figure 6-6. The classical rotator consists of two point masses connected
by a massless rigid rod. We assume free rotation about an axis perpendicular to
312 Quantization of Angular Momentum

Figure 6-6

Rigid body in free rotational motion about a

perpendicular axis through the center of mass.
The classical angular momentum vector L has
a fixed orientation. The direction of L is

uncertain in quantum physics.

the rod and write the classical energy relation in terms of the kinetic energy-
alone:

2
L
—
2/
= E.

The angular momentum L and the moment of inertia / appear in this formula.
The quantum mechanical rigid body is described by a wave function ^(6, t), <f>,

where 6 and <j> refer to the orientation of the rod as shown in the figure. We take
2
the operator rule for I from Equation (6-12) and apply the familiar operator
rule for E to obtain the Schrodinger equation for the system:

2
h d
A 2 * = ih— ¥.
2/ dt

The wave function for a stationary state is written as

where \p and E are found by solving

2
h
A-ty = Exp ,

21

a partial differential equation in the variables (6, <j>). We must learn to analyze
this kind of equation in order to finish the problem. When we are able to return
to the solution we find that quantization of energy and quantization of angular
momentum are again obtained as joint results. In this case, the behavior of the
angular momentum is found to be consistent with the uncertainty principle.
 6-4 Separation of Variables 313

6-4 Separation of Variables

The Schrodinger equation determines a unique wave function ^ if a description of ty

is given at = 0. Our procedure in one dimension has been to find the eigenfunctions
/

of the time-independent equation first, thereby establishing the spatial behavior of the
stationary states. This complete family of energy eigenfunctions can then be used to
assemble a unique solution ^ for any given description of the state at t = 0. We take
the same approach in three dimensions and look first at the time-independent
equation for the allowed spatial eigenfunctions \p(r, 6,<j>). Equation (6-16) is the
starting point for this investigation.
We solve the partial differential equation for \p by appealing again to the method
of separation of variables. The straightforward procedure runs into complications this
time, because of the intricate nature of the differential operations in spherical
coordinates. The first step is to propose a product form of solution, where the radial
dependence and the angular dependence occur in »// as separate factors:

4,(r,0,$)=R(r)Y(6 t 4>). (6-22)

The motive for this construction can be seen in the following rearranged version of
Equation (6-16):

2
3 3 2fxr

or or h"

We note that a purely radial operation appears on the left side of the equality, while a
purely angular operation appears on the and usefulness of this
right. The validity
observation hinge on the fact that the central potential energy V depends only on r.
Hence, the adoption of the product form \p = RY causes the radial and angular
operations in the equation to act separately on the radial and angular factors in the
eigenf unction:

d
— —Y +
dr dr
r
2
dR
—r (E- V(r))RY =
2ur 2

h
"
-RA 2
Y.

We divide through by RY to find

+ —r (E-
dR 2ur 2 KY
2

R
d
-r 2
dr
— dr n
V{r))R
Y

and we observe that the left side of the result depends only r, while the right side
depends only on 6 and (p. Such an equality can hold between functions of different
variables onlyif each side of the equality is a constant. We therefore set the two sides

equal to a separation constant A and obtain the following pair of equations for Y
and R:

-A2 Y=XY (6-23)

and
2
dR 2ur
- + ——(E- V{r))R = XR. (6-24)
dr dr
314 Quantization of Angular Momentum

Note that the two differential equations are linked together because the separation
constant appears in each equation. Thus, we conclude our first step by learning that
eigenf unctions exist in the product form \p = RY, provided properly behaved solutions
of Equations (6-23) and (6-24) can be found.
Our main goal in this section is to determine the angular dependence of \p. We set

aside the equation for R(r) so that we can concentrate on Equation (6-23), the partial
differential equation for Y{0,<$>). For this purpose we need to recall the detailed
structure of the differential operator A2 , as found in Equation (6-12). We apply this

operator in Equation (6-23), multiply through by sim#, and rearrange terms to

generate the equality

-
d Y
—
d<p
j = sin — d

da
sin —
dY
da
+ X sin
2
Y. (6-25)

This equation is set up for our second step in the separation of variables, since the
equality involves a pure <p operation on the left and a pure operation on the right.
The next move is to look for solutions in which the function Y depends on these angles
through two separate factors:

K(0,*) = 0(0)<D(4>)- (6-26)

We insert this construction into Equation (6-25) and divide through by 04> to find

d 2$ d®
1 1 /

sin 6 —d-sin# —— + X sin ^

2

<& d<f 0\ dO (16

= m2 . (6-27)

The resultan equality between a function of

is on the left and a function of on <j>

the right. We
argue as before that each side must be equal to a constant, and we build
2
this property into Equation (6-27) by introducing the indicated parameter m as a
second separation constant. We then conclude that solutions of Equation (6-23) exist
in the product form Y = 0$, provided properly behaved solutions can be found for

the two ordinary differential equations

d 2 <b
+ m2 <S> = (6-28)
# 2

and

1 d d€)

sin d0
sin i

d0
+ (
X - —^
sin-
I
= 0. (6-29)

2
Equation (6-27) has been divided through by sin in the second of these results.

We have seen differential equations like Equation (6-28) many times and are well
aware that the solutions are oscillating functions. In fact, the <J>-dependent part of this
analysis can be identified immediately with the purely azimuthal problem of Section
6-3. Accordingly, we choose the desired solutions of Equation (6-28) to have the
complex exponential form

<!>(<#)) = *""* with m positive and negative, (6-30)

 6-4 Separation of Variables 315

and we reject the alternative choices provided by cos m<$> and sin m<p. Section 6-3 has
taught us that these solutions have proper azimuthal behavior only if the functions are
periodic in <J>
with period 277. This requirement implies that m must be integer valued
in Equation (6-30), as it is in the case of the rotational wave functions in Equation
(6-21). Thus, m appears again as an azimuthal quantum number.
The 8 dependence of the eigenfunction is found by solving Equation (6-29). This
part of the problem presents a type of differential equation that has not come up in

any of our previous studies of quantum systems. Let us make the following brief
remarks about the solutions of the equation, without proof, and reserve the mathe-
matical details for later discussion. We note that the domain of the polar angle 6
spans the interval [0, -n] and that the differential equation contains infinities at the
endpoints owing to the zeros of the factor sin 6 at 8 = and m. The only solutions for
0(#) that are finite and single valued over the whole interval are those for which the
separation constant A has the special values

\ e = t{t+ 1) with {= 0,1,2,... . (6-31)

Thus, the integer m is joined by another integer { in the determination of the allowed
solutions of Equation (6-29). These two integers are linked by a further condition, as
each given nonnegative value of / is assigned a set of allowed values of m in the
range

m = -/, -t+ \,...J- 1/. (6-32)

The resulting properly behaved solutions are labeled by the two integers as © /m ( 6)
The labels are attached to reflect the fact that the functions vary with c" and m
through the explicit appearance of the two parameters in the differential equation.
Again, we emphasize that the unfamiliar assertions in this paragraph are presented
without proof and are not supposed to be self-evident. The particular statements in
Equations (6-31 ) and (6-32) are very important results; their content is essential to our
understanding of angular momentum. We provide some of the mathematics behind
these conclusions at the end of the section.
Our main interest in the quoted results lies in the physical interpretation of the
stationary states. Let us set the stage for this discussion by combining the acceptable
solutions for 0(0) and $(<£) and forming a family of functions of the two angular
variables:

Y, m (8,<!>) = ®, m (6y»>*. (6-33)

We call these functions spherical harmonics, and we characterize their properties by

means of the following eigenvalue formulas. The combination of Equations (6-23) and
(6-31) implies that Yfm must satisfy

-A% m = <?(/+ \)Yfm . (6-34)

The elementary <$> dependence in Equation (6-33) tells us that Y(m must also satisfy

1 d
-T7Y, m = mY, m - (6-35)
i o<j>

The members of this set of finite single-valued functions are indexed according to the
316 Quantization of Angular Momentum

scheme indicated in Equations (6-31) and (6-32). We arrange the indices represented
by m in steps of increasing ( as follows:

{= m =
t=0 m= -1,0,1
e= 2 m= -2, -1,0,1,2

The labels / and m are known as the angular momentum quantum numbers. The physical
meaning of these symbols is the primary topic of interest in Section 6-5.
We do not intend to write down specific expressions for the functions Q fm {8).
Instead, we follow established practice and present the 8 dependence along with the $
dependence in the combined form of the spherical harmonics Yf m (6,<§>). Table 6-1
furnishes a partial list of these functions for the £ values 0, 1, and 2. The tabulated
expressions are subject to a normalization condition and include certain multiplicative
constants as a result of this property. According to universal convention, all the
spherical harmonics are normalized to unity by the requirement

i = [ \Y, m {e,<i>)\
2
dsi, (6-36)
•',11 o

Table 6-1 Spherical Harmonics

/= m = *»-M*

t= 1 m = 1

m =

m= -1

/= 2 m = 2

m = 1 — sin# cos 8 e'

4"

2
m = (3cos - 1)

m= -1 F, ,
= 1/
1
—
877
sin 8 cos 8 e "*

m= -2 2fl<,-2«f>
 6-4 Separation of Variables 317

where the integration ranges over < 8 < tt and < $ < 277, and where the element
of solid angle is given by

d2 = sin OdOdQ.

It is Yem in Table 6-1 or in any other

straightforward to verify that any given ,

tabulation, has the properties expressed by Equations (6-34), (6-35), and (6-36).
One very significant point should finally be emphasized. We observe that the
potential energy V(r) has no influence whatsoever in the solution of Equation (6-23),
and we conclude that the determination of the angular behavior is independent of the
specific nature of the central force. This conclusion means that the dependence of the
wave function on 8 and <|> is always given by the spherical harmonics for every
central-force problem. We also note that V(r) appears in Equation (6-24), the
equation for the radial function R(r), and that the energy eigenvalue E makes its

appearance in the same radial equation. Thus, the energy and the radial behavior of
the eigenfunction are controlled by the choice of central force, but the angular
behavior is controlled by the mere fact that the force is central.

Detail

Equation (6-31) is sufficiently important to warrant the following mathematical

discussion. Let us proceed by transforming the structure of Equation (6-29). We
define a new variable by setting

£ = cos 8 so that d£ = — sm 8 dQ,

and we introduce a new notation for the solution by writing

@(8) = p(n.

The result is a differential equation for the function P(£) of the form

d dP I m2 \

n i-n-rr
'4 y
•
+ U
\ i-r
P=

in which the domains of the variables are related by the transformation

8 in the interval [0, it ] =» f in the interval [

— 1,1].

We in advance that m is integer valued, and we want to show that A must

know
Equation (6-31). For this purpose we consider first the special m =
satisfy case
and examine the solution of the corresponding differential equation:

dP
—d (1 - f
2
)— + \P= 0.
dr 'tf

Let us assert, without proof, that the only finite single-valued solutions of this
equation are polynomial functions. We define the integer ( to denote the order of
318 Quantization of Angular Momentum

each polynomial and write

P($) = ••• +a,£' witha,# 0.

This highly abbreviated expression suffices because only the highest power of £
is needed in the next few steps. We return to the differential equation and
compute the derivatives

dP
+ ^,?'- 1

and

dP
—d (i -J )— =2 —d •••+^,(r ,

-r ,

)i

•
+ <f(Y- l)^'"2 - /(/ + \)a^.

We then compare this result with the quantity

-XP= -\(--- + <,,£')

and find that the coefficients of J agree if A obeys the formula

A = <f(<f+ 1),

as quoted in Equation (6-31). The Ah order solutions in the m = case are

denoted as /^(f ) and are called Legendre polynomials, after the 18th century'
mathematician A.-M. Legendre.

Detail

Equation (6-32) is also important enough to justify a few mathematical com-

ments. We observe that the original differential equation for P(£) is not affected
by the sign of m and that only positive values of the integer need to be
considered in the search for solutions. Let us write the equations for m > and
for m = together,

d dP m
AY+ 1)
i - V
and
d dP,
-l-J 2
-/
d£
+ ^+l)^0,
«S

and make a series of swift remarks without further demonstration. The equation

for Pf can be differentiated m times to generate a new equation of the form

d2 d'" d dm dm
(l - f
2
)—
'
d$
7
2
P,-
f 'H(m + 1)
m P,+
((-
'
V
m)U+
A m + l)-—
m P,= '
d$
0.
df" d<, dl
 64 Separation of Variables 319

2 m/2
A newfunction can also be identified by defining the expression (1 — £ )
m m
d Pe/dK, The new equation can then be used to show that the new function
.

satisfies the original differential equation for P. These arguments tell us that a
whole family of solutions is obtained for each / and for every positive m by the
construction

2 m/2
JV-tt) - (l - f ) MS)-
dV

Since the highest power in Pf is f , the rath-order derivative produces a

vanishing result for Pfm if m exceeds t '. It follows that we must have m < /, as
we have stated in Equation (6-32).

Example

The (0, 4> )-dependent solutions are easy enough to confirm as specific cases. Let
us turn to Table 6-1 for the spherical harmonic with /= m = 1,

K„ = -l/ —
077
sin***,

and verify that this function satisfies Equation (6-34). We recall Equation (6-12)
to perform the differentiation:

A *»-v^
/ 1

sin
d

86
sin —
d6
+
i

sin'0 dp
d
sin v e

5
^— —-sinflcosfo'* +
1 1

t-t (-*'*)
sin0 do sin

e* /3
= V
V
/ 3

8tt sin 6
-(cos
2
- sin
2
- 1) = -2i/
V
—
8tt
sin0*'* = 2K, '

The answer agrees with Equation (6-34) since /( ^ + 1 )

= 2 for {= 1 . Equation
(6-35) is easily checked and gives the result

1
~
i
— d

<9<fj
Y„ = -i/--sin0
V 877
,"t> }"

as appropriate for m = 1. The normalizing constant in Yn is also in order:

(
•'all £2
\Yn \
2
dto= f
•'0
2
" d<t> /""sin
•'O
</0
\
— 877
sin
2

3 4
- 1
4-3 '
 .,

320 Quantization of Angular Momentum

using f = cos to transform the integration. Note that the minus sign in Y l ,

plays no part in these exercises. This sign is due to a phase convention and does
not need to concern us.

6-5 Angular Momentum Quantum Numbers

Bohr's model of the atom introduces quantization of angular momentum as a

supplementary quantum hypothesis. Consequently, an angular momentum quantum
number appears in the model as an ad hoc property of the classical angu-
lar momentum. These primitive notions can now be replaced by turning to the
Schrodinger formalism, where the actual behavior of the angular momentum is found
to be a consequence of the theory and not a matter of hypothesis. The way is clear for
this deduction of quantum properties, now that the mathematical results of Section
6-4 are properly in place.
Our approach to angular momentum in quantum mechanics is by way of the
spherical harmonics in Equation (6-33). The characteristics of this family of functions
are embodied in the two eigenvalue formulas found in Equations (6-34) and (6-35).

We can interpret these results at once if we recall the angular momentum representa-
tion rules

L2 -» -h 2A 2 and L, -»
h
-
i
—
d4>
d

and if we rewrite the eigenvalue equations as

-h 2A% m = h
2
t(S+ l)Y, m and
l

-
i
—o<j>
Y, m = hmY, m . (6-37)

The two equations tell us that the spherical harmonics are simultaneous eigenfunc-
tions of the L 2 operator and the Lz operator. Equation (6-22) transfers these
properties directly to the stationary states, since the spherical harmonics provide the
(0,<j>) dependence of the various stationary-state eigenfunctions.
Let us summarize our observations in the following two statements. The stationary
states are eigenfunctions of the square of the angular momentum such that

the eigenvalues of L~ are equal to h~c*(c* + l),

where ( is any nonnegative integer.

The stationary states are also eigenfunctions of the z component of the angular
momentum such that

the eigenvalues of L, are equal to hm ,

where the integer m lies between — f and {

for each given value of the integer (

These statements express the first principles of angular momentum quantization. The
occurrence of integers means that the allowed values of L and L, are discrete. The
eigenvalue properties also imply that the allowed values occur in the stationary states
 6-5 Angular Momentum Quantum (lumbers 321

with zero uncertainty. These quantized results L 1 and L, are

for the observables
determined by the angular momentum quantum numbers £ and m, the integers
introduced as indices for the spherical harmonics. The stationary states are labeled by
the same quantum numbers as an indication that any such state is assigned the precise
2 2
value h (?(tf+ 1) for L and the precise value hm for L,. This quantum mechanical
picture of angular momentum quantization is more complex than the rudimentary
concept proposed by Bohr.
The quantization scheme describes a peculiar treatment of the vector L in which
quantized values are assigned to L„, but no statements are made about L x and L y .

This property of the angular momentum stems from fundamental quantum principles
and deserves a closer examination. Let us identify the three Cartesian components of
L according to the rule

h
L^ -A
i

by writing

d d d d d d
A x =y-
oz
z—
ay
, A = z-
ox
x—
oz
, and A = x-
2
ay
y—
'ox
. (6-38)

It is not difficult to prove that the three differential operators obey the following
multiplication formulas:

A X A,-A,A,= -A z ,

A A, - A,A,= -A,,
v

A,A,-A,A,- -A r (6-39)

The proof of these remarkable relations is left to Problem 9 at the end of the chapter.
We wish to show that the uncertainty principle is at work in Equations (6-39) by

demonstrating that exact nonzero values cannot be assigned to all three components of
L. We proceed by assuming the existence of a state ^ in which L has the precisely
specified vector value

h(<?x x + yy
<? + ri).

The factor h is included for convenience, and the { 's are introduced as dimensionless
parameters. This hypothesis about the state Sk can be formulated in terms of
eigenvalue equations:

ft

-A,* = hfx <lr,

i

h
-A.* = i^t. (6-40)
i

Let us select the last of these statements and use the first of Equations (6-39) to obtain

tp- -iA,¥ = i(A x A y -A A )*.

 .

322 Quantization of Angular Momentum

Figure 6-7

Quantized angular momentum vectors for c°

= 1 . The allowed z components of L are +h

and 0.

\f2-h.

Uncertain

We then employ the first two of Equations (6-40) to find

W= i(itx it,-it,itx )*.

We conclude that the parameter c*z vanishes in the given state. Similar procedures
can also be used to obtain vanishing results for t"x and t* in the same state. It follows
that the vector L is allowed to have a precise vector value only if the state has angular
momentum equal to zero. Only one of the observables L L and L. can be specified x
, ,

with zero uncertainty in more general circumstances, and L. has been taken as the
chosen component.
Our quantization statement concerning L, tells us that each value of the quantum
number t° is assigned 2c" + 1 values of the quantum number rn between — ( and c"

We can interpret this property of the angular momentum by visualizing a collection of

possible L vectors with the same allowed length h\jc"(c*-\- 1) and with 2c" + 1 allowed
projections onto the z axis. Every member of this collection has a definite value of L,,
given by hm with zero uncertainty, and completely uncertain values of L and L y A x
.

precise direction for L is and so the vector may lie anywhere on a cone
not defined,
whose axis points in the z direction and whose apex angle is determined by the
quantum numbers c* and m. There are 2c" + 1 such cones corresponding to the
different m values for the given c° value. Figure 6-7 illustrates this state of affairs in
the t" =
There are three uncertain orientations for L, with three definite values
1 case.
of L z and with random values of L x and L
, subject to the length constraint ,
y

L 2x + Lyl + L 2Z = 2h 2 This representation of L vectors should not be confused with the

.

classical precession of L around a fixed axis. Precessional motion is a dynamical

process caused by an external torque, whereas Figure 6-7 is a schematic picture of
quantum kinematical behavior for a free L vector.
A quantized L vector is never permitted to point along the z axis because L x and
L y would then have the value zero with no uncertainty. We have just learned that the
largest eigenvalue of L, is he* and that the length of L is h\lc"(c*+ 1) . Therefore, the
 6-5 Angular Momentum Quantum Numbers 323

smallest angle between L and the z axis is equal to cos~' JS/(t+ 1) , an angle that
approaches zero only for very large values of the quantum number { . In this limit the
states having m = +£ are as close as possible to the case of a classical L vector with a
fixed direction. Figure 6-7 shows a situation far from this limit, where €= 1 gives a
minimum angle of 45° between L and the z axis.
The central-force problem is said to have rotational symmetry since the dynamics is

governed by a potential energy that is independent of angles. The analysis of the

problem appears to give the z component of L a privileged role associated with the
choice of direction for the polar axis. Since the central force does not single out a
preferred direction in space, it follows that the polar axis can be chosen in any
arbitrary direction as far as the dynamics is concerned. Our conclusions about the
quantization of angular momentum may be stated in more general terms as a
consequence of this symmetry. The arbitrariness in the choice of z axis allows us to
refer to the component of L along any direction and assign quantized values defined
by the eigenvalue hm accordingly.
The quantization of angular momentum should seem rather unnatural from our
macroscopic point of view. We have looked at quantum ideas in this light before, and
so we should be prepared to see h play its part again as a very small quantity. We
should also recall that h carries the units of angular momentum. Let us return to
Figure 6-5 and consider a macroscopic object orbiting a fixed point at constant speed.
If we let the angular momentum
be of order J s, we find that the smallness of h
1 •

causes the corresponding angular momentum quantum number to be of order 10 34 It .

would be unrealistic to insist (or deny) that the angular momentum must have discrete
values, and to claim that the direction of L must be uncertain, for such a classical
object. However, we can expect to find firm evidence for these notions in submicro-
scopic systems, where angular momentum quantization becomes a vital consideration.

Example

Let us recollect the rigid-body problem from the example at the end of Section
6-3 and show that a connection develops between the quantization of angular
momentum and the quantization of energy. This direct link comes about
because the problem is defined by angular variables alone, as in Figure 6-6. The
stationary-state eigenfunctions are known to satisfy the partial differential
equation

21
A 2^ 2^-

If we compare this with Equation (6-34), we can immediately identify the

spatial eigenfunctions

</7 m = Y, m (6,<!>)

and the energy eigenvalues

Ee( = —
2I
/(/+ v 1).

Hence, the desired stationary-state wave functions are uniquely determined by

324 Quantization of Angular Momentum

the angular momentum quantum numbers:

%m = Y,m {Q,$)e- iE< l/h

.

Note that the energy depends only on ( and that each / has 2/+ 1 different
wave functions corresponding to the different values of m. Thus, each of the
quantized energy levels Ef has 2/+ 1 degenerate states. Equation (6-36) tells us
that the wave functions are automatically normalized to unity over the total
solid angle:

= ( \%J
2
dQ.
•',11 o

Equations (6-37) imply that the stationary states are eigenfunctions of the Lr
operator and the L, operator:

h d
-h 2A2 *, m = hW+ l)% m and ~^-% m =
i o<j>
fim% m .

Because of the elementary dependence of the spherical harmonics, the

<f>

probability density is independent of in each of these states: <f>

2 2 2
\%J = \Y,J = \G, m (0)\ -

This simple observation has deeper roots in the uncertainty principle. We note
that the L. operator (h/i)d/d<f> is related to <£ as the momentum operator
{h/i)d/dx is related to x. Therefore, we might suppose that an uncertainty
principle for <f>
and L z should hold by analogy:

h h
AxAft
!x
>- => A<J>AL.z >-.
2 2

Since ty, m is an eigenfunction of Lz , it follows that the uncertainty in Lz is zero

and that the uncertainty in the azimuthal variable is maximal. The probability
distribution is uniform in <f>
and displays no trace of localization in the
azimuthal angle as a reflection of this property. It is instructive to sample some
of the angular probability densities by examining the /= 1 case. We consult
Table 6-1 to find

3 3
l*u|
2
= l*.-,f
2
= ^sin 2 and |* 10 |
2
= —cos 2 0.

The corresponding ^-dependent distributions are sketched in Figure 6-8. The

absence of a dependence allows us to visualize the probability distributions in
<t}

space by rotating these drawings around the z axis, as suggested in the figure.
We let the distance from the origin to the resulting surface represent the value of
2
I^J in that direction for the given value of t and m. Therefore, the quantity
2
\^/„,(&, <j>, t)\ dQ, expresses the probability of finding the rigid body in an
element of solid angle dQ, oriented in a direction defined by the angles (6, <p).

Let us suppose that observations of this orientation are made for a large number
 6-6 Parity 325

of systems with energy E( . Since E( has a (2/+ l)-fold degeneracy, the results
of the measurement must conform to the average of the 2^4- 1 probability
densities for the set of degenerate states with the given energy. This quantity
always turns out to be a constant, independent of angles for any { . To illustrate,

let us consider our results for ( = 1 and compute the corresponding average:

1(3
1

{i*, 1^
* HI I
2
+ 1^
T I
-
3 \
—
4tt
(sin
2
+ 2
cos 0)
7
\

= -
477
1

The rotational symmetry of the problem is the basis for this conclusion. The
result cannot depend on angles because the dynamics does not identify a spatial
direction to use as a natural choice of orientation for the z axis. The (2/+ 1 )-fold
degeneracy of the energy levels is the manifestation of this symmetry in
wave-function language.

6-6 Parity

Rotational symmetry guides the central-force problem, and angular momentum

provides the guiding principles. The symmetry is reflected in the angular momentum
interpretation of the stationary states and in the generality of the angle dependence
furnished by the spherical harmonics. These angular eigenfunctions exhibit another
symmetry associated with the concept of parity. This additional property of the
stationary states can be developed now, even though our solution of the quantum
central-force problem is still incomplete, since the angular part of the solution is the
only necessary ingredient.
Parity pertains to the reflection properties of the wave function. The concept is

unique to quantum physics and has no natural place in classical mechanics. We have
326 Quantization of Angular Momentum

Figure 6-9

Space inversion of the coordinate axes. The coordinates transform from (x, y, z) to
(-at, -y, -z).

seen the idea of parity in one dimension. In particular, we have learned that a
symmetric potential energy V(x) leads to eigenf unctions \p(x) with either even or odd
behavior under the reflection x —> — x. The parity operation in three dimensions is

defined by reflecting all three axes according to the coordinate transformation

(x, y, z) —> ( — x, —y, —z) indicated in Figure 6-9. The operation is also called space
inversion as the transformation changes a right-handed system of coordinates into a
left-handed system.
Parity complements the rotational symmetry of the quantum central-force prob-
lem. It is clear from Equation (6-6) that the transformation (x, y, z) -» (
— x, —y, —z)
has no effect on and that V(r) is likewise indifferent to the inversion of the axes. This
r

additional symmetry of V means that parity offers other information about the states
in addition to the angular momentum interpretation. Figure 6-10 shows how the
angular coordinates are affected by space inversion. Since the radial aspects of the
solution have nothing to do with this operation, and since the general spherical-
harmonic form of the angular solution is already known, it follows that the parity
properties are available for immediate inspection just by looking at the behavior of the
spherical harmonics.

Figure 6 10

Location of a point in spherical coordinates and in parity-inverted spherical coordinates. When

the Cartesian axes are reversed, the polar angle measured from the new z direction as m — 6
is

and the azimuthal angle is measured from the new x direction as w + <£>. The radial coordinate
r is the same in the two coordinate systems.
 6-6 Parity 327

Figure 6-10 shows that the spherical coordinates (r,0,<]>) are transformed in the
new spherical coordinates (r, m — 6, v + $). Let us apply this
inverted system into the
transformation to a stationary state with angular momentum quantum numbers if

and m, and with angle dependence given by F/m ( #,(£). The parity operation causes
the spherical harmonic to undergo the replacement of variables

Y, m (B,$) - Yem {*-0,v + $).

The new function turns out to be unchanged in value except for a possible change in
sign. We refer back to Equation (6-33) and obtain a sign-changing factor through the
relation

* + *> = (-i)"e/m (?r- ,m

Yfm {m - 9,7T + 4>) = ®, m {ir- e)e imi 0)e +.

The connection between ®^ m (w —

0) and 0^ m (#) acts as another source of minus
signs. We investigate this detail below and learn that the final expression for the
transformed spherical harmonic is

Y, m {ir - d t
v + *) = {-\)% m {e,+). (6-41)

This formula tells us that the stationary states have definite parity given by the factor
(— 1) j in addition to the angular momentum properties associated with the quantum
numbers £ and m. The parity is determined solely by i such that states with even /
have even parity, and states with odd ( have odd parity.
Our deductions about parity are going to seem rather sterile until some physical use
for the concept arises. Parity makes its appearance here as part of a classification
scheme for certain types of wave function. Let us accept this notion on kinematical
grounds and wait for dynamical applications to come up in due course.

Detail

Let us establish the relation between @^ OT (7r — 0) and Q fm {6), and supply the
missing link leading to Equation (6-41). We return to Section 6-4 and recall that
our solutions for 0(0) have the form

,/'"

^) = (i-n n/2
^(n, r = cos

We note that the parity operation produces the sign change

f
—> — £ since cos(tt — 6) = —cos 6.

It is a property of the Legendre polynomials that the functions P^) are

composed even powers of £ for even / and odd powers of f for odd ( (The
of .

differential equation for Pf (£ ) is not affected by the sign change I -» — f, and so

the solutions can be classified as even or odd.) The resulting parity of the
polynomials is described by writing

/>,(-{) = (-i)^(f).
328 Quantization of Angular Momentum

We use this formula to establish the corresponding behavior of the /^ m 's:

m
>\""/2
d
^ m (o-/v m (-n = (i-n d(~0 M-i:
</'

= (i - ni-i)^j(-i) /v(n = (-1)

'" ,j
/
r
p<i$)-

The desired result for the 6 dependence is expressed as

Hence, the operation of space inversion causes the spherical harmonics to

become

Yfm {ir - 0,77 + *) = B /m {n - 6)e'

m ^+^

= {-\Y+m ^ m {e){-\) m e^ = {-\)%m {e^),

as quoted in Equation (6-41).

Example

Let us test the parity formula by checking the behavior of the spherical
harmonic K n :

M" - 0,77 + <f>)

= — \ — sin(77 -0)e>

-\
V
—
877
sin0(- (0 +)

The result agrees with Equation (6-41), since the parity of K n is supposed to be
odd.

6-7 Quantization of Energy

The central-force problem is solved in two stages after the separation of variables is

introduced in Equation (6-22). All aspects of the angle dependence are established
first on grounds of rotational symmetry, without any regard for the actual nature of
the central force. The specific dynamics enters the problem through the choice of
potential energy V(r), only when consideration turns to the solution for the radial
dependence. This next phase of the procedure also includes the determination of the
allowed energies of the system. Thus, the two-stage approach demonstrates quantiza-
tion of angular momentum and then quantization of energy, as the investigation
proceeds from angular behavior in Equation (6-23) to radial behavior in Equation
(6-24).
 6-7 Quantization ol Energy 329

Our attention shifts to the differential equation for the radial factor R(r) in the
stationary-state eigenfunction. When we take Equation (6-31) into account and
rearrange terms, we find that Equation (6-24) becomes

2
dR h

2jur
2
dr dr
V(r) + --JV+
2/xr"
1) R = ER. (6-42)

An alternative radial equation can also be obtained by using the second version of the
2
formula for V given in Equation (6-8). If we substitute this expression for the radial
derivative in Equation (6-42) and multiply through by r, we generate the equivalent
radial differential equation

fi
2
d2 h
2

T (r/?) + V(r) + —J{(+

2/xr
1) (rR) = E(rR). (6-43)

Our interest is drawn immediately to the close resemblance between the second form
of the equation and the classical energy relation in Equation (6-2). We see that the
radial differential equation follows directly from the classical formula when the two
replacements

—
n
—d\ and L -> hY(£ + 1) (one dimension)
i dr J

are introduced as operations acting on the radial function rR(r). Note that the
substitutions are specifically labeled as one-dimensional rules, intended only for
application to the radial dependence of the stationary states. These replacements
should not be confused with the three-dimensional operator formulas for p~ and L~
found in Equations (6-9) and (6-12).
We collect the terms in brackets in Equations (6-42) and (6-43) and define the
effective potential energy for the quantum central-force problem as

2
h
ya t(r)= V(r)+ -—J{{+
2jur~
1), (6-44)

by analogy with the classical expression in Equation (6-3). This ^dependent quantity
provides the means by which the given potential energy V( r ) makes its entrance in the
problem. The energy eigenvalue E also makes its appearance along with V(r) in each
of the two versions of the radial differential equation. The structure of Equation (6-43)
is especially interesting because this differential equation for rR( r ) is identical in form
to Equation (5-25), the differential equation for the eigenfunction \p(x) in one
dimension. The parallel between these equations suggests that our insights about the
solution ip(x) for a given potential energy V(x) can be transferred virtually intact to
the solution rR(r) for a given effective potential energy Veff (r). Of course, we must
allow for a certain distinction between the variables, since x varies over ( — oo, oo) in
one dimension while r varies over [0, oo) in three dimensions. This observation tells us
that the question of evenness or oddness does not apply to the r dependence, and it

reminds us that the parity of the three-dimensional eigenfunction is a property of the

angular behavior alone.
Our experience with Equation (5-25) leads us to suppose that the radial differential
equation should have a family of properly behaved solutions, corresponding to a set of
 :

330 Quantization of Angular Momentum

allowed energies. A particular value of E is acceptable as an energy eigenvalue if the

accompanying solution R(r) is continuous and finite everywhere, including the point
r = and the limit r — oo. The £ dependence of Veff is an important feature of this
>

problem, since the explicit appearance of the quantum number £ in the radial
equation causes the form of the differential equation to vary with the choice of £ . It

follows that every £ has its own sequence of allowed results for E and R(r) and that a
must be introduced to label all the radial solutions. We see that
pair of integer indices
£ needed as one of the labels to define the differential equation through the £
is

dependence of Veff and that another new quantum number, denoted by n, is also required
to list the quantized solutions for a given choice of £ . We identify the family of radial
functions and energy eigenvalues by the notation

R„s(r) and EH „

and we summarize the arguments by rewriting Equation (6-42) as an eigenvalue

equation

2 2
h d d h
-r 2 - +
\

2
V(r) + -—>£(£+ !)*„,= E n ,R n ,. (6-45)
2fir dr dr 2jir

This formula indicates a different operation on the left side of the equality for each
integer £ and produces a correspondingly different set of allowed solutions as a result.
We use £ to label the various sets, and we use n to index the members of each set.
We have proceeded to the solution of the central-force problem by following a
series of steps beginning with Equations (6-14) and (6-22). The result of these
procedures is a collection of stationary-state wave functions with the general structure

% fm {rjA,t) = R ne {r)Yeak {9,+)r iB" l

'k . (6-46)

We note that the states of this three-dimensional problem are specified by the
assignment of three quantum numbers. The angular momentum quantum numbers £

and m
have already been interpreted in Section 6-5, and especially in Equations
(6-37). Let us return to these two eigenvalue formulas and observe that the eigenfunc-
tion behavior can be transferred directly to the stationary states:

-h 2A2 %, m = h
2
£(£+l)%, m (6-47)

and
h d ,

i o4>

The equations tell us that the ^

wave function n ^ m is a simultaneous eigenfunction of
2 2
the L operator and the L, operator, with Lr eigenvalue h £(£+ 1) and L, eigen-
value hm. Equation (6-41) then tells us that ^ nlr m
has definite parity, since the state
has the space-inversion property

~* _ under the transformation (x, y, z) -» (~x,—y,—z). (6-49)

^ntm ( ^ntm

The stationary states and energy eigenvalues are also designated by the third
quantum number n, whose meaning has been described in general terms in the
 6-7 Quantization o( Energy 331

preceding paragraph. Those observations can be formulated by the further property

ih — %, m = E
ot
nf%, m ,
(6-50)

<
whereby the wave function \f
nfm is identified as an energy eigenf unction with energy
eigenvalue E nf .

We may assume that n labels the energy levels for a given ( such that the energies
increase with n, as is the case in one dimension where n is the only quantum number.
The one-dimensional problem has taught us that the larger energy eigenvalues belong
to the eigenf unctions \p(x) with the greater numbers of nodes. The same must be true
for the function rR{r) in three dimensions, since $(x) and rR(r) satisfy similar
differential equations. This correspondence suggests that we call n the radial node

quantum number and identify the integer with the number of nodes of the radial
function R n {. We illustrate these remarks in the example below.
The main conclusion of the central-force problem is the fact that wave functions
exist as simultaneous eigenfunctions of the energy, the square of the angular momen-
tum, and the z component of the angular momentum. We have just observed that the
stationary states ^n(m are endowed with these remarkable properties. Such findings
are noteworthy indeed, because the situation enables us to determine all three
independent physical quantities at the same time with zero uncertainty. Again, the
rotational symmetry of the central force is the essential ingredient behind this

coincidence. Let us recall that angular momentum is a conserved quantity in the

classical version of the central-force problem. We now
find that the conservation law
for angular momentum emerges in the quantum problem through the occurrence of
states inwhich E, L 2 and L, are observable without uncertainty. The labeling
,

scheme provided by the quantum numbers n, <?, and m is supposed to be interpreted

in this context.

It should be noted that the quantum number m is not among the indices for the
quantized energy in Equation (6-50). This integer does not appear anywhere in the
radial differential equation, and so the absence of m from the allowed solutions for E
and R(r) an expected result. The existence of a degeneracy is signaled by the
is fact that
E n( does not depend on m. Degenerate states occur for a given choice of n and c"

because the corresponding energy eigenvalue E nf has a collection of If + 1 distinct

wave functions, one for each possible value of m. The different wave functions with
the same energy vary with m according to the expression in Equation (6-46) and differ
among themselves according to the various z components of the quantized angular
momentum. This degeneracy is another consequence of the rotational symmetry of the
central-force problem. The force does not provide a natural direction for the choice of
polar axis, and so observable quantities like the energy cannot depend on m, the
quantum number associated with this choice. We also note that E contains an L 2
term from the outset in Equation (6-2), and we therefore expect the energy eigenvalue
to vary with the L quantum number f
2

An important general observation can be made by examining Equation (6-45) at

small r. We see that two of the three terms on the left side of the equality contain the
factor h /2fir 2
2
and hence become infinite as r — > 0. Let us assume that the potential
energy is less divergent than \/r 2 (as is the case for the \/r Coulomb potential
energy), so that the V(r) term in the equation can be ignored for small r. We can then
show that the radial solution near the origin must obey the general power law

R{r) -» Ar e as r -» 0, (6-51)
 1

332 Quantization of Angular Momentum

Figure 6-1

Radial behavior of the eigenfunctions near

r = for various values of <?.

.« =

^3
where A an unspecified constant. We verify this behavior in Equation (6-45) by
is

first and third terms on the left behave as r

noting that the and dominate at small
r if Equation (6-51) holds, and by demonstrating that the two dominant contributions

satisfy the differential equation. The proposed power law results in the equality

d dR
—
dr
r
2
—
dr
= t(t+ \)Ar'= t(t+ \)R near r = 0,

and so the first and third terms achieve the desired solution for small values of r.

(Note that a 1/r power law also satisfies the equality but introduces an unaccepta-
ble divergence at the origin.) Figure 6-1 power behavior of R n {{r) for
1 illustrates the

various increasing values of (° . Our assumption about

V{r) means that the given
potential energy becomes important only away from the origin and that the ^depen-
dent centrifugal part of VrK (r) is the decisive term near r = 0. We interpret our result
by noting that the centrifugal contribution is always repulsive and tends to push the
wave function away from the origin, as the name of the term suggests and as the
figure indicates.
We know from Chapter 5 that the Schrodinger equation has familiar analytical
solutions for only a few special choices of potential energy. We also know that progress
can always be made from qualitative arguments pertaining to the solutions. The
following illustration falls in the latter category.

Example

Let the potential energy be a linear function of r and consider the /= case, so
that the effective potential energy is written as

Vef! = V=cr.

We are concerned with radial solutions of the form rR(r), and so we turn to
Equation (6-43) and rearrange terms to get

— (rR)=-^[E-V(r)](rR).
2

The analytical solutions of this equation are rather unfamiliar for a linear
 6-8 Observables in Spherical Coordinates 333

Figure 6-12

Energy levels and radial functions rR(r) for a linear potential energy with £= 0.

V=V,

potential energy. Let us proceed graphically instead and deduce the shape of
rR{r) for the two lowest /= energy levels. The differential equation describes
the curvature of the solution relative to the value of the function at each point r.

The function rR(r) is subject to the condition that the solution must vanish at

the endpoint r = 0, because of Equation (6-51), and in the limit r — * oo,

because of the requirement of normalizability. As the quantized energies in-

crease, the corresponding solutions exhibit more curvature over larger intervals
and display more nodes in the region where nodes are allowed. These arguments
tell us that the first solution should have only the one node at r = and that the
second solution should have a second node. Figure 6-12 shows Vcff along with the
two lowest energies E nf for n = 1 and n = 2 in the tf= case. A qualitative
sketch of the two ^=0 solutions is also included to illustrate our remarks about
curvature and nodes. Note that each energy gives a single classical turning point
where the curvature changes sign and that each solution decays without
of rR(r)
nodes for values of beyond the turning point. The £— case is special because
r

the centrifugal contribution does not appear in the effective potential energy.
We leave the /=£ situation to Problem 14 at the end of the chapter.

6 8 Observables in Spherical Coordinates

The main goals of this chapter are fulfilled in Equation (6-46), the expression for the
stationary states. Thesewave functions exhibit quantization of angular momentum
and quantization of energy as compatible properties of the central-force system. The
methods can now be used to evaluate and interpret certain physical quantities in
terms of the angular momentum framework.
We begin with the probability properties of a general wave function ^! . The
2
corresponding probability density |^(r, 6, <$>, t)\ represents a probability per unit
volume in spherical polar coordinates. Figure 6-13 shows that the element of volume
in these coordinates is given by the infinitesimal quantity

dr = r
2
dr sin0 dd d<$> = r
2
drdtt,

where dQ, denotes the familiar element of solid angle. The wave function is normal-
334 Quantization of Angular Momentum

Figure 6-13

Volume element dr in spherical polar

coordinates.

r sine d<t>

ized to unit probability over all space if ^ satisfies the condition

1 = \*\
2
dr.
j
all space

2
Thus, the element of probability \^(r, 0, <£, /)| d-r expresses the likelihood of finding
the particle in the volume di at the location (r, #, </>) at time /.

Let us examine the normalization condition for the special case of a stationary state
of the kind described in Equation (6-46). The multiplicative dependence on the
variables enables us to split the three-dimensional integration into separate radial and
angular factors:

all space

00 r
2 2 :
Jr r dr dSl\R n Ar)\ \Y, m (6,<i>)\
n •',11
'all O
a

If we then recall the normalization of the spherical harmonics from Equation (6-36),
we find that the normalization condition for a stationary state reduces at once to a
single integration over r:

/•OO
2
1 = /
\R n Ar)\ r
2
dr. (6-52)

This result invites us to introduce a radial probability density

2
Pn,(r) = r \R n ,(r)\
2
,
(6-53)

subject to the condition in Equation (6-52):

1 = CP Ar)dr.n

We interpret the differential element Pnf {r)dr as the probability of finding the
 6-8 Observables in Spherical Coordinates 335

particle anywhere in a spherical shell of thickness dr at a distance from the origin. r

We note that Equation (6-53) contains no dependence on the time, and we emphasize
that P„/-(r) is defined only for a stationary state (hence the indices n and c"). Attention
2
should also be drawn to the explicit appearance of r in Equation (6-53), since this
factor causes the radial probability density to vanish at the origin for every <^ n ^ m .

2lf+2 2 '

Equation (6-51) tells us that P„^(r) behaves as r while l^/J 2 behaves as r , ',

near r = 0. This distinction in behavior at the origin arises becauses the radial

probability density is defined with respect to the thickness of a spherical shell, whose
2
surface area supplies the extra factor of r .

The probability density has an interesting spatial structure in the case of a

stationary state. Equations (6-33) dependence and t
and (6-46) tell us that the <J>

t/h
dependence of ty„f m are given by the simple phase factors c""* and e^' En ' These .

functions have unit modulus, and so the probability density is independent of 4> and /
in such a state:

22 2
\%*J -\Rn*(r)\ \Q< m (*)\ - (6-54)

The resulting distribution in the variablesr and 8 forms a "cloud of probability"

whose configuration in and symmetric about the z axis. The cloud

space is stationary
has vanishing density on certain nodal surfaces defined by the zeros of the two factors
in Equation (6-54). Nodes occur in R nf {r) at definite radii for given values of n and i
and produce spherical surfaces of zero density. Nodes also occur in @^ m (6) at definite
polar angles for given values of ( and m and produce conical surfaces of zero density,
oriented symmetrically around the z axis. These nodal surfaces intersect at right
angles within the distribution of probability and divide the cloud into regions that
become more and more numerous as the quantum numbers become larger and larger.
We should emphasize that the cloud does not represent a "spatial smearing of the
2
particle," where ^t defines a "fraction of the particle" found in the cell dr.
|^|
2
Instead, a spatial smearing of the probability is intended, where |^| dr gives the
likelihood of finding the entire particle at the location of interest. We should also recall
the implications of the uncertainty principle in connection with the and t indepen-
<£
2
dence of Equation (6-54). The expression for |^n ^ m |
indicates maximal uncertainty in
the azimuthal angle and the time, since the distribution describes complete nonlocal-
ization of the particle with respect to these variables. This observation reflects the fact
that the z component of the angular momentum and the energy are known with zero
uncertainty in the state ^ n /m . Let us finally remark, once again, that the properties
described are those of a stationary state.

The evaluation of any physical quantity depends on the state of the system and
involves the determination of an expectation value. We evaluate a given observable
by performing measurements of the quantity for a large number of separate systems in
the same state \K The average of these measurements corresponds to the expectation
value of the observable in the given state. We follow the rules established in Chapter 5
and express this expectation value in terms of an integral

f^*Q^dT,

where Q is inserted as a multiplicative or differential operator to represent the

particular observable. The central-force problem calls for the evaluation of two main
types of physical quantity. We find that the angular part of the spatial integration
336 Quantization of Angular Momentum

reduces to a simple exercise in each case, because of the angular momentum properties
of the states.
We look first at the expectation value of r in the stationary state ^„ /m :

all space

The calculation simplifies immediately when Equation (6-46) is inserted and Equation
(6-36) is employed:

2
(r>= / r dr rffl r\Rjr)\ 2 \Y, m (6 , <|>)|
2

/
•'all Q
/•oo /-oc

= / r
3
\R„,{r)\
2
dr = / ri>fl/ (r)<fr. (6-56)
•'o •'o

Note that the final result can be given in terms of the radial probability density and
that the expectation value of any function of r can be similarly expressed:

(F(r))= rF(r)P Jr)dr. r

(6-57)

The same expectation value has the more general form

(F{r)) = j**F{r)*dj= C ' r

2
dr J dtt F(r)\V(r ,6 ,<j>, t)\
2
(6-58)

when ^ is not a stationary state. We note that Equation (6-58) may depend on t,

while Equation (6-57) must be time independent and stationary, as expected for a
stationary state.
Let us turn next to the computation of expectation values for some of the important
angular operators. We start with the evaluation of L in the state ^„/ m and recall the
operator formula from Equation (6-12) to find

(L 2 ) = j%*, m {-h 2h2 )%, m dT. (6-59)

No differentiation is necessary here, despite the appearance of the operator in the

integrand. Equation (6-47) is put to use, along with the normalization of the wave
function, to generate a simple calculation instead:

(L 2 ) = h
2
at+ l)f%%%, m dr
= h
2
t(t+ 1). (6-60)

We proceed in similar fashion to the expectation value of L, in the same state and use
the operator formula in Equation (6-10) to write

(Lz ) = j%*, m -jj^%, m dT. (6-61)

 6-8 Observables in Spherical Coordinates 337

Again, the indicated differentiation is bypassed, as the eigenvalue property in Equa-

tion (6-48) and the normalization condition lead directly to the desired conclusion:

= hm. (6-62)

1
Equations (6-60) and (6-62) tell us what the measured values of L and L z should be,

as averages over a large number of systems all in the same state.

We can make a stronger statement if we consider the uncertainty properties of the
state in the light of Equations (6-47) and (6-48). To this end we consider the following
quantities and apply the eigenvalue relations twice to obtain

2
<U 2
)
2
> = j%*, m {-h 2K2 ){-h 2K2 )% fm dr = [hW+ i)]

and

h d ( h d
< L-> = /*"*- *„a„^ = (ton)'
\1T*

These results imply the properties

2
<(L 2 ) ) = (L 2 ) 2 and {L]) = (L Z ) 2

for a stationary state, and hence confirm the claim that the uncertainties AL~ and
AL, are equal to zero in any such state. We conclude that the determination of L
1

and L z always gives the answers expressed in Equations (6-60) and (6-62) for every
measurement of every system described by ^,„/ m The examples at the end of the .

section illustrate these arguments further in situations where ^ is a different type of

state.

The last item on our agenda pertains to the orthogonality of the stationary states.
The proof of this property involves the use of vector calculus and is left as Problem 16
at the end of the chapter. Orthogonality has already appeared as a mathematical
concept in one dimension and is formulated as before in terms of the spatial
eigenfunctions in the stationary states

iE -' t/ ''.
%, m = t n , m (r,e,4>)e-

We let 4*n s m and *P„ t m be any two different members of the family of eigenfunc-
tions and write the orthogonality condition as

/ \L* , \b , dr = 0. (6-63)
all space

This integral vanishes whenever the two sets of quantum numbers («,/,?«,) and
(n 2 f2 m 2 ) are not the same in all three integers. The spherical harmonics have a
338 Quantization of Angular Momentum

similar property whereby

f Y*m Y,._ dU = (6-64)

•'all Q

whenever (^m,) and (t2 m 2 ) are different pairs of quantum numbers. These integral
formulas are used frequently as calculational tools to supplement the normalization
properties of the various functions. Their usefulness is illustrated in the following
exercises.

Example

We have concentrated on the properties of a pure state *„/„, and should now
consider a more general kind of wave function. We know that a superposition of
these states is a solution of the Schrodinger equation, so let us construct our wave
function by combining two pure states with different L, quantum numbers:

,,,/ *-
* = ^f (*... + *n-i) = ii(F " + ir
i-i)'""
7r*
We note that *,,, and *,, ,
are degenerate, so that the t dependence of * has
a unique frequency. It follows that a measurement of the energy in this state
must yield the result

(£) = Eu with zero uncertainty.

The factor 1/ v2 is included to ensure that * is normalized. Let us verify this

point by computing the normalization integral:

2 2
/|^| rfT=-/|^ ul 2 rfT+-/|^ u _ | 1 |
rfT=- + -.

We observe that the cross-terms drop out of the calculation because of the
orthogonality property, and we recall that every *„^ m is normalized by the
condition

1=/ I*./.!
2
*.
^all space

Each piece of * is an eigenf unction of L 2 with the same (— 1 eigenvalue 2h

2
.

Therefore, we can write

2
-h 2A 2 * = 2h
2
V and ( -h 2A2 )(-h 2A 2 )* = (2a
2
)
*
and apply these eigenvalue relations along with the normalization condition to
obtain the expectation values

(L 2 ) = j**(-h 2A2 )*dr = 2h 2

and

2 2
<(L 2 ) ) = [**{-h 2A2 ){-h 2A2 )*dT = (2h
2
)
.
 6-8 Observables in Spherical Coordinates 339

The equality between ((Z,

2
)
2
)
and (L 2 ) 2 implies that a measurement of L2
must yield the result

(L 2 ) = 2h 2 with zero uncertainty.

The uncertainty in L, is not zero for a particle in the state ty. To establish this
property we first consult Equation (6-48) to find

h 8

i o$
and

h d \( h d .

We then compute the expectation values

d
(L z ) = f**-—*dT=-f(%*u + *,!_,)*(*,„ - *„_,)rfT = o

and

^/""(^(t^H
1

/(*,?, + *,l- )* (*i„

1
2
+ *n-,)rfT-* a .

Again, the orthogonality and normalization of the individual stationary states

are put to use. The uncertainty in L, is obtained from these results:

2
(AZ-J = (I 2 ) - (L z ) 2 = h
2
so AL = 2
h.

Hence, measurements of L z for a large number of systems in the state ^ must

yield an average value

(L t ) = with fluctuation ± h about the average.

We consult Table 6-1 and find that the angle dependence of the wave function
is given by

= —i\ —
V 277
sin 6 sin d> = — M/
V 277 r
.

Consequently, the angular distribution of l^l 2 is described by the expression

y\2
\Yn + Y 1
_,|' = —3

Z77
sin'0 sirnf, = r
277
3 /

\ r
340 Quantization of Angular Momentum

This probability density is not symmetric about the z axis, unlike the situation
for a pure eigenf unction of L,. Instead, the distribution has lobes of maximum
density aligned along the ±y axes, so that the probability of finding the particle
is somewhat localized in the two directions 4> = 77/2 and <J>
= 377/2. Some
localization in <p is expected since the uncertainty in L, is not zero. The fact that
2
l^l behaves as (y/r) 2 tells us that the probability distribution is symmetric
about the y axis and suggests that our state is an eigenfunction of L y It is .

therefore apparent that a choice of polar axis in the y direction would yield a
simpler description of the state. We should recognize from the outset that we are
considering a rather contrived wave function. The state ^ is stationary since

l^l
2
is not time dependent, even though ^ is not a pure state of the form ^nfm .

In fact, any superposition

a%em + a '%<m' + «"%**- + "•

is perfectly acceptable as a stationary state, since each of the contributing

members has the same energy Enf This degeneracy with respect to the L, .

quantum number has already been interpreted as a consequence of rotational

symmetry. We can appeal to the symmetry and choose a new direction for the
polar axis so that any such superposition of degenerate states transforms into a
simpler single-term wave function.

Example

Let us construct a nonstationary state by forming an equal-parts combination of

two nondegenerate states with different values of (":

\U —
/?"
(<i,
°°
+ \U \ =
F)
(
*
p
10
v
°°
f-'
E \«'/''
^
+ R
nnV / io e
-' E \x'/ h
\
)•

It is easy to show that the probability density oscillates with frequency {E u —

E w )/h in such a state. The following calculations demonstrate that the energy
of the particle has nonzero uncertainty as a further related property. We apply
the energy operator to ^lf and find

d
'
10 °
"*"
"())
= ^10 MOO "*"
^UMIO
rit

and

I ih
^T: ih
T: (moo + *no) = £ 2omoo +
i ^?1*1 10-
dtj\ I
dt
I

The necessary expectation values are then given by the expressions

(E) = [**ih
J
—8 *d
dt
at

1 1
f
 Problems 341

and

<*•> -/«.(»!) (»!)«,

- j/(*,*oo + *,lo)(£?o*,oc, + £?,*,,» )</t = (£ '° + £|2|) -

The uncertainty in E follows from these two results:

2
(Ais) = (is
2
) - (is)
2
= \(El + E n2 ) - \(E l0 + E u f - \{E n - E w )\

and so

A£=i(£ n -£ 10 ).

Our conclusions should seem reasonable for an equal-parts wave function, since
the average energy (is) lies midway between the two levels E u) and En , and
the energy uncertainty A is gives the deviation in energy on either side of the
average. Let us apply the same logic to the calculation of (E 2 ). We have an
equal-parts admixture of £= 1 and /= eigenfunctions, and so we expect to
find

(L 2 ) = l
2
(2h
2
+ Oh 2 ) = h
2
and M 2
= l,(2f) 2 - Oh 2 ) = h
2
.

Direct confirmation of these results is left to Problem 18 at the end of the

chapter. It is clear that ^ is an eigenfunction of L, with eigenvalue zero, since
both ^ 100 and <r
i
u0 are m = states. We must therefore have

(L z ) = with zero uncertainty.

Hence, measurements of L z must always yield the value zero for any system in
the state ^ '.

Problems

1. Determine an expression for rmin , the distance of closest approach on the orbit of a
classical particle, for the case of a repulsive Coulomb potential energy

b
V(r) = -, b>0.
r

Assume that the particle has nonzero angular momentum.

2. Consider the orbit of a classical particle with an attractive Coulomb potential energy

b
V(r) = --, b>0,
r

and determine expressions for the radial turning points when E negative and when E
is is

positive. Note that, for E< 0, there is a minimum possible E for each nonzero value of
the angular momentum L.

3. Use the operator results for L x , Ly and , L,, as found in Section 6-2, to derive the operator
formula for the quantity L2 = L2 + L2 + L2 . ,.
342 Quantization ot Angular Momentum

4. The particle in Figure 6-5 has a wave function ^(^>, /) and a probability density
P(<f>, t) = 1^(0, t)\
2
. The wave function satisfies the equation

2
f>- d d
2 2
2iiR <9</> dl

in which V(<j>) is included as a real- valued potential energy. A probability current density
j(<p, I) can be defined such that j and P obey the probability conservation law

-,(,0 + -/>(, i)-o.

Deduce the appropriate formula for j.

5. Set V = in the previous problem, and let the wave function have the form

(m4, ' a,)

y(<t>,t) = Ae' ,

where m is an integer. Use the result of the problem to compute j(<f>, I) for this state, and
interpret the answer.

6. Consider a bead constrained to move on a circular wire, as in Figure 6-5, and assume the
existence of a barrier at <j> = that the bead cannot cross. (Imagine an inaccessible region
— <£ < () <f>
< <j>
()
in the limit <j>
()
—> 0.) What condition on the wave function SE'(^), /) does
this stipulation imply? Determine the allowed energies and the corresponding eigenfunc-
tions. Are there any degeneracies among the states?

7. A particle of mass \i moves freely on the surface of a sphere of radius R. Express the

classical energy relation in terms of the angular momentum L, and use the operator
formulas to deduce the Schrbdinger equation for the system. Let the wave function ^ be
an energy eigenfunction with energy eigenvalue E and spatial eigenfunction \p. What is

the form of the differential equation for ^?

8. Refer to Table 6-1 for the spherical harmonic Y22 , and verify that this function satis-

fies the eigenvalue equation -A 2

F^ m = £{(+ \)Yfm and the normalization condition
2
/|K,J rfO-l.
9. Let the angular momentum L be represented in terms of the differential operators A^,
A , and A z
introduced in Section 6-5, and derive the relation

A,A^ - A^A, = -A,.

The other multiplication formulas are obtained in like manner.

10. A hydrogen molecule in purely rotational motion may be visualized as a rigid dumbbell
like the example in Figure 6-6. Draw an energy level diagram for the stationary states of

the system, and indicate the quantum numbers and degeneracy of each level. Let the
separation between the hydrogen atoms in the molecule be 0.075 nm, and calculate the
2
numerical value (in eV) for the energy scale unit h /I, where / denotes the moment of

inertia. Determine the allowed transition energies if the transitions obey the selection rule
A<?= ±2. Calculate the emitted wavelength corresponding to the transition t= 2 -» /=
0. (Symmetry principles prevent transitions in which £ changes by one unit.)

11. Refer to the rigid-body example in Section 6-5, and consider the state obtained by
superposing two degenerate normalized £= 1 wave functions:
 Problems 343

Write out the explicit expression for ^ and show that ^ is normalized. Calculate the
expectation value

, ft d
(L.) = /** ^dQ,,
J i d<p

and determine the uncertainty AL. in this state. Show that the probability density

depends on <J>,
and interpret this observation in terms of the uncertainty principle.

12. Refer to the rigid-body problem at the end of Section 6-5, and calculate the average of the
five probability densities for £= 2:

2
\
5
I l*2 J -

m=-2
Interpret the result.

13. Determine the parity of the spherical harmonic X,, by examining the explicit behavior of
the function under the angle-inversion operation (0,4>) —* (w — #, 77 + $).

14. Consider a linear potential energy V(r) = cr, and assume a nonzero value for the angular
momentum quantum number t '.
Make a drawing of the effective potential energy and
identify the regions in which classical motion is not allowed. Consider the two lowest

energy levels, E x/
, and E2/ , and sketch the behavior of the solution rR(r) for each case.

Make a qualitative argument to explain why Enf exceeds E nf)

for <f =£ 0.

15. Consult Table 6-1, and determine the values of 6 for which the probability density van-
ishes in each of the five (=2 stationary states. Sketch the resulting conical surfaces of
constant 0.

16. The eigenfunctions ^ n( /

m (r, 6, <f>) satisfy the orthogonality property

\b* , \L , dr = 0.
/ all space

Prove this result for the case of two nondegenerate eigenfunctions by proceeding as

follows. Write out the time-independent Schrodinger equations satisfied by \p n ( m and

\p* ( m . Multiply the first equation by ^* ( m and the second by \p n ( m .
. Take the
difference between the two expressions and integrate the resulting equality over all space.

Assume a real-valued potential energy, and use an identity from vector calculus to
complete the proof.
17. Verify the orthogonality properties of the pairs of spherical harmonics K2 ,
and Y20 and ,

K2I and Yu by , explicit calculation of the integrals fY2 ^Y20 dQ, and fY2 *Yu dQ..

18. Consider the nonstationary state

^ = "Tr v moo + Mio)'

in which an equal-parts mixture is constructed using two of the normalized states v

l'„,,„.

Calculate the expectation value of Lr and the uncertainty in L 2

for a particle in this state.

19. The wave function ^ = a,^n

l ri
x
,
r x
m x
+ a-&„
^
_
n,c,2 m 2
is a combination of the normalized sta-
tionary-state wave functions ^nfm and is therefore a solution of the Schrodinger equation.
Show that, for ^ to be normalized, the complex coefficients a, and a2 must satisfy the
2
condition \a { \
+ \a
2 \
2
= 1. Calculate the expectation values (L 2 ) and (L. ), and the
uncertainties AL 2
and AL. , for a particle in this state.
 SEVEN
THE
ONE-ELECTRON
ATOM

uchrodinger discovered his version of the

quantum theory in 1925 when he found that de Broglie's matter wave could be
applied to the problem of atomic structure. His goal was to explain the atom as a
wave system whose discrete frequencies were related to Bohr's quantized energy levels.
At first Schrodinger tried a relativistic treatment of the atomic electron, but his
attempt to blend relativity with quantum theory was prematurely conceived and had
disappointing results. The nonrelativistic formalism followed with more success and
furnished a correct picture for the main properties of the atom. In 1926 he published a
series of articles on the principles of quantization, beginning with his theory of the
hydrogen atom. The Schrodinger equation made its first appearance in the literature
in the course of this project.
The solution of the Schrodinger equation for hydrogen constitutes the fundamental
problem in the theory of atoms. Hydrogen offers a unique opportunity to test the
Schrodinger theory since the one-electron atom is the only atomic system that admits
an exact solution to the Schrodinger equation. The importance of the hydrogen wave
functions extends beyond considerations of the simplest atom, because solutions much
like those for hydrogen can be used as the basis of an approximate formulation for the

more complex atoms.

We have already learned about the prominent status of the hydrogen atom in the

early development of the quantum theory. We know that the Balmer-Rydberg

formula for the spectral lines and the Bohr model for the energy levels are consistent
with the spectroscopic data. Results from the Schrodinger equation should agree with
these observations if the equation is indeed a valid foundation for quantum mechan-
ics. In fact, we might expect that such a fundamental approach should predict all

observable nonrelativistic properties of the hydrogen system. We examine the predic-

tions for a system governed by Coulomb attraction in this chapter, and we leave
certain important refinements to be discussed later in Chapter 8.

344
 7-1 The Radial Differential Equation 345

7-1 The Radial Differential Equation

Let us generalize the hydrogen problem immediately to include two features that have
already appeared in the Bohr model. We assume that a single electron is bound to a
nucleus of charge Ze, and we treat the atom as a two-body system in motion with
center of mass at rest. The groundwork for the quantum construction of this problem
has been laid in Chapter 6, beginning with our discussion of Figure 6-1. For the
electron-nucleus system with masses m and M, we
e
define a reduced mass

M
r e
M+m e

and then cast the analysis in terms of an equivalent one-body problem to describe the
behavior of a particle of mass fi. The correction factor M/(M + m e )
is very near
unity; nevertheless, this generalization is kept in the problem (at no extra cost)
because the reduced-mass effect is subject to experimental test. The binding force is

due to the Coulomb attraction between the charges Ze and — e. Therefore, the
potential energy of the system is given by

Ze 2
nr)=-~47T£ r
,
(7-1)

a rotationally symmetric function. This electrostatic interaction provides the dynamics

behind all the conclusions discussed in the rest of the chapter.
Our main objective is to find the stationary states of the atom. We have a central
force determined by an r-dependent potential energy, and so we turn right away to
the general procedures of Chapter 6 and use the spherical harmonics Y^ m (6, 4>) to
express the angle dependence of the stationary-state wave functions

%, m (r,0,<t>,t)=R n Ar)Y, m (e^)e-'^'^. (7-2)

The angular momentum quantum numbers c" and m convey the angular momentum
properties of these states, as discussed in Section 6-5, while the third quantum number
n remains to be clearly identified. We can determine the r dependence of a wave
function with angular momentum quantum number t° by solving the differential
equation found in Equation (6-42):

2 2
dR
ft

2jur- dr
d
r2 —dr
+ V(r)
h
+ —<<(<>+
2jir-
1) R = ER, (7-3)

where R(r) and E denote the radial function and energy eigenvalue appearing in
Equation (7-2). The Coulomb potential energy in Equation (7-1) is employed for V(r)
to give the explicit form for this radial equation. The result is an unfamiliar
second-order ordinary differential equation whose solution must be investigated in
some detail.
We gain considerable insight into the radial behavior if we first restrict our
attention to wave
functions ^fnim with no dependence on angle. Necessarily, these
spherically symmetric solutions have angular momentum quantum numbers

£= and m = 0,
346 The One-Electron Mom

since Y00 (6, <$>) is the only possibility for a constant angular function. We insert this
information along with Equation (7-1) into Equation (7-3) and find that R(r) satisfies

the differential equation

2
h l 2 \ Ze 2
\R" + -R'\ R = ER. (7-4)

Since the solution is expected to approach zero as r — > oo, it is reasonable to try an
exponentially damped radial dependence:

R(r) = Ae~ r/a ,

where the parameter a has units of length and sets the scale of distance to describe the
damping. This trial function provides a solution to Equation (7-4) for all values of r.
To prove our point we compute

A R
R' = - -e~ r/a = - -
a a

and

R" = —A e-^
2
/a
= —R 2
.

a a

Then, when we put these results into Equation (7-4) and divide by i?(r), we obtain

2
h t 1 2 \ Ze 2
= E.
2ju \ a ar J
4ire r

The equality holds for all r, provided the coefficient of \/r vanishes:

2
h Ze 2
= 0.
jUfl 47T£

Thus, our first conclusion is a formula for the length parameter:

a =
Ze
—
4<7TE
7,
2
ti
.

We consult Equation (3-51) so that we can rewrite the formula in terms of the Bohr
radius a :

2
m
a=
e
a
-, where a = —
4-7TE h
. (7-5)
ju Z e'm e

The energy eigenvalue is also obtained by returning to the equality and comparing
 7-1 The Radial Differential Equation 347

two constant terms:

2
h
2
2fia

2 2 2 2 2
2
h l M e ) e n'
e

~ >'"( 1

2f x\m e
47re
j
47re
0/ 1 2/T

We recognize this result as the Bohr formula for the energy of the ground state. Let us
introduce the Rydberg energy E into the expression by writing

2 \
2
/

E= Z EQ 2
, where E = (7-6)
y
47re j
2^ 2

as in Equation (3-53).
These conclusions are reassuring since our attempt at a simple solution has
produced an £= wave function with the correct ground-state energy for the atom.
The full wave function for this stationary state is written in the form

-r/a
e ^B.ihr
Y I00 / 7 e ' V' ' /
yira*

in which the multiplicative constant remains to be explained. We take n = 1 for the

Bohr
value of the third quantum number, and we call the energy eigenvalue 2? 1
as a
reminder of the Bohr result found in Section 3-6. We recall that the spherical
harmonic for £= m = is given by the function

Inn
°° '477

and we observe that our result can be expressed according to Equation (7-2) by
identifying the radial function and energy eigenvalue as

R w -)l '-"-
7
and
u
F = ZT Bohr _ 7 2p
m.

Other (= m = wave functions with n > 1 also exist as solutions of Equation (7-4)
for other discrete values of E. We proceed more systematically to find all the radial
solutions, for tf= and for ^# 0, in Section 7-2.
Let us conclude these opening remarks by quoting a useful integral formula:

/•OO
r/r
= +l
/ r"e- °dr n\rj . (7-8)

This expression has numerous applications throughout the chapter.

348 The One-Electron Atom

Example

The multiplying factor in Equation (7-7) is confirmed by applying the normal-

ization condition to the wave function ^ 100 :

2r/a

/l*,ool
2
^ (duTr
Jn
2
dr-
na~

4 77
-:
[ r
2
e~
2 '/ a
dr = -2\ - = 1.
Tra

We have made immediate use of Equation (7-8) to complete this calculation.

7-2 Solutions of the Radial Equation

We are concerned with the discrete bound states produced by the force of Coulomb
attraction in the one-electron atom. The corresponding energy levels are found by
solving the radial differential equation with V(r) given by the Coulomb potential
energy. This mathematical problem has a remarkable solution with a very interesting
physical interpretation.
We begin by adopting an equivalent alternative to Equation (7-3). Let us return to
Equation (6-43) and insert the Coulomb potential energy to obtain

fi
2
d2 Ze'
2
R Y(Y+ \)R = ER. (7-9)
2\ir dr 477e r 2/x;

We have learned in the Bohr model, and again in Section 7-1, that the Bohr radius a
and the Rydberg energy E ()
are natural parameters to use as scales of length and
energy in the atom. It is fruitful to introduce these scale parameters in Equation (7-9),
since the result is a greatly simplified expression for the differential equation. To this

end we refer to Equations (7-5) and (7-6) and define a dimensionless variable p and a
dimensionless eigenvalue tj by writing

2
4iTE h
"/' (7-10)
Ze fi

and

E=
m
Z E 2
r) = -- —
l\xa~
jtj. (7-11)
r

Equation (7-9) then becomes

/r
-apR
r R + e(e+ \)r = j^,
3 2 2 2 2
2ixa p dp \xa p 2[ia p 2\i.a'

2 2
and cancellation of the factor —ti /2\ia p produces the final form

d2 /M+
— pR + 2R-
dp
1)
-R = -qpR.
 7-2 Solutions of the Radial Equation 349

Thus, the use of the quantities p and tj enables us to remove all the excess constants
from the radial differential equation.

We take R to be a function of p, and we let this dimensionless variable range over

the interval [0, oo). The solution is required to vanish at infinity, and exponential
damping is expected, in view of the result obtained for the ground state in the
previous section. We can incorporate this behavior, and transform the differential
equation into a more useful form, if we introduce a new function F(p) by defining

# = ,-Ap-1^. (7-12)

The equation for R contains the term

—
'

d* d2 r p = —(e-fi
rp r- r d
1
pR = —e-fi F F' - J^e-^ P F)
/ \

dp dp- dp

= e~fi p {F" - 2 ]fqF' + tjF),

and so the differential equation can be stripped of the factor e~v np to read:

2 SU+ 1)
F" - 2yft]F' + -qF + -F F= t\F.
P p-

These maneuvers lead us to the final version of the differential equation for F(p):

2 <f(7+ 1)
F" - 2Ji]F' + F=0, (7-13)
P P

where F must satisfy the further condition

F(0) = 0. (7-14)

We impose this requirement so that the radial function R in Equation (7-12) remains
finite at the origin.

It is not obvious that any real progress is made by this procedure, since the
unknown function F obeys a differential equation that is just as unfamiliar as
the original equation for the desired function R. Let us look again at the solution for
the ground state to relieve some of this skepticism. We know from Section 7-1 that the
radial function has the form

R= Ae~ p for the /= ground state.

Equation (7-12) tells us that we must have

F(p) = Ap and yfr)

= 1

for this state, in clear agreement with Equations (7-13) and (7-14). Thus, we see that
F is a simpler function than R in the case of the ground state, and we might suppose
that this property of F relative to R persists for the other states of the atom.
350 The One-Electron Atom

The quantum number { can have any integer value in Equation (7-13). It is

instructive to isolate the ^=0 case and begin the investigation with the differential
equation

F" - 2AF' + -F=0. (7-15)

P

We may not recognize this as one of our familiar differential equations, but we can
still solve the equation by means of standard methods. The results of these procedures
include a determination of the dimensionless parameter tj in terms of an integer n:

A = -- n
(7-16)

This integer arises from the fact that F must be a polynomial in p, where n defines the
order of the polynomial. Thus, the integer n serves as a quantum number to label a
whole family of /= solutions. We examine the mathematics behind these conclu-
sions in more detail at the end of the section.
Equation (7-16) is our main result for the <f = case. The result tells us, through
Equation (7-11), that the energy eigenvalue is given by

u En
En0 =-^-Z*-i (7-17)
m t
n

in the nth (=
state. We follow the notation of Equation (7-2) and label the values

of by the integers n and t, taking <f = 0. This conclusion is very striking because
E
the formula reproduces the one given in Equation (3-52) for the «th energy level of
the Bohr model. Let us draw attention to this point by setting

Bohr
E n0 = £„ (7-18)

and writing

= Kjr)Y00 (6,<t>)e-^° '^.

h

* n oo

Taken together, these expressions give the eigenvalue and eigenfunction of the energy

in the nth /= state. The radial function must have the form

according to Equations (7-12) and (7-16). The details at the end of the section tell us
why F must be a polynomial and how n defines the order of the polynomial. We see
that the ground-state wave function of Section 7-1 is found among these results when
the n = 1 level is chosen.
The solution of Equation (7-13) proceeds in similar fashion for the /=£ states.

Again, we find that F is a polynomial in p of order n. Our purpose in separating the

cases for = and /# is to call special attention to the outcome

<f of this investiga-
tion. We learn in the mathematical details below that Equation (7-16) holds, not only
fort = 0, but also for any angular momentum state. Equation (7-11) then leads us to a
most surprising conclusion:

The energies allowed for each £ are independent of the value of t'.
 7-2 Solutions of the Radial Equation 351

We express the general result for the energy levels of the one-electron atom in the

manner of Equations (7-17) and (7-18) by writing

Ene = --Z^=E^\
m n
(7-19)
e

Thus, only the one quantum number n is needed to determine the energies, as in the
Bohr model, even though two quantum numbers are normally required to label the
energy eigenvalues in a central-force problem. Of course, the radial functions vary
with t* as well as n, since the differential equation for F(p) contains an explicit
^dependent term.
We have introduced the integer n in the stationary state n /m
of Equation (7-2) by ¥
defining n as the order of the radial polynomial F. This definition of a third quantum
number sets the hydrogen problem apart from the general central-force problem of
Chapter 6. Recall that in the general treatment the third index is introduced as a
radial node quantum number. Hydrogen is a special case, and so n is given a different
meaning and a special name. In the case of hydrogen we refer to n as the principal
quantum number, and we note that n alone determines the energy. Equations (7-12)
and (7-16) define a collection of radial functions

FAp)
-p/n JltlLL
r
R ,=n
e wit hp=-. (7-20)
P a

Note that F[p) bears the labels n and f to display the fact that both of these
quantum numbers control the composition of the polynomial. If we examine R n( {r)
for various n and c", we see that the principal quantum number n does not count

8
Table 7-1 Radial Functions for the One-Electron Atom

n = 1 /= R l0 =

n = 2 /=0 R 20 = |l- I*-"/

2

l2a' \ 2

'= 1
*2i = 7T=rP'- p/2
2V6a

« = 3 /= tf 30 = |1- -p
-o +
2
—-p 2
2
\e- p/3
3v/3a
3
\ y 27

4
i c n 32 . p e
SlV^Oa 3

The variable is denoted by p = r/a and each of the functions obeys the normalization condition
coo, r.
f(r(R„,fr
^2 Jl =
2 j„
dr= .
1.
352 The One-Electron Mom

radial nodes. Several of the radial functions are listed in Table 7-1, and graphs of the
functions are shown in Figure 7-1. It is easy to infer from either the table or the figure
that each R ni has
, n — £— \ nodes in the interval (0, oo). Hence, the combination of
integers n — /— 1 plays the role of a radial node quantum number for the one-elec-
tron atom. We emphasize once again that n has a new meaning in this special
problem and that the energy depends only on n. We also observe, from the (/
behavior of the functions in Table 7-1, that each R n( has an Ah-order zero at r = 0,
as required by Equation (6-51).

Figure 7-1

Radial functions R„, taken from Table

7-1. The variable is the dimensionless quantity
p = r/a. Each function has n — £— 1 nodes
in the interval (0, oo).

sla* Rn(
 7-2 Solutions of the Radial Equation 353

Figure 7-1

Continued.

J L J L
n= 3
e = 1

0.1-

J I L I I

10 15

The entries in the table contain certain multiplicative factors to ensure the
normalization of the wave function ^„^ m We know from Equation (6-36) that the
.

spherical harmonics Yfm are normalized separately over solid angle, and we recall
from Equation (6-52) that the radial functions R nf also satisfy their own normaliza-
tion over r:

\= C{RjrUr (7-21)
354 The One-Electron Atom

Finally, we observe that the radial functions obey the orthogonality property

00
Jr R n( R n( r 2
dr — when n ¥= «',
o

as a consequence of Equation (6-63).

Detail

Equation (7-13) can have only polynomial solutions for F(p) because, otherwise.
the associated radial function R would not remain finite in the limit p —» oo.
Let us accept this statement without proof so that we can determine these
polynomials as our next step. The differential equation for the f=Q case is

considered first, so that F is supposed to satisfy Equation (7-15). We im-

mediately assume a polynomial of the form

F{p) = A(p + a2p

2
+ a3p
3
+ +a n p n ) with a n * 0, (7-22)

where a 2 a 3 a n are coefficients to be determined in the analysis. Note that

, , . .
.
,

the polynomial has order n and satisfies Equation (7-14). The first two deriva-
tives of F are

F' = A(\
2
+ 2a 2 p + 3a 3 p + • • •
+na n p"-*)
and

F" = A(2a 2 + +n(n - l)a n p"-

2
6a,iP + • • •
).

If we insert these expressions into Equation (7-15), we obtain the equality

~
(2a 2 + 6a 3 p + • • • +n(n - l)a n p""
2
)
- 2^(1 + 2a 2 p + • • • +na n p n x

2
+ -{p + a2p
2
+ ••• +a n p") = 0.
P

This string of terms in powers of p can vanish for all values of the variable only
if the assembled coefficients are equal to zero for each power. We examine the
highest power and find

_1
-2\fr)na n + 2a n = from the p" term.

The stipulation in Equation (7-22) rules out the possibility that a n vanishes. The
important result is the determination of tj quoted in Equation (7-16):

]fn = -.
n

The lower powers of p in the equality provide the following further information:

2a 2 - 2^ + 2 = from the p° term,

6a 3 — 4y^a 2 + 2a 2 = from the p term,

1

We can solve these equations for the unknown coefficients in ascending order.
 7-2 Solutions of the Radial Equation 355

using Equation (7-16) in the process, and obtain

_ =
1

a> = -Jy - 1 ! >

2^-1 1/2
U.rx - 1 - - 1

3 3 «

The coefficients are related successively according to the general formula

2( k/n- 1

a,. (7-23)
k{k + 1)

The implied sequence of coefficients must start with the assignment a, = 1 to

conform to Equation (7-22). This formula concludes our summary of properties
of the <^= solutions.

Detail

The general case for <f # is considered next, so that F is now supposed to
satisfy Equation (7-13). We generalize the nth-order (= polynomial in
Equation (7-22), and thereby accommodate the additional independent term in
the differential equation, by adopting an F function of the form

F(p) =A{p'+l + a,+ 2 p<

+2
+ a,+ 3 p
M+ + a n p") with a n * 0. (7-24)

We note that the leading term in F must behave as p

(Jr
'
if the radial function in
f
Equation (7-12) is to have r behavior near the origin, as required by the
general rule in Equation (6-51). The coefficients o ,+l 2 , a^+3 ,. .
.
, an are de-
termined as before, by inserting the polynomial into the ^dependent differential
equation for F. The required derivatives are

F' = a[(<? + l)p' + (S+ 2)a,+ 2 p<

+]
+ (•+ 3)^+3 p'+2 + • • •
+nay-'}
and

F" = A[t(S+ Op'"

1
+ (•+ 1)(/+ 2)«,+2 p' + (/+ 2)(/+ 3)a,+ 3 p'+ >
+
••• +n(n- l)a n p- 2 ].
Equation (7-13) then provides the following lengthy constraint among the
various powers of p:

[t{S+ Op'" + (/+ 1)(/+ 2)«,+2 p' + {t+ 2)(/ +

1
+1
3)a /+3 p' +
••• + n(n- l)ay- 2 ]

-2i/y~[(f+ iy+(/+2)a,+ 2 p'+l + + na n p"~

l

2
+2
+ -[p'+1 + a,+ 2 p' + ••• +a n
p"}

<f(<f+ 1)
2 — .
+1
+ "t+2 p'
+2
+ ^+3 p/+3 + • • • +ay] = o.
 ,,

356 The One-Electron Atom

Note that the highest and lowest powers are p"" and p'', and that the terms in 1

f~
p cancel because of the choice of leading term in Equation (7-24). Again we
'

assemble the coefficients of each power of p and obtain

- 2^qna n + 2a n = from the p"~ '

term,

as well as

(£ + 1)(/+ 2)a,+ 2 - 2yfn(£ + 1) + 2 - £{£ + l)a,+2 =

from the p f term

(/ + 2)(£ + 3)a,+ 3 - 2<fi(£ + 2)a,+ 2 + 2a f+2 - £(£ + l)a,+3 =

from the p f+ '

term

The first of these equalities is the same as in the £= case. This most
remarkable result tells us that Equation (7-16) holds for any value of /. The
remaining equations can be solved as before to yield the coefficients of the
polynomial in ascending order:

] fn(<?+ l) - l l l

V+2 '

f+ 1 n f+ 1

fi{{+ 2) - 1 1 / £+ 2 \( 1

^+3 + 2
2£+ 3 /

2/+ 3 \ n ~j\n £+ I

The successive coefficients are connected by a general recursion relation of the

form

2{k/n - 1)
+,= (7 " 25)
fl
*
a-(a- +0-^+1)^
This formula generalizes the £= expression in Equation (7-23). We leave the
derivation to Problem 3 at the end of the chapter and illustrate the use of the
formula as follows.

Example

Let us pick quantum numbers n = 2 and £ = 1 and construct the wave function
^2\m with the aid of Equation (7-25). We must begin with the definition
a f+x = 1 to adhere to Equation (7-24), and so we set a 2 = 1 in this application.
Equation (7-25) gives the next coefficient as

a,=
3
—6-2
2(2/2 - 1)
-U) = 0.

The succession of contributions to the polynomial terminates at once so that

 7-3 Degeneracy 357

Equation (7-24) has only a single term:

F2 \(p) = A P 2 -

From Equations (7-19) and (7-20) we have

E2l = £2Bohr and R 2i = Ape~ p/2 .

The desired wave function can therefore be written as

% Xm
= —e~ r/2a Y Un (e,<$>)e-' E ^' ,/h with m = 1,0, -1.
a

The normalization condition in Equation (7-21) determines the remaining

constant A:

/•oo „ /-oo A~r~

1 = ( (R 2l ) 2 r *dr = f ^e-^ a
r
2
dr

A2 /-oo
/•OO A"
A'
/ r\- r/a dr= —4! a
5
= 24a 3A 2 ,

a ->o

using the integral formula in Equation (7-8). Thus, we obtain A = 1/ v24a :i

for the normalizing factor, and we observe that the resulting expression for R 2X
agrees with the entry in Table 7-1.

7-3 Degeneracy

It is remarkable that the main features of the hydrogen atom can be rigorously
understood with so little difficulty. We have been able to solve the Schrodinger

equation exactly and obtain convincing results from a detailed study of the radial
solutions. Let us move past this important mathematical phase of the problem and
show that the physical interpretation is even more interesting.
We have found that the energy levels in the Schrodinger theory agree with the
Bohr formula and vary only with the principal quantum number n. This unique
feature of the one-electron atom is expressed in Equation (7-19). We know from the
general central-force problem that every stationary state of the atom is assigned a set
of three quantum numbers (n/w). It is expected that the energy eigenvalue should be
independent of m on grounds of rotational symmetry, but it is surprising to find that
the energy does not vary with ( for a given value of n. This circumstance implies an
unusual degeneracy among the states, since a choice of n fixes the same energy for
several possible states with different values of /.
We can establish the nature of the degeneracy if we examine the structure of the
radial portion of the wave function

%, m = e~^"^^-Y, m (e,^e-
iE

p
^ withp--.
a
(7-26)

This rewritten version of Equation (7-2) incorporates Equations (7-19) and (7-20) and
358 The One-Electron Atom

introduces E n
as shorthand notation for the Bohr energy £' Bohr
n
. A glance at Equation
(7-24) reminds us that the polynomial Fn/ {p) has its lowest and highest powers in the
+
terms p and p". It is obvious from the construction that n cannot be smaller than
'

{+ 1 . Therefore, a given choice of the angular momentum quantum number i allows

the principal quantum number to range over the values

n = f+ 1,/+ 2,

A sequence of levels of increasing energy arises with this list of n values for the given
/. The degeneracy pattern is easier to see if the bookkeeping scheme is turned around
and hence a particular
so that a particular energy level, n, is chosen. The / values
with the same energy must be those for which

n > t+ 1,

namely
£= 0,l,2,...,n - 1. (7-27)

This degeneracy with respect to 4 is compounded further by the familiar degeneracy

with respect to m, whereby each £ admits 24 + 1 possibilities for the azimuthal
quantum number
m = — 4,-4 + 1 , . .
.
, 4— 1 , «f.

The combined array of allowed values of 4 and m embraces a collection of states ^fn f m
of the form expressed in Equation (7-26), all with the same Bohr energy E n We .

summarize these conclusions by listing the wave functions in ascending order of n in

Table 7-2 and by drawing the energy levels in Figure 7-2. Note that Table 7-1 has
already been organized to give the functions R nf in the same fashion. Note also from
the figure that the degeneracy of the nth. energy level is evidently given by

dn = n\ (7-28)

an expression for the number of distinct states with the same energy En .

Table 7-2 Degenerate States of the One-Electron Atom

n = 1 (= m = ^ 100 = R i0 Y00 e~' E,l/r '

nondegenerate

„ = 2 £=0 m = % 00
= R 20 Y00 e- E ?'/>>
four
degenerate StatCS
/= 1 *- 1,0. - 1
% lm = R 2l Ylm e-^l

= * l/h
„ 3 /=o ™ = * 300 = RwYm e- iE '

iE3 /h nine
4-\ m= 1,0,-1 %i m = R 3l Ylm e'
'

\
degenerate states
'=2 E /h\
m = 2,1,0,-1,-2 * 32m = R 32 Y2m e~"> it
 7-3 Degeneracy 359

Figure 7-2

Energy levels and degeneracies of the one-electron atom. There are n' distinct states ^tnim with

the same energy E„. Spectroscopic notation is used to label the various shells and orbitals. The
nth shell contains n orbitals, and the n£ orbital consists of 2/+ 1 states.

- n = 4 ——— 4s
l
. 1— 4p - — - Ad —— - Af N shell 16 states

E 3 - n=3 3s 3p 3d M shell 9 states

n=2 2s 2p L shell 4 states

(' =
Is K shell 1 state

An ancient form of spectroscopic notation is still in common use as a means of

designating these single-electron atomic states. We recall from Section 6-8, and
especially from Figure 6-8, that the different assignments of the angular momentum
quantum numbers £ and m have their own characteristic angular distributions of
probability. We let £ be known as the orbital quantum number, and we call the
distribution of probability for each £ an electronic orbital. Spectroscopic notation
identifies these configurations by the letter code

spdfgh

in one-to-one correspondence with the £ values

01 2345
The single-electron energy levels are called shells, with labels

KLMN
corresponding to the n values

1 234 ••
360 The One-Electron Atom

Bohr model. These notational schemes are included in Figure

as in the old 7-2. We
can become acquainted with their use through the following illustration.

Example

The n = 2 level of the one-electron atom is known as the L shell. The figure
indicates the existence of degenerate s and p orbitals in this shell, comprising
one 2 s state and three 2p states. The four different normalized wave functions
have the same energy E 2 and appear in Table 7-2 as follows:

where

Y200
= "20*00
= " 1
'

12a
1
2 /477

for the 2s state, and

r2i + l
= "2\Y\ ± = pe -P/2 sin ue
l
3
2\/6a

T2I0
= "21M0 = TP e -P/2 cos
2vW 4w

for the 2p states. Entries from Tables 6-1 and 7-1 have been used to assemble
the (r,d,(j>) dependence of these energy eigenfunctions.

74 Probability Distributions

The Bohr model of the atom is based on the classical notion of planar electron orbits.
We know from the quantum treatment of angular momentum that this picture has
only qualitative validity, and then only in the classical limit of large angular
momentum quantum numbers. The proper way to visualize the atom in any of its

states is provided by the relevant distribution of probability.

We deduce the physical properties of the atom in a stationary state by applying the
probability interpretation to the appropriate wave function ^n f m The probability of .

locating the electron relative to the nucleus, in a volume element dr = r'drdQ,, is

given by the familiar expression

2 2
\%,J dr= [(R n ,)\ dr][\Y, m dQ]
2
\
(7-29)

We have considered the spatial configuration of the probability density |^ n ^ m |" in

general terms in Section 6-8, and we have found that the distribution in angle is
2
determined by the universal angular factor |F/m |
. This ^-independent quantity varies
with according to some graphical representation of the sort described in Figure 6-8.
Figure 7-3 shows a larger assortment of these axially symmetric angular distributions,
corresponding to the angular momentum states listed in Table 6-1. We have also
found that the probability in Equation (7-29) can be integrated over solid angle to
 7-4 Probability Distributions 361

Figure 7-3

Polar-angle distributions \Y/m \

in various angular momentum states. Axially symmetric angular
distributions of the probability density are generated by rotating these graphs around the z axis.

The distributions satisfy the normalization condition 27r/ 7|K .-,„|"sin 6

( (
dO = 1.

generate the radial probability density

Pn*(r) - r
2
(R m <? (7-30)

This quantity is introduced only for stationary states and has a different structure for
each central-force problem. We interpret P nif
(r)dr in the case of the atom as the
362 The One-Electron Atom
 74 Probability Distributions 363

probability of rinding the electron at a distance between r and r + dr from the

nucleus.
The ground state of the atom is described by the wave function in Equation (7-7).

Spherical symmetry is an obvious property of the corresponding angle-independent

probability density
-2r/a
2
1^
IMOO I
I
3 '
777/

in marked contrast with the plane circular orbit of the simpler Bohr model. We can
2
integrate l^ool over the surface of a sphere of radius r to find the radial probability

density

2 ' /a
Pjr) = V'~
(or we can take R l0 from Tableand apply Equation (7-30) to obtain the same
7-1

answer). This radial distribution shown in Figure 7-4 to have a sharp peak at p = 1,
is

where r = a. Thus, we make contact with the Bohr model to the extent that the most
probable distance of the electron from the nucleus is equal to the radius of the first

Bohr orbit.

The figure also describes the radial probability distributions for the other states
listed in Table 7-1. We note that the existence of nodes in R n/ -
causes the occurrence
of peaks in Pnf and that the distributions with a single peak are those for which
{= n — 1. These states of maximum / correspond to the circular Bohr orbits, since a
single most-probable radial distance is defined in each case.
The average distance between the electron and the nucleus is given by the
expectation value of r. In a stationary state we find

2
(T)-
J**/m
r%, m dr- fr'iR.,) di rrPn ,(r)dr, [7-31)

as in Equation (6-56). General formulas exist for R nf , with arbitrary values of n and
t, and so genera! expressions also exist for (r) and for other expectation values
involving functions of r. We are not concerned with the derivation of these quantities,
so let us just quote the following results:

1 /(•+ 1)
<r> -A* 2 1 + - 1
- (7-32)

2
' (7-33)
an

2 3
(7-34)
a n (2S + 1)'

3
(7-35)
a «Y(/+ 1)(2/+ 1)

Note that the appropriate power of the length scale a appears in each expression. We
can apply Equation (7-32) right away and calculate (r) for n = 1 and /= to find
the average distance (r) = ^a for the ground state. The point (p) = (r)/a is
364 The One-Electron Atom

Figure 74
Radial probability distributions for the radial functions in Figure 7-1. The graphs describe the
dimensionless quantity aPn ^ = i
a p
1
(R n/^) 1 versus the dimensionless variable p = r/a. The
expectation value (p) = (r)/a is shown for each of the states. The distributions satisfy the
normalization condition \^aPn( dp = 1.

0.1 -

a/' ,,,

aP 30

0.1-
<P>
J I*

10 15

„/\

0.1 -
<P>
I T J L
10 15
 7-4 Probability Distributions 365

DDBD
Distributions of probability in various states of the one-electron atom

3d m • 3d * > 4f

QEJ©D 4f
m ° 2S

m m id
3p o
4(j 4d '
"

E2SHE1 sf -' sf — <P

"

sd m ' sd

indicated for this case, and for each of the other radial probability distributions, in
Figure 7-4. Equation (7-33) can also be used immediately to determine the expecta-
tion value of the Coulomb potential energy:

Ze 2 / 1 \ Ze
<F>= -
47T£ \ r
J 477e a«"

All of these formulas have applications in atomic physics.

Example

Let us confirm our observations about the ground state. We can obtain the
probability density by computing

Pw = 47rr
2
I*
1MOOl
2
I
= —4 3
r
2
e~
2 r/a
.

a
366 The One-Electron Atom

The derivative of this function is

dP 10 4 / 2
2r r\\ ~ 2r/a
dr a'

and so P l0 maximizes at r = a, as claimed above. The expectation value of r is

given by Equation (7-31):

a\ 4 3
(r) = j rP l0 dr=-f rV 2
'"«fr = -3! -
2

inagreement with the result from Equation (7-32) for this state. Note that we
have again found use for the integral formula in Equation (7-8).

Example

We have seen how (V ) follows

s
in one step from Equation (7-33) for any
stationary state of the atom. Let us pursue this result and extract some
additional physical information about the system. We first use Equations (7-5)
to find

2 2 2 2
Ze' Ze jti e m r
\

(V) 2 2 2
4Tre n a 47re n m r
4 nt n h
f
477£ I h~n

We then note that (E) is the same as E n

in the state ^nfm , and we employ
Equations (7-6) and (7-19) to write

ju Z
-- —
Zli
,2 \2
Z2 { e
2
V M
<£>= TE
= 2 2 2
m. n 47TE
°/
2h 477£ I h n
'

The two results for (V) and (E) satisfy the equality

(V) = 2(E),

and so the expectation value of the kinetic energy becomes

W W .<K>-- W
- -
Z"
T |— j^.
I JLI

These relations among the average energies (V), (E), and (K) hold also in
classical mechanics, where the result is a special case of the virial theorem.

7-5 Electric Dipole Selection Rules

The states of the atom reveal their existence by the radiation emitted in transitions
between pairs of energy levels. These radiative processes cause the instability of the
excited states and generate the emission spectrum of the atom. Figure 7-5 reminds us
 7-5 Electric Dipole Selection Rules 367

Figure 7-5

Energy shells and radiative transitions in hydrogen.

-0.85 - n AT shell

-1.51 - n M shell
Paschen
series
(infrared)
.,,

-3.40 L shell
Balmer
series
(visible)

E n (e\J)

"-
1360 n= 1 K shell
Lyman
series
(ultraviolet)

of the organization scheme for the familiar spectral lines of hydrogen, in which each
series of lines corresponds to a complete set of transitions downward to a particular
energy shell. We have learned in Section 5-8 how quantum mechanics predicts the
and determines the intensities for the various
probabilities for the different transitions
emitted wavelengths. Selection rules emerge from these predictions to tell us that the
transition mechanism allows only certain changes in the quantum numbers between
the initial and final states of the atom.
We convert our one-dimensional treatment of transitions in Section 5-8 to the case
of the one-electron atom by introducing transition states for the three-dimensional
system. Let us construct such a state by superposing two stationary states of the atom:

ncm n c m

= C*n<m<-
iE " t/h
+ f'W^ With E„ > E,. (7-36)

This wave function represents a situation in which the atom is found in both
2
stationary states at once, with probabilities |c| and \c'\ 2 and thus describes an atom
,

in transition between the given energy levels E n

and En The transition itself is caused
,.

by the interaction atom with the electromagnetic radiation field. The perturb-
of the
ing effect of the radiation is time dependent, and so the probabilities \c\ 2 and \c'\ 2
vary with time to indicate the course of the transition. The oscillatory time depen-
dence of the probability density is the main feature of this construction. We know
368 The One-Electron Atom

from Section 5-8 that |^|" oscillates with the Bohr frequency

n n
(7-37]

and we conclude that the expectation value of the electric dipole moment of the atom
oscillates with the same frequency. Our semiclassical picture of the interaction of the
atom with the electromagnetic field identifies this system' of oscillating charge as a
source of electromagnetic waves emitted in a characteristic electric dipole pattern.
Hence, the construction describes the emission of electric dipole radiation at the Bohr
frequency v.

We express the electric dipole moment of the atom as — ?(r), where r denotes the
coordinate vector of the electron relative to the nucleus. (Actually, the electric dipole
expression is given exactly by — ex only in the case of the hydrogen atom or in the
limit of infinite nuclear mass. This subtle point is addressed in Problem 1 1 at the end
of the chapter.) We then use Equation (7-36), and set co = 2ttv, to obtain

-*(r) = -ei-ty**^ di

= -ejr{\c^ nfr f + c*c'^J ^e n

iut

+ c'*c^,m 4 nfm e-' ut + kWv/'J 2 )

dr, (7-38)

in analogy with Equation (5-69). The coefficient of the time dependence e~'°" may be
taken to represent the amplitude of the oscillating dipole. The squared modulus of this
complex quantity determines the probability for the transition between the initial and
final atomic states, labeled respectively by the quantum numbers (nfm) and (nY'm').
The amplitude coefficient contains the integral factor

fer«r4, m/m dT (7-39)

as its principal contributor. This important quantity is called the dipole transition
amplitude for the transition (n£m) -» (nY'm').

We observe that this integral carries all the essential quantum mechanical informa-
tion about the two atomic states involved in the electric dipole transition. The integral
defines a vector quantity in which r has the Cartesian components

rsin#cos<|>, rsin#sin<|>, and r cos .

Let us recall that the spatial eigenfunctions have the form

*„, B (r,M)=* B
,(r)y, m (0,*)

so that we can write the three components of the transition amplitude as

JY&wxB<x»lYim Xk
2
f™R n .,.rR n ,r dr
JYfm .smO sin+Y, m dQ (7-40)

[YAs*»$Y,m JQ.
 7-5 Electric Dipole Selection Rules 369

Note that only the angular part of the integration differs from one component to

another. The selection rules for the radiative process follow upon inspection of these
integrations, since the integrals over and <f>
are nonvanishing only if the quantum
numbers (^m) and (£'m') are related in a special way.
The <f>
integration presents the more straightforward part of this analysis because of
the elementary $ dependence of the spherical harmonics:

We transform cos <f>

and sin<£ to complex-exponential form and find that the .v,
y,
and z components of the transition amplitude contain the azimuthal integrals

"t> -><t> "t> _ -"t>

V' m V m *</4>.
_|_
e e e e
f~"e -»»'+ m4, %-'""'
e' d<l>, [ :
e'^dQ, and /
Jq 2 •'o 2* •'o

These expressions are easily integrated to yield the following conclusions:

/"

•At
2
V '

, m >, ±,
Vm *</<f>
= unless m - m' + 1 = 0,

and
2
( " €-""'*€""+ d$ = unless m - m' = 0.

The first result implies a restriction on m and m for the x and y components of the
dipole amplitude, while the second result applies only to the z component. We
summarize these restrictions by writing

Aw = 0or±l. (7-41)

This selection rule expresses the allowed change m — m for the azimuthal quantum
number of the atom in a transition accompanied by the emission of electric dipole
radiation.
The 8 integration is not so easy to evaluate in general terms. The three components
of the transition amplitude contain the following two integrals in the polar angle:

fe^-sin 6 0, m sin 6 d6 and fe^cos d 0, m sin 6 dO.

We may assume that the quantum numbers m and rri are already constrained as in
Equation (7-41) when we consider these expressions. Evaluation of the integrals for
arbitrary quantum numbers involves the recursion relations and orthogonality proper-
ties of the Legendre functions /^ m (cos 6 ). We have looked briefly at these functions in

Sections 6-4 and 6-6, but we have not developed the mathematics far enough to
perform the desired integrations. The general result is easy enough to state, however:

The 6 integrations vanish unless ( and £' differ by one unit.

We express this selection rule for the orbital quantum number by writing

A/= ±1, (7-42)

and we illustrate the result by evaluating certain specific integrals in the example
below.
370 The One-Electron Atom

Figure 7-6

Lyman transitions allowed by the A/ = ±1 selection rule.

Ad 4/
E3 -3d

- n= 2

- n= 1

It should be emphasized that radiative transitions are not strictly forbidden if the
quantum numbers of the initial and final states fail to obey Equations (7-41) and
(7-42). Such transitions are actually allowed to occur, but not with the emission of
radiation characteristic of an oscillating electric dipole. These other kinds of radiative
processes are highly suppressed whenever the wavelength of the radiation is very large
compared to the size of the radiating system.
The hydrogen transitions in Figure 7-5 can be displayed in more detail if the
degeneracy with respect to ( is included and if the A/ selection rule is taken into
account. Figure 7-6 provides such a display in which all the wavelengths of the
Lyman series are seen to arise from transitions of the type np —> Is. Figure 7-7 goes on
to show that all the wavelengths of the Balmer series are due to transitions connecting

Figure 7-7

Balmer transitions allowed by the A/ = +1 selection rule.

 7-5 Electric Dipole Selection Rules 371

{= to /' = 1, or <f = 1 to c" = 0, or /= 2 to t' = 1. We can look for experimental

evidence of this detailed structure and verify the A/ selection rule, provided we have a
suitable experiment to distinguish levels with different values of c" for the same n. The

Aw selection rule can also be confirmed if the experiment is able to split the
degeneracy of the states with different values of m for the same n and /. The means
to these ends are found Chapter 8.in

Let us return to the transition amplitude and inspect the parity properties of the
integral j4/ *y m TXPnt'm ^ T We observe that a nonvanishing result is obtained only from
-

integrands that are even under the inversion r —» — r. (Odd integrands contribute with
opposite signs for volume elements in opposite directions. These contributions to the
integral cancel pairwise in the integration over all space.) We then recall from Section
6-6 that each factor in the integrand has a well-defined behavior under the parity
operation. The vector r is odd by definition, while the eigenfunctions i/v^'m' ar*d ^ n (m
have parities given by (— Vf and (— 1) , respectively. Therefore, inversion produces
an overall-even integrand only if the two atomic states have opposite parity. We can
state this conclusion as a selection rule:

The parity of the state must change in an electric dipole transition.

It follows that the quantum numbers c" and (' must differ by an odd integer, in
agreement with the more restrictive result in Equation (7-42).
It is instructive to put these mathematical selection rules in terms of conservation laws
involving parity and angular momentum. Let us describe the radiation process as

(nc*m) -* (n'c°'m') + y ,

in which y denotes an electric dipole photon. We then assign an odd parity to y and

use Equation (7-42) to find that the overall parity of the atom-radiation system is
conserved according to the multiplicative law

(-l)'=(-lf(-l).

The overall angular momentum of the system must also be conserved. In fact, the
rules in Equations (7-41) and (7-42) tell us that the electric dipole photon carries away
a single h unit of angular momentum in the radiative process. We express the vector
conservation law for the angular momentum of the system in the schematic form

{= t + 1,

where the three vectors have lengths y7(<?+ l) V V"(/' + l) and \/2 with ( and , , ,
('

constrained to differ by one unit. This interpretation of the selection rules by means of
conservation laws is used often in atomic and nuclear physics.

Example

The Lyman transition 2p -» Is is allowed by the A/ selection rule. Let us

confirm this fact by explicit evaluation of the three components of the dipole
transition amplitude f4/ *r m rxPnt'm df. '
The relevant quantum numbers in the
372 The One-Electron Mom

transition {nt'm) -» (n'/W) are

n = 2 t=\ m= 1,0,-1 and «' = 1 /' = m' = 0.

The radial integral is the same for each component in the calculation. We
consult Table 7-1 and carry out the following integration over r, again with the
aid of Equation (7-8):

2 1

/ R l0 R 2l r 3 dr = -=«"" -=p,-P/ 2a y dp
f

a ,oo a / 2\ 5
128 ^

The Aw selection rule implies that the angular integration of the z component is

nonvanishing only for the m = case. We use Table 6-1 and Equation (6-36) to
perform the relevant angular integration:

We find the calculations of the x and y components easier to perform if we

consider the combinations x + ty and x — iy first and then extract the desired
results for x and y. This procedure takes advantage of the complex-exponential
<p dependence in the expression

x ± iy = r sin #(cos <f>

+ i sin <f> ) = r sin Oe
± '*

and blends the result with the similar (j> dependence of the spherical harmonics.
Thus, the angular integrations for the (x ± iy) components assume the general
form

JY^smOe^+Y^dSl.

We again refer to the Aw selection rule and observe that a nonzero result follows
for the case at hand only if we take m= — 1 for the (x + iy) component and
m = 1 for the (x — iy) component. The angular integrals in the two instances
are evaluated with the aid of Table 6-1 and Equation (6-36):

fYJunBeVY^dQ- J-tL^y Y*_ l

Y l
_ l
dSl=
^ for x + ty

and

f
Y»™ e <-* Y»*~f^[-{r '

j for * - iy.
 Problems 373

We combine the radial and angular portions of the three integrations as follows:

IY 256
for the ( x + iy ) component if m = — 1

V 3 243
128 IT 256
v/oV
~ a for the {x — iy) component if m= 1
243 V 3 ~ 243

1 128 ^
for the 2 component if m= 0.
, fi 243

Vanishing results are found if the three components of the dipole transition
amplitude are evaluated for any of the other possible values of the quantum
number m.

Problems

1. Show that the function

r/2a
R(r)=A\\ - —I

is a solution of the radial differential equation for the one-electron atom in the f = case.

What is the corresponding energy eigenvalue?

2. Determine the normalizing constant A for the wave function in Problem 1

3. For any /, the radial solutions for the one-electron atom have the form

, HP) r
R = e
p/ " with p = - ,

P a

where F is the nth-order polynomial

F{p) = A £ aK p
k
with fl
%
, ,
= 1.

* = /+!

Derive the recursion formula,

k/n - 1

relating the successive coefficients in the polynomial.

4. Use the recursion relation in Problem 3 to construct the radial polynomial in the case
where n = 2 and { = 0.

5. Use the recursion relation in Problem 3 and apply the normalization condition to
construct the wave function ^ 31m .

6. List the degenerate orbital states that belong to the M shell, giving the explicit (r, 6, <J>)

dependence for each of the wave functions.

7. Let the one-electron atom be in a state with quantum numbers n = 2 and /= 1, and
determine the most probable distance between the electron and the nucleus. Calculate the
 ,

374 The One-Electron Atom

expectation values (r) and (F) by explicit integration, and compare the results with the
general formulas given in the text.

8. Repeat the calculations of Problem 7 for a state with quantum numbers n = 3 and t= 1.

9. Let the one-electron atom be in its ground state, and calculate the probability of finding

the electron beyond the radius of the first Bohr orbit.

10. Consider a one-electron atom in a stationary state, and derive a formula for the rms speed
of the electron relative to the nucleus. Compare the answer with the result obtained in the
Bohr model.
11. Derive a formula for the electric dipole moment of the one-electron atom shown in the

figure, taking the origin to be at the center of mass. The result should be proportional to
— er and should reduce to — er if Z= 1 or if M— » oo.

12. Derive the results

rlii e
"n
( * ' '*e - 'V ra
* d<f> = unless m - m = ± 1
Jn
'0

and
lv
( e ""'V"" f>
d<j> = unless m' - m = 0.

These calculations appear in the demonstration of the selection rules for electric dipole
transitions.

13. Show by direct calculation that all three components of the dipole transition amplitude
vanish for the forbidden transition (« = 2, /= 0) — » (n' = 1, £' = 0).

14. Evaluate the z component of the dipole transition amplitude for the Balmer transition

3p -> 2s.

15. Evaluate the z component of the dipole transition amplitude for the Balmer transition
3d-> 2p.

16. Stationary states of the one-electron atom can exist in the form of superpositions of
degenerate states. An example is given by the wave function

,£2 ' / *-
*=-^(^200 + V'210)'"

Comment on the parity properties of ^, and compute the components of the electric

dipole moment vector — er for an atom in such a state.

 EIGHT
SPIN
AND
MAGNETIC
INTERACTIONS

/he Schrodinger theory of the atom is based

on a nonrelativistic treatment of electron motion. The effects of relativity are
appropriately ignored in first approximation, but the resulting picture of the atom is

incomplete until such behavior is taken into account. One of our goals in this chapter
is to introduce relativistic corrections as secondary contributions to the leading
approximation. We are interested in these corrections because we can detect their
influence in experiments of sufficient accuracy.
The Schrodinger theory has also been restricted to a treatment of the electron in
which the spatial coordinates are the only variables. Our main goal in this chapter is
to show that the behavior of the electron cannot be fully understood unless the particle
is endowed with an additional intrinsic variable known as electron spin. This new

observable is quantized like angular momentum and is detectable in experiments

where the electron system interacts with an applied magnetic field. Several of the key
experiments, and even a few of the important concepts, predate quantum mechanics.
In fact, the earliest experimental evidence for spin stems from roots in the 19th
century.
The first clues to spin came from studies of the influence of magnetic fields on the
emission of light by atoms. An experiment by P. Zeeman in 1896 showed that two of
the prominent lines in the visible spectrum of sodium were broadened when a sodium
flame was placed between the poles of a strong electromagnet. Zeeman concluded that
the frequency of the emitted light was altered by the application of the magnetic field.

Lorentz interpreted this effect in terms of his classical electron theory and predicted
that the magnetic field should split each spectral line into a fixed number of separate
components with different frequencies and definite polarizations. Line splitting was
later observed when the sodium lines were examined with improved resolution;
however, the number of split components did not agree with Lorentz's predictions.
This puzzling result became known as the anomalous Zeeman effect because the

375
376 Spin and Magnetic Interactions

Normal Lorentz triplet in zinc and anomalous Zeeman patterns in sodium and in zinc

Zinc Single! Sodium Principal Doublet

No field

111
Normnl Triplet
HI 111
Anomalous Patterns
Weak field

Zinc Sharp Triplet

. •
eld

inn mi
Anomalous Patterns
Weo* "f'ela

observations differed inexplicably from the normal effect associated with the classical
theory. Normal splitting could be detected only for certain types of lines in certain
elements. The early quantum ideas were also applied to this phenomenon, but the
application shed light only on the normal effect. Thus, the observed anomaly in the
Zeeman effect remained an unsolved problem through the period of the old quantum
theory.
Improvements in spectroscopic resolving power also revealed the splitting of lines
into multiplets of closely spaced components without the influence of an applied
magnetic field. This behavioratoms was given the name fine structure. It was
in free
discovered that the split multiplets were the ones that developed an anomalous
Zeeman pattern when an external magnetic field was applied. Hence, a link was
believed to exist between the phenomenon of fine structure and the anomalous
Zeeman effect, indicating the possibility of a common solution for the two problems. It

was also found that the spectra of the elements in a given column of the periodic table
displayed multiplets with common
features. This connection between the structure of
multiplets and the periodicwas the crucial piece of evidence that inspired W.
table
Pauli to make the first contribution toward the eventual discovery of spin. Pauli was
able to explain the occurrence of multiplets by letting the electron have a nonclassical
two-valued property, which appeared as a fourth quantum number in the description of
every atomic electron. Others later identified this peculiar quantized variable as the
electron spin. All these remarkable developments preceded the coming of the
Schrodinger equation and were carried over without difficulty into the new formula-
tion of quantum mechanics.
We confine our discussion in this chapter to the role of electron spin in the
one-electron atom, and we extend the treatment to atoms with many electrons in
Chapter 9.

8-1 Atoms and Light in a Magnetic Field

Faraday believed that magnetism should influence the light emitted by atoms, but he
could not develop apparatus sensitive enough to demonstrate an observable effect. His
expectations were not realized until Zeeman's experiment was performed on the
 8-1 Atoms and Light in a Magnetic Field 377

Figure 8-1

Classical Lorentz-triplet predictions for an atomic source in a magnetic field. The source emits
a spectral line of frequency V and the application of the field splits the line into three
,

frequencies v - 8v, v , and + Sv, where the shift 8i> depends on the field strength B. Light
v

observed along the direction of B has only the two shifted components with circular polarizations
in opposite directions. Note that the up-shifted frequency v + 8i> corresponds to circular
polarization in the same sense as the current in the electromagnet. Light observed transverse to

B has the two shifted components with linear polarizations perpendicular to B, and the one
unshifted component with linear polarization parallel to B.

Electromagnet _

H\ £7\Circular polarization

spectrum of sodium in 1896. Lorentz's interpretation of the Zeeman effect attributed

the emitted light to the oscillation of charge within the atom and showed that the
oscillation would be modified by the application of a magnetic field. His theory
selected a given spectral line, with frequency P in the absence of the applied field,

and predicted a splitting of the line into three different frequencies owing to the
interaction between the field and the atom. He determined a frequency shift 8v such
that this triplet would occur as v — 6V, vQ and v + 8i>. The members
of frequencies ,

of the triplet were expected to have certain polarization properties depending on the
direction of observation of the light relative to the direction of the applied field, as
described in Figure 8-1.
The classical theory of the Zeeman effect is interesting because the analysis
identifies the basic parameters of the interacting system. A similar parameterization of
the interaction between the atom and the applied field appears in the quantum
version of the problem. Lorentz's model associates the effect with the oscillation of the
electrons in the atom and treats such an oscillation at frequency v as a source
emitting classical radiation of the same frequency.
The application of a constant magnetic field B fixes a direction in space to which
the electron motion can be referred. Let us look first at the oscillation of a single
electron in a plane perpendicular to this direction. Any such linear oscillation at
frequency v (with no field) can be resolved into clockwise and counterclockwise
circular motions in phase, each with angular velocity 2ttp , as shown in Figure 8-2.
We can attribute the oscillation of the electron to a simple-harmonic binding force of
the form — b and define the force constant by means of the frequency formula

277 1/ m.
 .

378 Spin and Magnetic Interactions

Figure 8-2

Resolution of linear oscillation into two counter-rotating motions in phase.

Angular velocities 2ttvq

Radii 4
Frequency v
Amplitude A

The magnetic field subjects the electron to the additional Lorentz force — ^v X B,
which acts in opposite radial directions for the two counter-rotating motions of the
oscillating charge. This effect produces two different values for the new angular
velocity 2tTv and for the new orbit speed

2mrv

We use this expression to write the centripetal force

m.v'
= A^2„2
4ir v rm t ,

and we assume a small Lorentz force so that we can take the radius of the orbit to be
unaffected by the field as a first approximation. Figure 8-3 describes the centripetal

Figure 8-3

Effect of the Lorentz force -«vX B for

clockwise and counterclockwise rotations. The
magnetic field is directed away from the reader
as in Figure 8-1.

kr
2nvreB

Clockwise

.' rrirrH

kr
©,
Counterclockwise
 81 Atoms and Light in a Magnetic Field 379

force as

\m 2 v 2 rm = 2mvreB +
e
kr

for clockwise motion, and

\ rn 2 v 2 rm e = —2'rrvreB + kr

for counterclockwise motion. We employ Equation (8-1) to eliminate k and rewrite the
results as quadratic equations for the unknown frequency v.

eB
v — Vq = (clockwise)

and
eB
v
2
+ v — Vq = (counterclockwise).
277 772,

The linear terms in v must be small compared to v£ because of our assumption of a

small Lorentz force. Consequently, when we solve the quadratic equations for the
frequencies we find

v = vQ + —— eB
for the clockwise case
,
(8- 2a)
x

477171.

and
eB
v = vQ for the counterclockwise case. (8-2b)

The two electron motions are therefore supposed to generate classical radiation at
these two shifted frequencies. Note that the frequency shift has the form

eB
8p = (8-3)
477W f

in each case.
If we view the source along the direction of B, as suggested in Figure 8-3, we expect
the observed light to have circular polarization in the clockwise sense for v = p + 8i>,

and in the counterclockwise sense for v = v — hv. This conclusion agrees with
Zeeman's observations of the light from his broadened spectral line. Note that the
result also confirms the fact that the sign of the oscillating charge is We have
negative.

predicted circularly polarized shifted components of light for electrons oscillating in a

plane perpendicular to B. When we view the source in a direction transverse to the
applied field, we see these shifted components as light with linear polarization in the
plane of the oscillating charge. The electrons in the atom may also oscillate along B to
produce light with polarization in that direction. No shift in frequency is predicted in
this case, since v X B vanishes. Radiation of this kind is seen unshifted if the source is

viewed transverse to the direction of the applied field. All these conclusions from
Lorentz's theory are illustrated in Figure 8-1.
We should note the presence of the factor e/m e in Equation (8-3). This aspect of
the analysis was appreciated at the time of Thomson's cathode-ray experiments,
because it was possible to measure the frequency shift in a magnetic field of known
380 Spin and Magnetic Interactions

strength and thereby determine the charge-to-mass ratio for the radiating charge in
the atom. The resulting determination agreed with the value obtained for Thomson's
cathode rays and thus supported the idea of the electron as a universal constituent of
the atom.

Example

The frequency shift 8v is quite small compared to the line frequency v , even
for rather large values of the magnetic field. We illustrate by choosing B = 1 T
in Equation (8-3):

eB (1.76 X 10" C/kg)(lT)

8v = = 1.40 X 10
10
Hz.
477

(The figure for e/m e

is quoted from Section 3-2.) This result is to be compared
lj
with values of order 10 Hz for the frequency of visible light. The units in this
calculation should also be mentioned. We recall Faraday's law relating the rate
ofchange of magnetic flux to the induced emf and pass from teslas to volts by
means of the conversion

T m2•

V=

We then obtain the units

C C V-s J-s
—
kg
T=
kg m-
=-
kg •
m 2

for the computation of 8p.

8-2 Orbital Magnetic Moments

The quantum version of the Zeeman effect involves familiar observable quantities and
makes no use of the oscillatory motion described in the classical model. Quantum
mechanics teaches us to recognize a shift in the frequency of a spectral line as evidence
for a change in the transition energy of the emitted photon. This change in turn
implies a shift in the quantized energy levels of the atom owing to the application of
the magnetic field. Hence, the observation of Zeeman splittings in spectral lines

translates directly into the deduction of Zeeman energy splittings among the states of
the atom.
We are concerned with the additional energy of the atom associated with the
presence of the applied magnetic field. We treat the atom as a system of moving
charges and identify a magnetic dipole moment |i, so that we can introduce a magnetic
interaction energy

F„=-|i-B (8-4)

as an added contribution to the potential energy of the system. The magnetic moment
vector parametrizes the magnetic structure of the atom, and the applied magnetic
 8-2 Orbital Magnetic Moments 381

Figure 8-4

Magnetic moment p. for a circular Bohr orbit.

The direction of the angular momentum L is

opposite to the direction of (J..

Angular
velocity 2ttv

field acts as an external probe of this structure. We take B to be constant in space and

time and observe from Equation (8-4) that the magnetic configurational energy is
minimized when \i is aligned along B. The dynamical behavior of \i is determined by
angular momentum considerations, since the magnetic moment of the atom is directly
related to the angular momentum. This section is devoted to the relation between
these quantities for the case of the one-electron atom. We are dealing with small
energy shifts, and so we can ignore the small correction for nuclear motion and simply
replace the reduced mass by the electron mass throughout. (Thus, the symbol ju. for
reduced mass does not appear in this chapter and cannot be confused with the new
symbol \l for magnetic moment.)
We consider a circular Bohr orbit for an electron around a fixed nucleus, and we
take the angular velocity of the electron to be 2 77 p. The current in the electron orbit
2
has magnitude ev, and the orbit has area 7rr , so that the product of these quantities
gives the magnitude of the magnetic moment vector

ju, = irr ev.

The direction of |X is shown along with the various parameters of the orbit in Figure
8-4. We recall that the magnetic field of such a current loop is similar to that of a bar
magnet, at distances far from the respective dipoles. The electron orbit also represents
mechanical motion with angular momentum of magnitude

L = m e
vr = lirr m e
v.

We note that the quantities /x and L contain the kinematical factor r

2
v and that their
ratio depends only on fundamental constants:

2rn

The figure shows that the vectors |i and L have opposite directions for an orbiting
particle of negative charge. We take this observation into account and relate to L by
|i,

the vector formula

L (8-5)
2m.

The final result holds for elliptical as well as circular electron orbits.
382 Spin and Magnetic Interactions

The proportionality between |x and L is a general property of a rotating charge

distribution. The magnetic moment and angular momentum of an arbitrary rotating
body with mass M and charge Q always satisfy a relation of the form

ft.
p S
2Af

where the details of the rotating distribution determine the value of the g-factor
denoted by the symbol g. We are using Q= —e for an electron orbit in Equation
(8-5), and so we identify the corresponding orbital g-factor as

g= I-

A special symbol is introduced to represent this dimensionless quantity, in preparation

for other g-factors and other kinds of magnetic moments to be encountered later on.
Let us also adopt standard practice and give the angular moment in h units so that we
can rewrite Equation (8-5) as

V- = ~Wb~£ with § = l > ( 8"6)

where
eh
Ma-TT-
lm
(8-7)
t

This combination of physical constants is known as the Bohr magneton. The dimensions
of ju
fl
are the same as those of \i,
b serves as a natural unit for the magnetic
so that jx

moment of the atom. We express the numerical value of the Bohr magneton in two
ways,

HB = 9.274 X 10" 24 A •
m = 2
5.788 X 1(T 9 eV/G,

and observe that the second figure has the especially useful units of energy per
magnetic field strength.
We can use the relation between fi and L to determine the classical behavior of |i.

in an applied B field. The magnetic moment experiences a torque equal to fi X B, and

so the angular momentum vector varies with time as

—
dh
dt
= a
P X B.

We employ Equation (8-5) to obtain the dynamical equation

—
dL
=
dt 2m
e
Lx B
e

= to X L, (8-8)

introducing the constant vector

co = —
2m,
B. (8-9)
 8-2 Orbital Magnetic Moments 383

Figure 8-5

Behavior of \i and L according to the dynamical equation dh/dt = to X L. The dynamics

causes a Larmor precession of the magnetic moment about the direction of the applied field.

The dynamics described by Equation (8-8) is exactly the same as that for a spinning
top in precessional motion about a fixed axis defined by the direction of to. Figure 8-5
summarizes the physical properties of the oppositely directed vectors p. and L. We
observe that the magnitude of L is constant:

dL
-L l
= -L • L = 2L • — - = 0,
dt dt dt

using Equation (8-8) in the last step. We then use conservation of the energy |x • B to

argue that the polar angle 6 between L and to also remains constant. It follows that
the angular momentum varies only with respect to the azimuthal orientation of L
about the to axis. We consider a time interval dt and identify an increment in the
azimuthal angle
dL

L sine/

according to the figure. We can then express the precessional angular velocity of L
and |x by writing

1 dL u>L sin
= to,
~dt L sin 6 dt L sm8

again using Equation (8-8). This behavior of the magnetic moment vector is an
example of Larmor precession, a phenomenon in mechanics treated by a general
theorem due to J. Larmor. Equation (8-9) gives the frequency of precession as

U eB

2tt ^irm.

an expression identical to the formula for the frequency shift bv in Equation (8-3).
Thus, the classical dynamics magnetic moment presents a picture in which the
of the
applied field affects the orbital motion in the atom by superimposing a precession at
 .

384 Spin and Magnetic Interactions

the Larmor frequency about the direction of B. A schematic rendition of this effect is
shown in the figure.
The main result of this section is the relation between fx and L in Equations (8-6)
and (8-7). We are aware that (X and L have been handled classically, and we should
question whether the resulting formula can be carried over to quantum mechanics. A
proper quantum approach would show how electrodynamics is incorporated in the
Schrodinger theory and would prove the validity of the relation between fx and L as
quantum observables. We leave the demonstration of these steps to a more thorough
treatment of quantum mechanics. It should also be noted that precessional motion is a
classical phenomenon involving the behavior of a well-defined L vector. We must
reinterpret the word if we wish to speak of precession as a concept in quantum physics.

Example

Let us prove that Equation (8-5) holds for any elliptical Bohr-Sommerfeld orbit.
We consider an element of angle dO swept out by the electron in a time interval
dt and identify the area of the resulting sector as

2
r
dA = — dO.
2

This element of area makes a contribution to the magnetic moment given by

dq dO
r = dA
da — = dq.
dt 2 dt '

2
The force on the electron is a central force, and so the quantity r dd/dt is a
constant proportional to the angular momentum:

L = mr 2 '
—= dt
constant

We use this observation to obtain the formula for the magnetic moment:

!' f
J,„w,,
rbit
du = —
Am
2m.
/.

J
[ dq =
2m
/..

as in the case of a circular Bohr orbit.

Example

Let us also verify the value quoted for the Bohr magneton:
_,9 34
eh (1.602 X 10 C)( 1.055 X 10" J •
s)

^B ~ 31
2m e '
2(9.110 X 10" kg)

= 9.274 X 10' 24 A •
m 2

24
9.274 X 10 J/T -
- .
ir . . , .
=1 7rt<"t
3 /OO
.
v
A in
1U
9
eV/G,
19 4
(1.602 X 10~ J/eV)(l0 G/T)

using the unit conversion from the example in Section 8-1.

 8-3 The Hormal Zeeman Effect 385

8-3 The Normal Zeeman Effect

The angular momentum L is quantized according to the rules developed in Chapter 6.

These quantization properties are passed along to the magnetic moment p., since |x is
directly related to L. The magnetic moment determines the behavior of an atom in an
applied magnetic field via the p. B interaction, and so the quantization of
• accounts |jl

for the Zeeman splitting in the energy levels of the atom. Thus, the Zeeman effect
provides evidence for the quantization of L as a result of the quantization of |i.

Let us suppose that the one-electron atom is in the stationary state ^fn f m in the
2
absence of an applied field. The quantity L has the value h c*(i* + 1), and so the
magnetic moment of the atom has magnitude

gf-B

by virtue of Equation (8-6). The z component of L is given by

(L z ) = mh

in this state, and so the z component of |x has the expectation value

00 = - -y< L *> = -gts"- (s-io)

These remarks suggest that we employ the interaction of the magnetic moment to gain
access to the angular momentum properties of the state through the dependence of
(ju..) on the quantum number m.
The applied B field is a constant vector whose fixed orientation in space offers a
natural direction to choose as the axis of quantization. We align the z axis along B for
the definition of L z and we specify the state ^nfm with azimuthal quantum number
,

m according to this choice. The interaction energy in Equation (8-4) then assumes the

simpler form

VM =-ii z B, (8-11)

so that the expectation value becomes

(VM )= -</*,>*= +g^ B Bm (8-12)

with the aid of Equation (8-10).

The quantity (VM ) represents the additional energy acquired by the atom in the
state ty n tm when the magnetic field is applied. We note that the added energy depends
only on the integer m in a field of given strength. Hence, the effect of the field is to
produce a discrete energy shift for each of the any w^orbital
2c" + 1 values of m in
configuration. We illustrate this phenomenon by adapting the energy level diagram in
Figure 7-2 to the new situation displayed in Figure 8-6. The previous diagram reminds
us that the nth energy level of the atom has energy E n and that the states ^„
/m are
degenerate with respect to the quantum numbers t* and m in the absence of a field.
The new diagram shows how these states split apart so that the various m values yield
energies different from En by the amount predicted in Equation (8-12). We note that
the states ^ln fm are still degenerate in their dependence on <f and that the states with
successive m values have the same energy spacing

8EM = gli B B (8-13)

386 Spin and Magnetic Interactions

Figure 8-6

Normal Zeeman splittings in the energy levels of the one-electron atom.The magnetic field
breaks the degeneracy of the states with respect to the quantum number m. States ^„^ m with
adjacent values of m are spaced in energy by an amount SE U = gfi B B, for any choice of n and
/. The scale of the Zeeman splitting is grossly exaggerated in the diagram.

(=2
e=i - 2
1 1
- n= 3 m =

<L

f= 1
-*
i
n = 2 m= m = -r-
6EM
-1 *

f =0
n = 1 m =

in OT7 n<£orbital system. The sign of the energy shift (VAf ) is the same as the sign of
m, and only the m = states are unaffected by the field. We let each of the split levels

shown in Figure 8-6 refer to a distinct precessional state of the atom, whose energy
maintains the fixed value

E + ms Bm
n

in the presence of the constant magnetic field. The azimuthal quantum number m is

also called the magnetic quantum number because of this property.

The most obvious feature that distinguishes Figure 8-6 from Figure 7-2 is the
removal of the degeneracy with respect to m. We interpret the m dependence of the
energy levels as an indication of a breakdown of rotational symmetry. The applied B
field introduces a preferred direction in space for our selection of z axis, and so the

energies of the states vary with the L, quantum number as a result.

The Zeeman splitting of the energy levels causes a frequency shift in the radiation

from the atom. We determine the shift by identifying the allowed radiative transitions

according to the selection rules discussed in Section 7-5. The rule A/= + 1 has
already been used to pick out the electric dipole transitions for the Lyman and Balmer
series in Figures 7-6 and 7-7. The other rule requires

Aw = or + 1
 8-3 The Hormal Zeeman Effect 387

Figure 8-7

Lyman a transition and normal Zeeman splittings.

•= 1
1
(= o e=
E: n = 2
i
t <5£\
m =
-1
T

n=l -1-1-1 m =
e = o f=

and gives more pertinent information about the Zeeman effect, as illustrated in
Figures 8-7 and 8-8. We observe that all the indicated transitions involve only three
distinct emitted-photon energies,

kE-SEM , A£, and A£ + SEM ,

where A£ denotes the usual Bohr transition energy without the applied field. A triplet

of spectral lines is the predicted result, implying a shift in frequency to either side of
the usual line by an amount

8EM g^B B eB
Sf = '

2'ITh 4:77171,

in agreement with the classical formula in Equation (8-3). The illustrations refer
specifically to the Lyman a line (where n = 2 -* n = 1) and the Balmer a line (where

Figure 8-8

Balmer a transitions and normal Zeeman splittings.

=
t 2
2
(= i
1
t = o t = i e = 2 f
-n=3
SE,
, n m = m =
1 1 -1
-2

1 I 1
-n=2 • m = -m = m =
( = o e = i e = o -1 -1
t = 1 ( = 1
388 Spin and Magnetic Interactions

n = 3 —> n = 2). It is clear, however, that the triplet prediction is quite general, since
the normal Zeeman splitting 8EM is common to all nt° orbitals. The figures tell us that
the photon energies AE — 8EM and AE + 8EM are associated with the Am = + 1

and Am = — 1 transitions, and that the unshifted photon energy AE is due to the
Am = transitions. It follows that the Am = + 1 linesw correspond to the shifted
frequencies in Figure 8-1. We know that these lines exhibit circular polarization when
viewed along the direction of the field. We also know fromSection 7-5 that the single
unit in Ac" and Am represents a single h unit of angular momentum carried away by
the radiated electric dipole photon.
The predictions of the normal Zeeman effect are not borne out in observations of
the spectrum of hydrogen, as anomalous splittings are seen instead of the expected
triplets. The classical results have not been altered by taking a quantum approach to
the problem. We have included the flawed classical treatment as background in order
to point out the fact that the preferred quantum solution also fails to resolve the
anomaly. We are forced to concede that our picture of the magnetic structure of the
atom is incomplete.

Example

The Balmer a processes in Figure 8-8 have transition energy AE = 1.89 eV and
emitted wavelength

he
X = = 656.1 nm
AE
with no applied field, as in the calculations at the end of Section 3-6. Let us
consider the abundant collection of normal Zeeman transitions for the illustrated
case

(n = 3,/ = 2) -» (n = 2J= 1).

The Aw selection rule allows nine different transitions, as shown in the figure,

with three distinct photon frequencies:

AE - 8EM AE AE + 8EM
, , and .

h h h

We define the shift in wavelength by the relation

he
X + 8\
AE- SEM
'

and we use the condition AE s> 8EM to make the following approximation:

A + 5A= --
AE\
he I

1 + —
8EM
AE
\=\
-
\
I

1 +
8EM
—
AE
^ \
- 8X = \-
8EM
AE
I I

For B = 1 T we find

8E M = gn B B= (1)(5.788 x 1(T 9 eV/G)(l0 4 G) = 5.788 X 10" 5 eV

 8-3 The Hormal Zeeman Effect 389

and
5.788 X 10- -5
8X = (656.1 nm ;
— n noni nm,
u.uzui m-n
1.89

a very small departure from the zero-field value for the Balmer (V line.

Example

Let us prove that the stationary-state wave function of the atom is unaffected by
the application of the constant magnetic field, while the energy of the state
undergoes the normal Zeeman energy shift. Without the field, the stationary -state

eigenfunction ty nfm and the energy eigenvalue E n obey the equation

—V
2/i
2
+ V(r) 4>nfm = E nt n / m ,

where V( r ) denotes the Coulomb potential energy. Application of the field

introduces another differential operator on the left, arising from Equation

(8-11). We employ Equation (8-6) and recall Equation (6-10) to assemble this

additional term:

gV B B gV-B B h
-fi.B = +
h
,
L, -»
h i
:
—d

d<f>

The newly defined problem calls for a new stationary state,

whose eigenfunction \p and eigenvalue E satisfy the equation

1
h Q&rB d

2ju i d<j>

We note that ip„f m is an L z eigenfunction since

1 3

and we recognize at once that \p n ^ m is a valid solution of the new differential

equation:

^ gV B B
— V
2/i
,
' + V ( r ) +
i
3
^ntm = Er&n(m + £M B Bm 4> n(m-
d<t>

We may therefore take \p = ^ n/m and claim the new energy eigenvalue to be

E = En + gV-B Bm ,

in agreement with Equation (8-12).

 . ,

390 Spin and Magnetic Interactions

8-4 The Stern- Gerlach Experiment

It was known by 1920 that spectral lines were split into multiplets without the
influence of an applied magnetic field. The phenomenon was originally attributed to a
force within the atom, where the outer electrons interacted with a proposed " magnetic
core" consisting of the inner electrons and the nucleus. This interacting system of inner
and outer magnetic moments was supposed to explain the structure of multiplets in
the absence of a field, as well as the anomaly in the Zeeman effect in the presence of a
field.These ideas were tested in 1922 by O. Stern and W. Gerlach. Their classic
experiment employed a magnetic field of special design to study the behavior of a
beam of atoms. Their observations demonstrated the quantization of the magnetic
moment and also appeared to confirm the magnetic-core hypothesis. Soon, however, it
became necessary to reject this idea and reinterpret the outcome of the experiment as
unequivocal evidence for the spin of the electron.
The Stern-Gerlach experiment examines the dynamics of a magnetic dipole in a
nonuniform magnetic field. Let us refer to Figure 8-9a and recall that a uniform field
produces a torque but exerts no net force on such a dipole. Figure 8-9b goes on to
show that the forces on the two poles of a magnet yield a net force, as well as a torque,
if the field is not uniform. Let us assume that the nonuniform field varies appreciably
in the z direction component of the net force according to the
and consider only the z
details shown in the figure. We express the z component of the field at the locations of
the N and S poles of the magnet by the expansions

BM = B, + z —
8BZ
oz
and B Z
(S) = Bz0 - z —
dBz
oz

to first order in the indicated distance z . The coefficients Bz0 and dBJdz denote the
field strength and the field gradient, evaluated at the center of the dipole. We let the
magnet have hypothetical pole strengths +g , and we write the net force as

F =
z g BM - go Bz (S)
= 2 go z —
3BZ
oz

= M, —
dBz
(8-14)

Note that the z component of the magnetic dipole moment appears in the last step.
The force causes a beam of magnets entering the field along the y axis to experience a
vertical deflection, up or down depending on the sign of ju.., as illustrated in Figure
8-10. The classical quantity \i
z
is continuous in value because of the arbitrariness in
the observable orientation of the dipole. The beam therefore produces a continuously
distributed image beyond the region of the field.
in a detector

Very different results are found in such an experiment if the beam of magnets is
replaced by a beam of atoms. Each atom has a certain probability to be in some
quantized state of the angular momentum component L,. The corresponding mag-
netic moment ji z is then observed with the same probability to have one of several
discrete values. If we consider a beam of hydrogen atoms as an example, we expect to

find magnetic moments given by

(ii z)
= ~iii B m with w =-/,..., /
 8-4 The Stern- Gerlach Experiment 391

Figure 8-9

Forces on the poles of a magnet in a uniform field and in a nonuniform field. The field gradient
exerts a net force on the magnet in the second case.

(a) (b)

for atoms in definite Lz states. The force F, becomes a discrete-valued quantity in this

experiment, so that a fixed number of vertical deflections of the beam is detected in a

given nonuniform field. Thus, an arbitrary hydrogen atom in the beam may have L z
2
equal to hm and ju. equal to —gji B m with probability \c
m \
, and it may then be
deflected by Ft along a certain discrete path with the same probability. We call this

phenomenon space quantization because we imagine the effect to occur via discrete
trajectories in space. The result is actually observed as a discrete distribution of the
beam image in a detector beyond the region of the field, as sketched in Figure 8-11.
Hydrogen atoms with orbital quantum number c* are expected to display a (2f+ 1)-

fold splitting of the beam, and no deflection is supposed to be seen for a beam of
ground-state t"= atoms. Complex atoms are also expected to undergo an odd

Figure 8-10

Deflection of a beam of classical magnets in a nonuniform magnetic field.

Beam of
magnets
 1

392 Spin and Magnetic Interactions

Figure 8-1

Space quantization for a beam of hydrogen atoms. An odd number of deflections is expected for
a purely orbital magnetic moment, but a twofold splitting of the beam is observed in a
Stern-Gerlach experiment.

(2( + 1) - fold image fold image

number of discrete deflections if the magnetic moments are due entirely to orbital
electron motion.
The employed a beam of neutral atoms ob-
original Stern-Gerlach experiment
tained by evaporating silver in a heated oven.The silver atoms were passed through a
strong transverse field gradient and were deposited on a glass plate where their
deflections could be measured. This image of the beam was found to be discrete rather
than continuous, in striking agreement with the notion of space quantization. In fact,

the beam was observed to form a two-fold image, the result predicted on the basis of
the prevailing magnetic-core theory of the silver atom. was The core interpretation
discredited, however, when a subsequent experiment
same design was per- of the
formed with a beam of hydrogen atoms. It was expected that hydrogen should show
no deflection for atoms in the ground state and should give an odd number of beam
splittings for excited atoms if the magnetic moment of the atom were attributed solely
to the orbital motion of the electron. Instead, the beam of hydrogen atoms again
displayed a two-fold splitting, so that expectations and observations conflicted in the
manner described in Figure 8-11. The " magnetic core" could not account for this

result, since the core consisted of the nucleus alone and the nuclear magnetic moment

was too small to explain the observed effect. (It was recognized that the natural unit
for nuclear moments should be the nuclear magneton eh/2M instead of the Bohr
magneton eh/2m f The substitution of the proton mass
. for the electron mass m e M
made the scale smaller for nuclear moments than for atomic moments by three orders
of magnitude.)
The hydrogen experiment demonstrated that (/a.) had a nonvanishing two-valued
quality in the ground state of the atom.The two-fold splitting indicated a quantiza-
tion of the magnetic moment in which two, and only two, quantized states contributed
probabilities to the discrete deflections of the beam. It was apparent that this aspect of

the magnetic moment of the atom was attributable to the electron but was indepen-
dent of the orbital motion of the electron. Thus, a new intrinsic property of the
electron seemed to be in evidence as a quantized two-valued variable. The bifurcation
of the beam of silver atoms in the original Stern-Gerlach experiment also appeared to
be due to this same two-valued magnetic moment for the outermost electron in the
silver atom.
 8-4 The Stern - Gerlach Experiment 393

Pauli's contribution to the understanding of this problem came in 1924. He argued

that the structure of multiplets and the anomaly in the Zeeman effect could be
explained if a new formal two-valued degree of freedom was assigned to the electron.
The research students S. A. Goudsmit and G. E. Uhlenbeck took up Pauli's idea in the
following year and expressed this proposed two-valued quality in terms of a quantized
variable with the properties of an angular momentum. They imagined an additional
spinning motion for the orbiting electron in the atom, somewhat like the axial rotation
of a planet in its orbital revolution around the Sun. The spin of the electron was
supposed to produce an intrinsic magnetic moment whose magnitude was to be found
from experiment. Goudsmit and Uhlenbeck put forward these properties of the
electron as a quantum hypothesis, acknowledging that the classical picture had serious
flaws on relativistic grounds. Pauli did not accept this representation of his own
fundamental idea until he was convinced that spin was essential to a correct theory of
multiplet structure. He finally sanctioned the concept in 1927 by showing how the
new principles should be incorporated in the nonrelativistic Schrodinger theory. By
then was clear that spin was needed in the quantum theory to explain the
it

Stern-Gerlach experiment, the fine structure of spectral lines, and the anomalous
Zeeman effect.

Example

Equation (8-4) offers an alternative route to the expression for the force on a
magnetic dipole. We write out the interaction energy as

VM = -P x Bx -ti y By -n 2 B z

and treat VM as a function of the coordinates (x, y, z) of the dipole. The z

component of the force is then found from the formula

oz

If we assume that B makes

z
the dominant ^-dependent contribution to VM we
,

find

dB,

as in Equation (8-14). The deflection of the beam can be predicted on the basis
of familiar classical arguments. We use the temperature of the sample to obtain
the beam velocity according to the relation

M
— 2
3
= -k„T.
v
B
2 2

where M is the mass of the atom and k B is Boltzmann's constant. then let y We
denote the beam distance across the field as in Figure 8-10 and identify the time
of traversal as t = y/v. The vertical acceleration FJM is a constant, and so the
 .

394 Spin and Magnetic Interactions

final result for the vertical deflection is easily derived:

1 Fz 1 dBs y 2 dBz y
:M z4 "= =
2 M 2M' 3z v'
? rz
P,
dz 6k B T

The predicted deflections follow for a given field gradient and a known
magnetic dipole moment. We take the latter quantity to" be quantized when we
apply the formula to a beam of atoms.

8-5 The Properties of Electron Spin

We have taken the Stern-Gerlach experiment and the Goudsmit-Uhlenbeck hy-

pothesis as grounds for the concept of electron spin. The hypothesis introduces a spin
vector S as a new quantum mechanical variable for the electron and endows S with
quantization rules patterned after the behavior of the orbital angular momentum L.
We continue to follow this inferential approach, based on experiment, as an alterna-
tive to a more formal treatment of spin.
Let us choose an arbitrary direction for the z axis and consider states of the
electron in which the z component of S is known with zero uncertainty. These
determinations of Sz are expressed in terms of a new spin quantum number m by s

eigenvalues of the form

Sz = hm s . (8-15)

We identify this variable with Pauli's formal two-valued degree of freedom, and we
attribute the results of the Stern-Gerlach experiment to its discrete properties. The
vector Sbe treated like the quantized angular momentum vector L. We know
is to
that L, has 2/4- 1 discrete eigenvalues for some choice of the quantum number /,
and so we argue that there must exist a number s such that m s
has the analogous set

of 2 s + 1 allowed values

m =
s
—s,. . , s.

The fact that m s

must be two-valued then implies

s=\ and m =-\-or+^.

s
(8-16)

The quantization rules also require S to have a fixed magnitude determined by the
eigenvalue

S 2 = h 2s(s + 1) = ffc
2
. (8-17)

These properties are illustrated schematically in Figure 8-12. The z direction has been
selected arbitrarily, and so the quantized behavior of S holds for any chosen direction
in space along which the component of the vector may have either of the two definite
values +h/2. The figure reminds us that only one component of S can be specified
with certainty, as must be the case for any angular momentum vector. The two
illustrated orientations of S describe the spin-up and spin-down states of the electron.
We call the electron a spin-^ particle to summarize the quantization properties
contained in this description.
 8-5 The Properties of Electron Spin 395

Figure 8-12

Quantized spin angular momentum vectors.

The z component of S has the values ± h/2
with zero uncertainty.

Uncertain

The quantum number m becomes part of a revised picture for the states of the
s

atom. Now that we have adopted the symbol m to define the discrete values of Sz we
s
,

must go back and refine our previous notation for the magnetic quantum number m
associated with L,. Hereafter we denote the eigenvalues of L, as

hm, where mf *,...,/,

and employ the two independent indices m ( and m s to specify states according to the z
components of L and S. A stationary state of the one-electron atom is then assigned a
set of four quantum numbers {n£m ( m s ) to determine a complete configuration of the

quantum system. We express the corresponding wave function ^nfm ,„ for the given
energy state of the atom, with definite orbital description in space and definite up or
down orientation of electron spin, by writing

%, m , m ,
= R„Ar)Y, m ,(9,4>)e- E ^Hl or 1). (8-18)

We use the rightmost symbol to convey the meaning of the new electron quantum
number; spin up ( T ) denotes m =
s
~, and spin down ( J, ) denotes m = —
i \. This new
two-valued property doubles the number of states that appear in the energy level

diagram of Figure 7-2. Thus, Equation (8-18) is the basis for the revised scheme
shown in Figure 8-13, in which the energy levels depend only on the principal
quantum number n, and the degeneracy of the states at energy En is equal to 2n 2 ,

twice the degeneracy found in Figure 7-2.

The properties of Sz and S 2 are rather unlike those of L, and L 1 from the
viewpoint of the correspondence principle. We recall that a macroscopic orbital
angular momentum L is obtained in the classical limit h —* 0, provided the limit of
large / and m e is also taken. No such regime of large quantum numbers exists in the
case of electron spin, since Equations (8-15) and (8-17) define a vector S of fixed
magnitude with only two quantized orientations. It follows that S disappears in the
limit h — > 0, as befits the purely quantum nature of the concept of spin. We should
not look for much insight from the classical planetary picture of a spinning orbital
electron because of this observation. In fact, we should expect spin to behave quite
differently from any classical angular momentum.
396 Spin and Magnetic Interactions

Figure 8-13

Energy levels E n
and degenerate states ^f„/ m m for the one-electron atom. The dynamics of the
atom is governed only by the Coulomb force, as in Figure 7-2. The spin of the electron may be
either up (T) or down (i) for each assignment of the set of quantum numbers (nc'm^).
e=o e = l < = 2 e=3
I or 1 t or l t or I i or 1

n = 4 4s 4p Ad "4/ N 32 states
(1 x 2) (3 x 2) (5 x 2) (7 x 2)
K-. n=3
(1 x 2)
3s
(3 x 2)
3d
p
(5 x 2)
3d M 18 states

- n = 2
(1x2)
2s
(3x2)
2p 18 states

- n = 1 Is K 2 states
(1 x2)

The Stern-Gerlach experiment implies that both L and S have their own unique
magnetic moments and g-factors. Let us rewrite the orbital magnetic moment from
Equation (8-6) in the form

L
= 8 " 19 )
V-l -SlVbJ (

and take the orbital g-factor to be

as before.We then introduce the new spin magnetic moment of the electron by the
analogous relation

S
V-S
= -gsPBj- ( 8 " 2 °)

We regard this formula as the defining equation for the spin g-factor g s a parameter to ,

be determined by experiment. Classical mechanics is unable to provide any guidance

 8-6 Magnetic Resonance 397

about the value of this quantity. In the relativistic quantum theory of the electron,
however, it is possible to show that the spin g-factor should be given by

fo-2.

This number is interesting because the predicted value is exactly twice that of g L and,
furthermore, is in good agreement with experiment. It is customary to express
measurements of g s in terms of the deviation from unity for the ratio g s/2. The
current value for this deviation is quoted to astounding accuracy as

fa- = 0.001159652193.

A technique for measuring magnetic moments to very high accuracy is discussed in

Section 8-6.

Example

Figure 8-12 provides a way to visualize the two electron spin states in which Sz
has the values h/2 and — h/2 with zero uncertainty. The spin vector S makes a
fixed angle with the z axis, given by

h/2
cos = cos 54.7° in the spin-up state.
fih/2

Notice that S has a completely random azimuthal orientation in each case. The
spin magnetic moment p, 9 is aligned antiparallel to S, according to Equation
(8-20). The magnitude of this vector is given in Bohr magnetons by the value

This fixed result should be contrasted with the magnitude of the orbital
magnetic moment for a one-electron atom,

The latter expression gives the sequence of values 0, v2 fi B Vo n B

, , . . . for orbital
quantum numbers t= 0, 1, 2, . . . .

8-6 Magnetic Resonance

The Stern-Gerlach apparatus is useful as a device for separating magnetic states, or

spin states, in a beam of atoms. We can employ the device to observe the phenomenon
of magnetic resonance in atoms and use the resonance effect to make precise
measurements of magnetic properties. This type of resonance is analogous to the large
response obtained for a driven oscillator when the frequency of the driving force
matches the natural frequency of oscillation. It is possible to subject a beam of atoms
to certain contrived magnetic fields and produce the same behavior.
398 Spin and Magnetic Interactions

A constant magnetic field causes a precession of the magnetic moment of an atom.

We have described the classical problem of precessional motion in Section 8-2 and
Figure 8-5, and we have introduced the quantum concept of precessional states in
Section 8-3 and Figure 8-6. The Larmor frequency appears in each situation as the
natural frequency for the behavior of the dipole in the applied field. The energy of
such a system remains fixed if no mechanism is included to bring about a change in
energy. In this circumstance, the classical dipole maintains -a constant angle with the
applied field in Figure 8-5, and the quantum dipole makes no transitions between the
split energy levels in Figure 8-6. We must impose some kind of additional driving
influence on the system if we wish to change the energy and demonstrate magnetic
resonance.
Let us look first at the classical problem as displayed in Figure 8-5. We let B
denote the applied constant field, and we write the Larmor angular frequency and
magnetic interaction energy as

OJ,
^0 and VMn = -V-' Bo
2m.

The energy VM is altered, and the angle between and B is changed, if a second
\l

weaker field is imposed so that its direction varies to accommodate the precessional
motion of p,. Figure 8-14 illustrates the effect of a second field B^, which oscillates with
frequency u/2tt along the indicated y axis. The additional torque \i X Bw acts in the
left part of the figure to give an increase in the polar angle 6. If to is chosen to equal
to the direction of Bu reverses after half of a Larmor cycle and acts in the right part
,

of the figure to give another increase in 6. Hence, a resonance occurs at to = to as ,

periodic increases appear in the configurational energy VM . We note that the

precessing system absorbs these increments in energy from the applied oscillating field.

The quantum version of the magnetic-resonance problem treats the precessing

system as a collection of magnetic substates like the ones shown in Figure 8-6. The
magnetic splitting of these energy levels is given according to Equation (8-12) by an
expression of the form

(V M ) = g^B B m -

Figure 8-14

Influence of a transverse oscillating B field on the classical precession of a magnetic dipole.

Resonance occurs when the frequency of oscillation matches the Larmor frequency.
 8-6 Magnetic Resonance 399

Figure 8-15

Microwave absorption causing a transition

between adjacent magnetic substates.

Hui - gftWQ

&vbB„

(We refrain temporarily from specifying g and m so that we can discuss magnetic
resonance as a generic process.) Figure 8-15 shows two such levels for successive values
of the magnetic quantum number, with energy spacing

8E Mn g^B B

as found in Equation (8-13). An applied oscillating field Bw provides oscillating

electromagnetic energy and acts as a source of photons of energy hie. A photon is

absorbed by the precessing system when cc satisfies the resonance condition

eh
hu = 8EM = g—t-B =ghuo, (8-21

so that the result is the upward transition indicated in the figure. (Note that c" may
remain unchanged since the electric dipole selection rules do not apply in this
instance.) We know from our calculations in Section 8-3 that the magnetic splitting is

only of order 10~

4
eVina 10
4
G field. These numbers tell us that the oscillating field
must operate at gigahertz (microwave) frequencies if the atom is to exhibit magnetic
resonance in a constant magnetic field of tesla strength.

The resonance condition in Equation (8-21) can be used to make precise g-f actor
determinations from precise measurements of the resonance frequency. Of course, a
prior calibration of the field B is necessary in such an experiment. The resonance
technique can be employed in a situation where the transition occurs between the
spin-down and spin-up states of an atomic electron. In this case the relevant g-factor is

and the process is called electron spin resonance. The quantity g s is very
identified as g s ,

well known, and so a measurement of the frequency at resonance provides a

determination of the field strength at the site of the electron. This procedure has been
used in chemistry to probe the local magnetic fields inside molecules.
Figure 8-16 describes an ingenious device for making high-precision measurements
of magnetic moments and g-factors. The apparatus employs nonuniform magnetic
fields, of the kind used in the Stern-Gerlach experiment, to guide beams of neutral
atoms and molecules. The magnetic-resonance principle is implemented by two other
magnetic fields, one constant and one oscillating, located at the center of the
apparatus. A typical experiment is sketched in the figure in terms of the behavior of a
beam hydrogen atoms. We assume that the atoms emerge from the source in the
of
ground state so that we can attribute the atomic magnetic moment solely to the spin
The discrete vertical force on the magnetic dipoles splits the paths of
of the electron.
the atoms when they enter the first nonuniform field, in the manner of the original
Stern-Gerlach experiment. If we apply Equations (8-14), (8-20), and (8-15) in that
400 Spin and Magnetic Interactions

Figure 8-16

Schematic layout of a molecular-beam magnetic- resonance apparatus.

Bo

Signal

Vapor
chamber
T
A/, M 2
Resonance
Magnetic
Stern-Gerlach field resonance Stern-Gerlach field
fields

order, we obtain a force of the form

dBz 3B
gsVB m s
(8-22)
oz

for an atom in a definite m state. We let the field strength increase vertically as
i

indicated and find that an m = + \ atom experiences a downward force and

i

assumes a downward-curving trajectory, while an m = — \ atom follows an opposite s

course. The figure shows how the slit S, selects two such orbits, one curving down and
one curving up in A/,, the first Stern-Gerlach field. These paths cross and continue
into a second nonuniform field M 2
where the field gradient is reversed relative to v M
The split beams with m = + s \ and - \ are steered through 2
M
as shown and are

finally recombined at the slit S>

2
where the atoms are detected. Intervening between
M, and 2
M a magnetic-resonance element consisting of a vertical constant field B
is

and a horizontal oscillating field B w This part of the apparatus does not introduce
.

transitions and does not affect the paths of the atoms unless the frequency w is at
resonance. The magnetic-resonance effect flips the electrons from spin-down to
spin-up, so that atomic transitions from m = - \
i
to m = +
s \ occur where the
beams Those atoms that flip
cross. from - \ to +
\ are deflected up rather than
down in the field
2
and M
fail to take the proper path for detection at S 2 Hence, fewer .

atoms are collected at resonance, and a sharp dip in signal is observed in the detector.
A high-resolution measurement of the resonance frequency and an accurate calibra-
tion of the constant field BQ can then be used to give a precise determination of the
g-factor (gs in this case), with the aid of Equation (8-21).
The first studies of directed beams of neutral molecules were carried out in 1911 by
L. Dunoyer, and the earliest molecular-beam techniques were developed subsequently
by Stern. The magnetic-resonance method was built into atomic- and molecular-beam
experiments by I. I. Rabi in 1938. This innovation enabled Rabi and others to make
precise measurements of various kinds of magnetic moments, first for nuclei, later for
molecules, and finally for atoms. P. Kusch developed another resonance technique
and used it to measure the spin magnetic moment of the electron.

8-7 Spin-; Thought Experiments

We can illuminate the unfamiliar concept of spin by "conducting" hypothetical

experiments on the behavior of beams of particles. The experiments are aimed

specifically at the properties of spin- \ particles and are " performed" with the aid of
 8-7 Spin-' Thought Experiments 401

Figure 8-17

Splitting of a beam of spin-^ particles in a Stern-Gerlach field.

dz I

Beam of
•ground-state
H atoms

Stern-Gerlach fields. These studies are interesting because they illustrate some of the

basic language and notation of quantum mechanics, without the intrusion of differen-
tial equations.
We suppose that the beam particles are hydrogen atoms in the ground state. The

atoms have orbital angular moment ^=0 and exist in two quantum states labeled by
the quantum number m s . Let us first consider a beam directed along the horizontal
axis of a Stern-Gerlach magnet, where the field gradient points in the negative z
direction. We find from Equation (8-22) that atoms in the m = +
s \ state curve
upward and atoms in the m = —
s \ state curve downward, as indicated in Figure
8-17. Note that the orientation of the magnet defines the z axis for the specification of

the Sz eigenvalue hm s
.

We can guide the two split components of the beam back together by introducing
other Stern-Gerlach magnets in the manner of Figure 8-18. The three indicated field
sections are aligned in tandem with their z axes parallel to the same direction and are
assigned field gradients of equal magnitude and alternating sign. The central section is

twice as long as each end section so that the curvature of the trajectories causes the
two paths to rejoin at the left end of the apparatus. (We let the beam travel from right
to left to accommodate the quantum mechanical notation introduced below.)
It is clear that this system of fields has no net effect on the composition of the beam.
Atoms enter together on the right and follow discrete orbits up or down with random
probabilities. The same atoms rejoin and leave together on the left, as long as the
device contains nothing in between to affect one or the other of the two m i
pathways.
We can convert the instrument into a polarizing filter if we insert an absorbing
obstacle in one of the paths. Figure 8-18 indicates how such a barrier removes atoms
in the m = —
s
-, state and transmits a polarized beam in which every outgoing atom
has spin up with respect to the z axis defined by the direction of the fields. The figure
also shows a simplified version of the apparatus, with and without the barrier, for use
in the following thought experiments. We emphasize that the indicated signs of the
quantum number m i
refer throughout to a particular choice of z direction. We denote
this direction by the symbol Z in the figures as a reminder of this important point.
Let us now examine what happens when we send the beam of atoms through two
such devices in series. The polarizing filter of Figure 8-18 is used to prepare a
polarized beam for transmission into a second apparatus with the same coaxial
alignment. We assume that the fields are designed with equal strengths and equal
gradients. The fields are oriented in this part of the experiment so that the z axis
defined in the second device has the same direction as the z axis defined in the first.
402 Spin and Magnetic Interactions

Figure 8-18

Stern-Gerlach fields with alternating gradients.The nonuniform fields divide and rejoin a spin- 7
beam in the first apparatus. The second apparatus acts as a polarizing filter to transmit only
m = +
t
7 atoms. Schematic pictures of these transmitting and polarizing devices are shown at
the bottom of the figure.

Figure 8-19 shows the results of three simple thought experiments. The transmitting
apparatus in (a) presents no barrier to upward- or downward-curving trajectories and
simply transmits any polarized beam without modification. The filter at the second
stage in (b) allows only m = +
s ^ atoms to pass and has no effect on the given
polarized beam. The second filter in (c) terminates thebeam because the apparatus
passes only m = - s \ atoms. Note that the quantum number m retains its meaning
s

from the first filter to the second, since the z axis has the same direction in each
device.
It is instructive to associate quantum mechanical probabilities with experiments of
this kind. We begin by defining the complex-valued quantity

X(d,p)

as the quantum mechanical amplitude for an atom, prepared in the state p by the first
apparatus, to be detected in the state d by the second apparatus. We then express the
 8-7 Spin-' Thought Experiments 403

Figure 8-19

Stern-Gerlach apparatuses in series. The z axes have the same direction in each case, as
indicated by the common label Z.

(a)

(6)

(c)

corresponding probability of detection by the squared modulus

2
\x(d,p)\ -

(Note that the preparation and detection states read from right to left in these
expressions, while the atoms proceed from right to left in the accompanying figures.

The final <— initial notation for a quantum process follows a commonly adopted
convention. We have already used this notation in the transition amplitude of
Equation (5-70).)
The experiments in Figure 8-19 are described in terms of states specified by the sign
of m s , where the quantum number is defined according to a certain direction for the
axis of quantization. We are using the label Z to indicate this direction in the figure,
so let us represent the experiments in parts (b) and (c) with the aid of the same
notation. We introduce the amplitudes

X ( + Z, +Z) and x(~Z,+Z)

an atom with spin up and down along Z, given that the atom is
for the detection of
prepared with spin up along Z. These two particularly simple situations have rather
obvious probabilities:

X ( + Z, +Z)\ =
2 2
\
1 and \ X (-Z, +Z)| =

in case (b) and Another simple thought experiment can also be performed
in case (c).
with a beam of atoms prepared in the m s = — \ state. The resulting probabilities are

\ X (+Z,-Z)\
2
= and \ X (-Z, -Z)\
2
= 1

for the two alternatives at the detection stage of the experiment.

We now want to make the analysis more interesting by allowing a rotation of the
second filter. Let us confine our attention to rotations that maintain the coaxial
alignment of the two Stern-Gerlach magnet systems. The scheme is illustrated in
Figure 8-20 by means of two apparatuses designated as the polarizer and the analyzer.
We observe that the second set of Stern-Gerlach fields defines a new z' axis of
quantization, oriented at an angle /? with the z axis defined by the first set of fields.
Consequently, the spin quantum numbers denote different kinds of states in the two
404 Spin and Magnetic Interactions

Figure 8-20

Coaxial Stern-Gerlach devices. The quantization axis in the analyzer makes an angle /? with
the quantization axis in the polarizer.
_, 2

^ •

z
Analyzer Polarizer

devices, since the notation m = s

-V \ refers to spin up or down with respect to the z
axis in the polarizer and the z' axis in the analyzer. We use the label Z' in the
analyzer to distinguish its spin-up and spin-down states from those with the label Z in
the polarizer.
We are concerned with the detection probabilities for all the different polarization
states. The probability that an atom prepared with spin up along Z is detected with
spin either up down along Z' depends on
or the angle /? between the two axes. We
therefore expect new probabilities such that

2 2
\X(+Z\ +Z)\ # 1 and \x{~Z', +Z)\ *

when we deviate from the simple /? = situation. The two alternatives are shown
schematically in Figure 8-21. Again, note that the indicated signs specify values of m s

peculiar to the particular quantization axis. Only these two detection alternatives
exist, and so the sum of the two expressions must give unit probability:

|X( + Z',+Z)| 2 + X (-Z',+Z)| 2 = |

1. (8-23)

If we let the polarizer prepare a beam of atoms with spin down along Z and conduct
another thought experiment, we find another pair of probabilities whose sum must
obey a similar relation:

lx(+z\ + X (-Z',-Z)| 2 =
|
1. (8-24)

These equations are constraints on the four amplitudes parametrized by the angle /?.

It is reasonable to suppose that the amplitudes are periodic functions of /?. We already
know the probabilities for the special case fi
= 0, and we can also deduce the

Figure 8-21

Thought experiment with nonzero angle of rotation between analyzer and polarizer. Atoms
prepared with spin up along Z are detected with spin up and with spin down along Z'.
 8-8 Addition oi Orbital and Spin Angular Momenta 405

probabilities for the special case of a rotation with angle (i = it. It is possible to use
these logical arguments, and no other mathematics, to obtain the following general

results:

| X (+Z',+Z)|
2
= X (-Z',-Z)| 2 =
|
J (8-25)

and

\X(~Z', +Z)\ = X (+Z\ -Z)| =

2 2
\
.

sin
J-.
2
(8-26)

We leave the proof to Problem 10 at the end of the chapter.

These important formulas provide the answer to an interesting question. We
suppose that a given state refers to a definite value for the component of spin along a
given axis, and we ask for the probability of finding the particle with a certain
component of spin along another direction. It is enlightening to find that the question
can be formulated operationally and that the answer can be found in terms of a
conceivable experiment.

Example

Let us suppose that the directions Z

and Z' make a 180° angle and that the
polarizer prepares atoms with spin down along Z. Equations (8-25) and (8-26)
give the probabilities

| X (-Z',-Z)|
2
= cos
2
- =0 and | x( + Z\ -Z )|
2
= sin
2
- = 1

for finding the atoms with spin down and up along Z'. We might have
anticipated this result on logical grounds and put the argument to use in the
deduction of the general equations. If we take fi
= tt/2 as another case, we find
the probabilities

77

|X(+Z',+Z)| 2 = 2_ _ and — Z', +Z)| 2 = sin

2
—
|x(

Hence, we conclude that there is a 50-50 chance for an atom with spin up along
some direction Z to be found with spin up or down along another direction Z'
at right angles to Z.

8-8 Addition of Orbital and Spin Angular Momenta

The angular momentum of the one-electron atom includes both orbital motion and
electron spin. Each contribution has its own magnetic moment, and hence its own
interaction in an applied magnetic field. We have been able to concentrate on the spin
of the electron by selecting states in which the orbital angular momentum is equal to
zero. The quantized vectors L and S must be added together in situations where more
general kinds of states are considered.
 m

406 Spin and Magnetic Interactions

We define the total angular momentum of the atom by the addition of vectors

J = L + S. (8-27)

This sum of terms is analogous to the combined angular momentum of an orbiting

spinning body, except for the fact that in the classical case the vectors L and S may
have any magnitude and direction and may add up to any magnitude in the range
|
|L| - |S| |
to |L| + |S|.

Equation (8-27) is intended to hold for orbital and spin angular momenta with
quantized magnitudes and orientations. The resulting vector J is itself a quantum
mechanical angular momentum, and so the quantities J and Jz are supposed to
obey quantization quantum properties of L and S. Hence, there must
rules akin to the
exist a discrete nonnegative number j such that the quantized values of J~ occur as
eigenvalues of the form

2
h j(j+ 1).

The numerical variable j is called the angular momentum quantum number. Each
total

allowed value of j has an associated set of quantum numbers w and a corresponding ;

set of J. eigenvalues

hm )
with m = -j,-j + l,...,j-
/
1 , j.

These rules employ the quantum numbers j and m to express the quantized ]

magnitudes and orientations of the vector J, just as the quantum numbers £ and m f
determine the quantized behavior of the vector L.
The quantum number m takes on 2j + possible values in integer steps between
f
1

m = —j and m. = +j. It follows that j must be either an integer or a half-integer.

Equation (8-27) implies a relation among the various z-component quantum num-
bers:

tn
j
m,+ s
since J =
2
L z + Sz . (8-28)

Hence, we conclude that m )

must be half-integral, as m ( is integral and m s
is

half-integral, so that j itself must range over the positive half-integers \, |, |, . . . . The
allowed values of j vary with the orbital quantum number /. We note that L makes
no contribution to J in the special £ = case, and so we find

j = \ for any £= state. (8-29)

The determination of j for nonzero £ requires the addition of two quantized angular
momenta L and S to yield a third quantized angular momentum J. Only two possible
values of j result from this procedure:

j = £+ % or £- \ for any f* state. (8-30)

We look more closely at the addition of these vectors in the example below.
The vector-addition problem is described schematically in Figure 8-22. We choose
for illustration the £= 1 states of the vector L and combine these configurations with
the spin-up and spin-down states of the vector S. This combination of angular
 8-8 Addition of Orbital and Spin Angular Momenta 407

Figure 8-22

Vector addition of orbital and spin angular momenta. The factors of h are suppressed, and the
£= 1 case is chosen for L. The sum 1 + \ produces the
results § and \ for the vector J.

momenta can be represented (without the h factors) according to the addition formula

1 + \ = | or £

as stipulated in Equation (8-30). It is understood that the lengths of the vectors in the
figure are L/k, ]/3 /2 for S/h, and either /l5 /2 or
]/2 for /2 for J/h. In part (a) $
add = 1 and m s = 2 to § et m = i an<^ obtain j = A as the only possible
, ' ,

result. In part (b) we show that the combination of m ( = 1 with m, = and [he-
combination of m { = with m = ^ contribute together to m = \. Consequently,
s

both of these vector sums can be arranged to produce a j= configuration. In part '

(c) we find that the same orbital and spin states can also be combined in another
arrangement with m- = \ to form a j = % state. Note that the pictures incorporate
'

the feature of azimuthal uncertainty, as required for any angular momentum with
definite z component. This aspect of the vector-addition problem is rather difficult to
408 Spin and Magnetic Interactions

Figure 8-23

Vector model for the angular momentum sum

J = L + The drawings
S. symbolize the two
results j = ( + \ and j = t'— \.

IVA

<-i

visualize and represent in a figure. A more intuitive view of Equation (8-30) is

provided for convenience in Figure 8-23.

Let us now and reconsider the energy level diagram for the
return to Figure 8-13
one-electron atom. We organized by the quantum numbers
recall that the states are
(n^m^m s ) and that the wave function ^„^ m m is expressed according to Equation
(8-18). Our purpose is to introduce an alternative method of bookkeeping that employs
the total angular momentum quantum numbers j and m in place of m f and m s The , .

new scheme is based on the construction of wave functions of the form ty„f m where ,

states assigned to specific values of j and m are assembled as combinations of states

)

with definite assignments of m f and m Figure 8-22 suggests how such constructions
s
.

might be represented. The states {m ( = 1, m = — \) and (m^= 0, m = ^) s i

are shown together as a (j = \, m = L,) state in configuration (b) and are again
shown together as a (j = \,m-= \) state in configuration (c ).
'

A transformation of the wave functions takes the original set of quantum numbers
{n^m f m s ) into the alternative set (n^jm^. We observe that a given energy level En
has orbital quantum numbers

c°= 0,1,2,..., n - 1

as before, where each / value (except (= 0) allows two choices for j,

j=f+ \oxt- \,

and each of these j values permits 2j + 1 assignments of m. This transformation of

quantum numbers reorganizes the array of states in the manner described in Figure
8-24. We note that the number of degenerate states at energy E n
now given in terms
is

of the totalnumber of m values and is still equal to 2n 2 as

j
, expected. The figure also
introduces a new spectroscopic notation in which the states appear with the designa-
tion nL labeled by a subscript j and a new capital letter L. We use the capital letter
,
f

to denote the orbital quantum number according to the letter code

Sfor^=0, PfoiV=l, Dior ^=2, Ffor/=3,

 8-8 Addition oi Orbital and Spin Angular Momenta 409

Figure 8-24
En atom. Each assignment of
Energy levels and degenerate states
%y m for the one-electron

quantum numbers (ntfj) implies 1j + 1 possible values of m as indicated in parentheses at f

,

each level. The spectroscopic notation nL is used to designate the states. This scheme is an
j

alternative to the one described in Figure 8-13. The Coulomb force provides the only
interaction in each of the two figures.

(= 1 (=2 (=3
i ._ 3 5
;
=
2
'- 2 >= 2

EA 4Sy2 4 '%-
78T 4F ^
n = 4- 4Pi,
74T 4P % -4D3/ -4D5/
(2) (2) (4) (6) 76T
n=3- 3Sy2
1W 3D ^ Wb
(2) l2T 3P '/
2 (4)
3P3L
~W l2

-2P*
T2T 2P %-
- n=2-
l2T 2Sl /2 (4)

- n= 1' •lSi
(2)

This part of the designation is equivalent to the use of the symbols s, p,d, /, . . . for
single-electron states.
It should be emphasized that the energy levels in the figure are still those
determined by the effects of the Coulomb force alone. We have yet to be given a
physical reason for setting aside the quantum numbers {n£m f m ) s
of Figure 8-13 in
favor of the quantum numbers (nfjm ) of Figure 8-24. We may continue to use mf
and m as long
s
as L, and 5. maintain their status as separately conserved angular
momenta. The necessity for the alternative scheme based on j and m emerges in
Section 8-9.

Example

Let us examine the reasoning that leads to the possible va lues of J in Eq uation
(8-30). We consult Equations (8-28) and argue that 3 cannot exceed ^+ l
,

because

max m, =j, max m.f = /, and max m _ .

i
2
'
410 Spin and Magnetic Interactions

This conclusion is supported by the inequality

IJI * ILI + |S|.

The vectors must also satisfy another inequality

IJI > |L] - |S|,

which turns into the following constraint on the quantum numbers:

j(j+ l)>(v^+l) -v/3/2)''

01

jU+ i)-f(f+ 0-f > -pt(i+ 1).

We may test this constraint by inserting any value of j in the quantized range of
possibilities

s
7 '
2 » 2 ' 2 > 2 >
'
• *
'

The proof that j cannot be smaller than ( — 7 is left as Problem 13 at the end
of the chapter.

8-9 The Spin-Orbit Interaction

The energy levels of the one-electron atom deviate from the results shown in Figure
8-24 because of two additional dynamical effects. Both of these further contributions
to the energy of the atom are relativistic in origin and secondary in influence
compared Coulomb potential energy. One of the effects is associated with the
to the
spin of the electron and is known as the spin-orbit interaction. This source of
interaction energy introduces a fine structure among the degenerate states in the figure
and splits the levels into multiplets of states with slightly different energies. The
multiplet structure of the energy levels is observed in the emission spectrum of the
atom and is interpreted as direct evidence for electron spin.
A coupling occurs between the spin of the electron and the orbital angular
momentum, owing to the existence of a magnetic field internal to the atom. We employ
Figure 8-25 to deduce the nature of this interaction. The figure shows an electron in

orbit around a nucleus at rest and also shows the motion with respect to a reference
frame moving with the instantaneous velocity v of the electron. The nuclear charge Ze
has velocity —v in this frame, and the resulting current produces a magnetic field at
the instantaneous location of the electron. We can use the Biot-Savart law to write the
field in terms of the variables indicated in the figure:

Mo Ze{-\) X r
B — ;
3
.

477 r

Let us express the Coulomb field of the nucleus as

Ze r
E = 3
47re r
 8-9 The Spin - Orbit Interaction 41

Figure 8-25

Atomic orbital motion in two frames. The nucleus is at rest in the original frame, and the
electron is instantaneously at rest in the transformed frame.

and recall the relation

Mo e o 2
c

in order to rewrite the magnetic field in the form

v X E
B = =—

This expression describes a relativistic effect in which a motional magnetic field is

experienced by an electron moving at small velocity v through an electric field E. Let

us return to the original formula for the internal magnetic field and write

Ze r X v
B internal 2
i

477C,i C r
3
477£ m ec 2 r 3

We note that the final result contains the orbital angular momentum L = m r X r
v.

The electron spin magnetic moment interacts with the internal B field at the site of
the electron, with the same interaction energy as in the case of Larmor precession. We
make a provisional definition of this potential energy by setting

Km = ~~ V"S' B internal'

and we consult Equation (8-20) to obtain

Ze
l\si
(*"T' 4:TT£ m e
c
2
r
3

Equation (8-7) is recalled and the value g s = 2 is inserted in the following steps:

Ze
VSL =
m e
4WE »?/V

Ze 2 S • L
2 2 3
(8-31)
47T£ m e
c r
412 Spin and Magnetic Interactions

We emphasize that this derivation is based on a classical picture of Larmor precession,

taken in the instantaneous rest frame of the electron.

Our formula for the interaction energy must be transferred to the original frame
where the nucleus is at rest. An additional relativistic term is needed along with
Equation (8-31) to allow for the fact that the orbiting electron is in accelerated
motion. This extra kinematic ingredient is known as the Thomas precession term
(after L. H. Thomas, the first person to analyze the entire problem correctly). It is

possible to showLarmor precession and Thomas precession give similar contribu-

that
tions of opposite sign and that the overall effect is a modification of Equation (8-31)
l
by a factor of ,, the so-called Thomas factor. Hence, the spin-orbit interaction energy
assumes the final form

Ze 2 S • L
vsL=-7—rm-
477£ 2m e
c r
( 8 - 32 )

The Thomas precession term can be deduced as a technical exercise in relativistic

kinematics. Let us not pursue this point but remark instead that relativistic quantum
mechanics generates Equation (8-32) in straightforward fashion. The latter approach
is the more satisfactory one to follow in the first place, and so the final result is simply
quoted on that authority.
The spin-orbit interaction undermines the usefulness of the states ^nfm ,„ in
Equation (8-18) and Figure 8-13. We can use m f and m s as good quantum numbers to
determine the stationary states as long as we are able to specify eigenvalues indepen-
dently for the observables L, and S,. The circumstances require that L. and S. obey
separate angular momentum conservation laws. These two quantities are separately
conserved whenever there exist states of definite energy in which L. and S. also have
definite values. We illustrate this situation in Figure 8-26 by showing mutually
unrelated angular momentum vectors L and S whose orientations about the z axis are
completely random with respect to each other. The spin-orbit interaction changes this
picture because the factor S • L in Equation (8-32) implies a dependence of the
energy on the relative orientation of L and S. The two vectors are coupled together as a
result of this new dynamical variation of the energy. We can see the coupling in the
figure if we fix the energy by fixing the angle between L and S and attempt to
maintain the z components of the two vectors. Such states of definite energy generally

Figure 8-26

Independently oriented L and S vectors

representing a state with good quantum
numbers rn
f and m s
. In this case L refers to
the £-

Random orientations
 8-9 The Spin- Orbit Interaction 413

Figure 8-27

Coupling of spin and orbital angular momenta owing to the spin-orbit interaction. The effect

is represented as a precession of L and S about J. The indicated vector additions correspond to

the configurations displayed in parts (b) and (c) of Figure 8-22.

require combinations of L and S in which L, and S, cannot be assigned definite

values. A state of definite energy can have a definite value of J,, however. The
still

total angular momentum of the system is conserved as long as the system consists of
the isolated atom. We therefore turn to j and m as good quantum numbers and use
these parameters instead oi m f and m s
to designate the stationary states. The wave
functions *&„?.„ have been introduced and Figure 8-24 has been drawn in anticipation

of this relabeling maneuver.

We can by recalling parts (b) and (c) of Figure 8-22. The
illustrate the strategy

indicated configurations are composed of two distinct (m^m^ states with the same
value of m-, where the combinations of L and S are arranged to form states with
j = c* — j = i + l Let us picture the synthesis of the two states with the aid of
'
\ and ' , .

Figure 8-27. The influence of the spin-orbit interaction is indicated in the figure as a
precession of the coupled vectors L and S around
the vector J, while J assumes an
uncertain azimuthal orientation about the axis of quantization. Precession is used in
this instance as a schematic device to represent the behavior of the two (m^mj states
in the construction of the two possible values of j. We are about to learn that these
constructions of the quantized total angular momentum correspond to states of the
atom with different values of the energy. This mechanism causes the degenerate states
nfjn in Figure 8-24 to split apart so that atoms with the same n and c" acquire
slightly different energies for different choices of j. Let us also observe in passing that
the properties of L, and Sz in Figure 8-26 become interesting again in cases where the
spin-orbit coupling has a negligible effect. This situation prevails when the atom is in
an external magnetic field whose strength greatly exceeds that of the internal magnetic
field leading to Equation (8-31).
The spin-orbit interaction is one of two relativistic effects that contribute to the
fine structure of the atom. We recall from Section 3-6 that a useful dimensionless
parameter is furnished by the fine structure constant

a = '

Aire hc

and now we are able to appreciate the meaning of this parameter. We incorporate a
into Equation (8-32) to get

h S-L
VSL = Za 2
2m c
 4

414 Spin and Magnetic Interactions

and we use the relation

J =
2
(L + S) • (L + S) = L 2 + 2L • S + S2

to reexpress the spin-orbit interaction energy:

J -L -S
2 2 2
h
VSL = Za ir-r -3 .
(8-33)
\m 2c

When the expectation value of this quantity is evaluated in the state ^„^. m , the
expression takes the form

(VSL ) = Za-^yh 2 \j(j+ l)-/(/+l)-

The quantum numbers appear in this result as a consequence of the relabeling scheme
for the wave functions. Each wave function is denoted by the quantum numbers
2
(ntfjm^ so that the observables J , L2 , and S2 have the definite values
h j(j + 1), /iV(/+ 1), and \h in the given state. The expectation value (VSL ) is

interpreted in terms of Figure 8-24 as the amount by which the spin-orbit interaction
shifts the energy levels for the various assignments of these quantum numbers. Note
that the square-bracketed quantity in Equation (8-34) vanishes for {= states, where
j can only be equal to £ , and is double-valued for / ¥= states, where j can be either
/+ l or
, t- \.
The computation in Equation (8-34) is completed by inserting Equation (7-35)
from Section 7-4:

3
/ aW(/+ 1)(2/+ 1)

(We observe that the expectation value of any function of r in the state ^ n ^ ]m can
only depend on n and ( the quantum numbers for orbital motion.
, The calculation of
(1/r ') therefore reduces immediately to the integral

/;
-P Ar)dr n

as in Equation (7-31), where P„f(r) is the radial probability density for the given
state.) We also recall Equation (7-5) and again use the fine structure constant to get

2
477£ ^

Ze m. Zamc

(The reduced-mass correction m e /\i. is replaced by unity for this purpose.) The desired
expectation value is then written as

1 \ / Zam r
c

r
1) " \ hn j /(/4 1)(2/
 8-9 The Spin- Orbit Interaction 415

for /^ states. We insert this result in Equation (8-34) and obtain the final formula
for the energy level shift due to the spin orbit interaction:

Zam/
<ySL ) = za j(j +l)-/(7+l)- -
4m~c hn f(f+ 1)(2/+ 1)

zv j(j+ i)-/(/+ i)
(8-35)
3
2n ' /(/+ 1)('_V+ 1)

This version of the formula gives the energy shift in terms of m e c the rest energy of ,

the electron. We can refer back to Equation (3-54) and substitute the Rydberg energy
unit instead. We use the equality

m c

and find

=
ZV j(j+ 1) -/(/+ 1)-
Wsl) '•^o
(8-36)
e(t+ \){2t+ i)

This version of the formula gives the shift in terms of E , the natural scale of energy
2
in the atom. The spin-orbit energy is proportional to <x EQ and is therefore a rather
small correction to any given energy level.

These results can be applied to the states with nonzero ( in Figure 8-24. We see
that the values of the quantum numbers (n£j) are indicated at each of the energy
levels in the diagram, and we note that j is equal to either tf+ ^ or ( — \ for each
selection of n and /. Equation (8-36) determines an energy shift at every /=£ level.

Thus, a state with j '

= /+ \ has

Z A
a 2E
j(j+ l)-S(S+ 1)- 7 =£ and (VSL ) =
«V+
'

1)(2/+ 1)

while a state with j '

= (— \ has

Z*a 2E n
j(j +!)-/(/+ 1)- - = -€- 1 and (VSL )
nV(2/+ 1)

The spin-orbit splitting is found by taking the difference of these two expressions:

M.i^i.
'

z * a 2E ° l

8ESL I (8-37)
n\2t+ 1)\ t+ 1
" {)" «V(/+ 1)'

Hence, the coupling of L and S causes the state nL,+ l/2 to lie higher than the state
nhf_ x/2 and results in a doublet of states with the same n and ( as shown in Figure
8-28. The remaining contribution to the fine structure of these levels arises from
another relativistic effect, to be discussed in Section 8-10.
 .

416 Spin and Magnetic Interactions

Figure 8-28

Spin-orbit splitting of the state nL in the

)

one-electron atom.

nl

i'<-\

Example

Let us apply Equation (8-36) to the 2P states of the atom and compute the
magnitude of the splitting illustrated in Figure 8-28. The energy shifts for n = 2
and (— 1 are

=
ZV f -2-
— J
=
Z'a'% 3
= -
(VSI
sl/) E for j
\
8 ° 1-2-3 48 2

and

=
ZV -\-1~\ =
Z 4 a% 1

= -.
<Fe,>
\ w./
E° for j
8 1 •
2 3 24 2

We take Z= 1 in the case of the hydrogen atom, and we find the difference of
the two shifts to be

a 2E eV
8E S/ = a'E.A
/
—
1

48
+ —
1 \

= -

16
()
13.6
r
2
= 4.53 X 10~ 5 eV.
I 24 J 16(137)

The smallness of this splitting is due to the smallness of the factor a'. The
spin-orbit interaction has an even smaller influence on the states of the
one-electron atom for larger values of n and (

8-10 Results from Relativistic Quantum Mechanics

The Bohr energy levels reveal a doublet substructure when the analysis of the atom is

refined to include relativistic contributions. We have just found spin-orbit splitting to

be one such effect. We now want to identify the other contributor to the fine structure
of the levels so that we can combine the two corrections. Both of these features of the
atom are properties that emerge naturally from the relativistic quantum theory of the
atomic electron.
We can assess the relativistic nature of the spin-orbit interaction by establishing
the manner in which (VSL ) depends on the velocity ratio v/c. Let us recall that the
Bohr energy is

Z2 I.
—M
E =
.

^-E ignoring the factor

n \ m.
 8-10 Results from Relativistic Quantum Mechanics 417

and observe from Equation (8-36) that the ratio of (VSL ) to E n is of order Z a We
2 2
.

know (from Problem 14 in Chapter 3 and Problem 10 in Chapter 7, for example) that
v/c is proportional to Za for orbital motion in the atom. It follows that the spin-orbit
energy shift is a relativistic correction of order (v/c) relative to the Bohr energy. The
other fine structure effect is of the same order in v/c and should therefore appear to
the same order in powers of Za.
This second correction involves the relativistic treatment of the kinetic energy of the
electron. We recall that the Schrodinger equation for a particle of mass m is associated
with the classical energy relation

—P
2m
+ V= E,

in which the energy E excludes the rest energy mc and the kinetic energy varies with
p in nonrelativistic fashion. The relativistic formulas in Equations (1-35) and (1-37)
give the desired version of the kinetic energy as

p + m c — mc
2 2 2 A 1
\c .

The expansion of this expression in powers of (p/mc) 2 yields the following result:

1/2

—rr-j
2
p
1 1 p*
+ - -^
\
mc~\ 1 + I
- mc 1 = mc' 1 )
1
~ ~
o —r-7
4
+ l>
• •

m
<-

m~c 2 m c o c

1
P P"
2m 8mY 2

We recognize the leading term as the familiar nonrelativistic kinetic energy, and we
regard the next-to-leading term as the first relativistic correction. The leading contri-
bution turns into the usual differential operator — {h 2 /2m)\7 2
acting on the wave
function in the Schrodinger equation. We define the correction term for application to
the atomic electron by the formula

4
P
*rel=-7-TT- ( 8 " 38 )
8m c e

2
It is easy to verify that this correction is of order (v/c) relative to the leading
nonrelativistic term.
The extra kinetic energy # rel
is treated as another small interaction to be added to
the energy of the atom along with VSL . We compute these corrections by obtaining the
expectation value of K kX in the state

- lE ,/h
^ncjm =
, xb ,
T nejm e »

and by combining the result with the already-derived evaluation of (VSL ) in the same
state. The formula for (A' re ,
) is found in the derivation at the end of the section:

ZV 3
^m/ —
/ 1 \

(^rel) = 3 f \ c
•
(8-39)
rc 2/+ \ 1 8n
 \

418 Spin and Magnetic Interactions

This expression contains the same power of Za as occurs in Equation (8-35) for (VSL ).
We then determine the total fine structure shift in energy for any /¥= state by adding
the two corrections:

^ 4« 4 Jj(j+ !)-'('+ 0- f 2 3
<ySL ) + <* rel > = ^r^|- /(/+1)(2 , + 1)
-
^TT +
^
This combination of terms simplifies considerably to become

ZV / 2 3
<^> + <^> = -^r^ (^-TT-^)- 2
< 8 - 40 >

We leave the intervening algebra to Problem 1 7 at the end of the chapter.

The /= states require special handling. Let us accept the fact that the relativistic
happen to give the same final conclusion as in Equation
corrections to these states
(8-40). We
can then rewrite our results in terms of the Rydberg energy E and add the
Bohr energy E n to obtain the final formula for the energy in any state of the
one-electron atom:

ZV /
—— - —
2 3 \
Enj = En
J rE . (8-41)
n
\

\ +
2j 1 in J

The corresponding energy level diagram is shown in Figure 8-29. We magnify the
small effect of the fine structure so that we can see the emergence of a remarkable
pattern of degeneracies. We observe that the energies of the states nL, depend on the
values of n and j, but not on the value of /. The resulting degeneracies appear
,
throughout the figure in the pairs of states (26'
1/2 ,2/ 1/2
),(35'
1/2 ,3/ 1/2 ),
)
(3P 3/2 ,

3D 3 /2 )>> where each pair has a certain energy for the given n and j, without
regard for /.

The fine structure of the energy levels affects the wavelengths and splits the spectral
lines in the emission spectrum of the atom. The electric dipole selection rules
determine which initial and final states of the atom are linked in the various radiative
transitions. We have studied these rules in Section 7-5, prior to our introduction of
electron spin. The properties of the electric dipole vector are spatial and do not
pertain to spin, so that the spin quantum number plays no part in these selection rules.
We know that atomic states can participate in a given transition if a change in parity
and a change in the quantum number c" occur such that

A/= ±1. (8-42)

We also know that the emitted electric dipole photon carries away one h unit of
angular momentum. Therefore, the initial and final quantum numbers j and j' in the
process

(nSjmj) -» (n'l'j'm'i) + y

must obey the vector-addition formula

in order for the total angular momentum to be conserved. It follows that changes in j
 810 Results from Helativistic Quantum Mechanics 419

Figure 8-29

Energy levels En for the one-electron atom. Each choice of n and j gives a pair of degenerate
nL with two different values of /. The fine structure
states
t
effects shift the levels away from
their positions in Figure 8-24. The greatly exaggerated splittings indicate how the shifts
diminish with increasing values of the quantum numbers.
e= (= 1 e = l f = 2 6=2 ( = < = 3
= ._ 3 ._ 5 7
} 1 1-2

- n

- n
= 4

= 3
4Si/ 4J>i/
2

3Si/ 3Pi/
2

-
- -4P3/ 4Z)3
2

-3P 3/2 3Z)

/2

3/2
-

-
-Ws/AFs,

3D
W
51
AFi.

2 2

-2P3/,
n = 2

-2S 1/2 2i>1/2 .

'2
- n= 1- lSi/.

must satisfy the selection rule

A> = 0or±l (but -/» 0). (8-43)

The provision in parentheses notes that transitions from j = to ;' = violate

conservation of angular momentum and are not allowed. Our previous statement
about Am,, in Equation (7-41) converts directly into the new selection rule

bntj = Oor ±1. (8-44)

This conclusion holds because m- = m^+ rn

i
and because m s
is not affected in an
electric dipole process.
420 Spin and Magnetic Interactions

Figure 8-30

Lyman a transitions allowing for the fine

structure of the energy levels. The splitting is

greatly exaggerated, as in Figure 8-29.

-2P3
I

Figure 8-30 shows the Lyman a transition in hydrogen as an illustration of these

selection rules. It is clear that theLyman a process 2p — » Is actually consists of the

two atomic transitions

IP, '
15 i ::
and 2P 1/2 l.S
1/2)

resulting in two distinct wavelengths for the two different transition energies. The
difference is small enough to require high-resolution interferometry as a means of
distinguishing the spectral lines.

A consistent fine structure theory was developed by Pauli in 1927 as part of his

method for incorporating spin in the Schrodinger equation. This treatment of relativ-
istic corrections belonged to the framework of nonrelativistic quantum mechanics and
offered no theoretical explanation for the origin of electron spin. Another theory of the
was put forward with more spectacular consequence by P. A. M.
relativistic electron

Dirac quantum theory was constructed as a single-particle

in 1928. Dirac's relativistic

formalism based jointly on the principles of relativity and the principles of quantum
mechanics. His differential equation for the wave function employed the relativistic
relation between energy and momentum and assumed a form entirely different from
Schrodinger's wave equation. This new relativistic theory automatically allowed for the
spin of the electron and reduced to Pauli's theory in the nonrelativistic limit.
 810 Results from Relativislic Quantum Mechanics 421

Paul Dirac

Let us recount the successes of Dirac's theory and leave the elegant formulation to
a more advanced treatment of quantum mechanics. The theory starts with the free
electron and imposes the classical relativistic energy relation appropriate for a particle
of mass m:

2„4
c~p~ + m^c

Since the relativistic momentum p and energy E appear with the same exponent, the
corresponding differential operators d/dx, d/dy, d/dz, and d/dt occur to the same
order in the differential equation for the wave function ^(x, y, z, t). A first-order

time derivative is assumed so that the wave function evolves in time from a
specification of the state at / = 0, as in the Schrodinger theory. The Dirac equation is

therefore of first order in the spatial derivatives of ^ . It follows that the differential
equation for ^ can be properly constrained by the relativistic relation between p and
E only if ^ has a certain multivalued structure. The wave function has a two-valued-
ness corresponding to the spin-up and spin-down properties of a spin- -, particle, as

described by the Pauli quantum number m s The wave . function also has another
two-valuedness associated with the characteristics of particle and antiparticle . Thus, the
free-particle Dirac equation predicts the existence and describes the behavior of
spin- 7; particles and antiparticles (such as electron and positron) with spin up and
down.
An B can be introduced in Dirac's theory of the electron.
external magnetic field
The result an interaction with B via a spin magnetic moment whose g-factor is
is

exactly given by g s = 2. The Dirac equation can also be applied to an atomic electron

in the Coulomb field of a nucleus. When the interactions of the electron are examined
in powers of v/c, the relativistic corrections describe K rel as given in Equation (8-38)
and also VSL as written in Equation (8-32). The latter result automatically expresses
the spin orbit interaction in correct form, complete with the Thomas factor of l t
. The
Dirac equation can also be solved exactly to determine the energy eigenvalues for the
422 Spin and Magnetic Interactions

hydrogen atom. These solutions contain the effects of relativistic motion to all orders
in v/c and all orders in the fine structure constant a. The resulting exact energy levels
depend only on the quantum numbers n and j and reduce to the energies E n in
Equation (8-41) when the solution is expanded through terms of order ct 2E .

Dirac's theory was verified decisively in every relevant experiment. The prediction
of antiparticles was especially significant as a bold new innovation in theoretical
physics. The proposed existence of the positron was finally confirmed by the discovery
of the antiparticle in 1932. The theory p rovided the general basis for a complete
understanding of the relativistic quantum behavior of any spin-^ particle and was
hailed as one of the great accomplishments in 20th century physics.

Figure 8-31

Highly schematic plan of the Lamb-shift experiment. A beam of ground-state hydrogen atoms
is passed through an electron-bombardment region where the atoms can be raised to excited
states by electron collision. Atoms excited by the 15, ,
2
-* 25, ,., transition are left in a
metastable state where the electric dipole selection rules prevent radiative transitions back to the
ground state. The excited atoms proceed through the waveguide to a detector designed for the
collection of metastable atoms. A field is applied to the beam in the waveguide
radio-frequency
and induces transitions from 2S
2 l
, when the frequency corresponds to the difference in
to 2-P,/
energy between the two nondegenerate states. The radiative transition 2P1/2 lS 1/2 is allowed
so that excited atoms in the 2/>1/2 state radiate to the ground state before they reach the

detector. This depopulation of the metastable 25, /2 state is observed as a decrease in signal at
the detector for an rf frequency around 1060 MHz.

$
<&+[
-» Waveguide Detector
H atom source
r
$ "I
Electron bombarder

?S:
-2Pu
rf-induced
transition

Collisional excitation
e+ H - e+ H*

IS:
 810 Results from Relatimtic Quantum Mechanics 423

The multiplet structure of hydrogen has been presented in Equation (8-41) and
Figure 8-29. This system of levels was investigated experimentally with high-resolution
radio-frequency techniques by W. E. Lamb and co-workers during the late 1940s. In
studies like the one sketched it was found that the predicted
in Figure 8-31,
degeneracy of the (n 2, j = was =
actually broken and that the 2S ,2 state
r,) states X

had a slightly higher energy than its partner the 2P, /2 state. This measurement
became known as the Lamb shift. The observation was important because it indicated
the influence of phenomena that were not yet included in the relativistic quantum
theory. The departure of the spin g-factor from the value g s = 2 was another
slight

property of the electron that had no explanation in Dirac's theory. These discoveries
took place in the next period of exciting developments in quantum physics.

Detail

We derive the formula for the extra kinetic energy in Equation (8-39) by first

relating the relativistic correction K rel

to the nonrelativistic kinetic energy:

1 1

K„,=
- r.-l 2
o(e- vy
2m c 2m, 2m c

The expectation value of this quantity consists of three terms,

(* e.) r
((E 2 ) - 2(VE) + (V 2 )),
2m c

lE » t/h
to be evaluated in the stationary state ^ = ^ n fjm e . We are using a state
with energy eigenvalue E n , and so we find

2\ = ZT2
<^> = e:
and

(VE) = j**Vih — *dT = E j**V*dT = E (V). n n

The Coulomb potential energy appears in the second and third terms of (K rel ).
We employ Equations (7-33) and (7-34) to obtain the expectation values

Ze 2 I 1 Ze<
(V) =
4we \ r 4iTE an~

and

Ze' 2
(V 2 ) 2 i
47T£ f 477£ a n (2f+ l)

We then introduce a wherever possible, using the relation

= ahc ,

477£ r
424 Spin and Magnetic Interactions

and we ignore the reduced-mass factor \i/m f to rewrite the Bohr formulas:

Z" Z1 m e
c h
-EQ = —a" and a =
1
n n 2 Zamc

The expectation values of V and V 2 are thereby rewritten as

Zahc Zamc Z 2
a2

and

,,(
2
Zamc\ 2
2 Z 4a 4 m 2c'
(V 2 ) = (Zahc) l—r-) =2-
3/0/i
3 ,, 3
'

h J « (2/+ 1) « (2/+ 1)

All three contributions to the expectation value of KM can now be assembled:

7?
1
1
/
Z-74 a 4 m,c
2 4 /
I Zamc
7 2 2 2 \
\
/
/ Zamc- 3 2

<**> = -7T-2—
2m.r 4n
T-4
4
2
2n

+2 J
n (2/+ 1)

4
Z
— ^mc
a4
2
/

\
1 1

)n 2n 2tf+ 1

The formula quoted in Equation (8-39) follows immediately from this result.

Example

Let us investigate the small shifts in wavelength for the Lyman a transitions
shown in Figure 8-30. We set Z = 1 in Equation (8-41) and obtain the following
energy levels:

a2 / 1 3 \ a2
E(2P.
v i/2)
i/2 )
= E,2 EA - -
- = E2 - -E°Q
64
,

8 \ 2 8/ "

2
a2 5a
E(2P X/2 )=E2 - -E \\-
1

-j
3 \

=E 2
- —E ,

3 a2
E(lS l/2 ) = E, - a 2 E Q ^\
1
-
-j =£,-
\
-£ .

The two transition energies are

15a 2
£(2P 3/2 ) - £(lS 1/2 ) = £2 -E x
- a 2£
(
— --
-j = A£ 4-
64 °

and

11a 2
£(2P I/2 ) - E(lS 1/2 ) = E2 -E x
- a 2£
(
—-- j
= A£ 4-
64
F
°'
 811 The Zeeman Effect 425

where AE denotes the difference in Bohr energies:

AE = E2 - E = l
10.2 eV.

The corresponding wavelengths are

he he I
l5a L E t)

\(2P3/2 - lS l/2 ) = 1

A£(l + 15a'£ /64A£) AE 64 AE

and

2
In hi 1 la £
X(2/> - lS l/2 ) =
AE{\ + lla%/64AE) AE 64 A£

to order a2 in the respective correction terms. We recognize the leading factor

he/ AE to be the familiar Lyman a wavelength from the Bohr model:

he 1240 eV •
nm
= 122 nm.
Je 10.2 eV

The wavelength shifts are given by the residual quantities

2
15a'£ he 15/ 1 \ 13.6
(122 nm) = 2.02 X 10" 3 nm
64 A£ A£ 64 137 10.2

and

1 \a'E he 11 1 \-13.6
(122 nm) = 1.48 X 10
(
nm.
64 A£ AE 64 \ 137 / 10.2

We conclude that the two wavelengths must be measured with at least six-figure
accuracy to be resolved as separate lines.

8-1 1 The Zeeman Effect

The Stern-Gerlach phenomenon and the multiplet structure of the atom demonstrate
the influence of electron spin. Further evidence for spin is found when the spectral
lines of the atom are observed in an applied magnetic field. We have discussed these
observations of the Zeeman effect early in the chapter in Sections 8-1 and 8-3. We are
now prepared to learn why the prediction of triplet line splitting is not confirmed, and
why the so-called anomalous pattern is seen instead. Once the Zeeman splitting is

fully understood, there is no longer any reason an anomaly.

to regard the effect as
An external constant B field interacts with an atom through the magnetic-moment
interaction given in Equation (8-4):

Both orbital and spin magnetic moments contribute to \i, but only the former
426 Spin and Magnetic Interactions

contribution appears in our earlier treatment of the Zeeman effect. We obtain the
total magnetic moment of the one-electron atom by recalling Equations (8-19) and
(8-20) and inserting the g-factors g L = 1 and g s = 2:

|i = |ii + |i5= -^(L + 2S). (8-45)

n

We then determine the magnetic-interaction shift for a particular energy level of the
atom by calculating the expectation value

(vM )= -</*,>£

This formula employs the usual choice of z axis along the direction of B and calls for
the evaluation of (ju.) in a state that describes the atom without the application of the
field.

Let us first assume conditions in which the applied B field is much stronger than
the internal magnetic field responsible for spin-orbit coupling. This situation has
already been mentioned in our discussion of Figure 8-26. We neglect the spin-orbit
interaction and let the vectors L and S be decoupled so that the orbital and spin
magnetic moments perform independent Larmor precessions in the strong applied
field. The calculation of the magnetic interaction is then based on states of the atom

defined by m e and m as good quantum numbers. We use the wave function ^nfm m
v ,

with properties given by the expectation values

(L z ) = hrrif and (St ) = hm s ,

and take the z component of Equation (8-45) to find

(VM ) = + + 2S*> B = /V(»V + 2m

y< L * t ).
(8-46)

A given orbital configuration has quantum numbers n and £ and contains 2(2/ -t- 1)
different magnetic substates. These magnetic energy levels are shifted by the energy
(VM ) according to the values of m f and m s We emphasize that we cannot label the
.

states by these quantum numbers unless the spin-orbit interaction VSL is dominated
by the magnetic interaction VM . This strong-field phenomenon is called the
Paschen-Back effect, a special case of the Zeeman effect, named after the spectrosco-
pists Paschen and E. Back.

interesting case arises when both VSL and VM come into play, particularly
The more
where the latter is the weaker of the two interactions. Our solution of this
in situations

problem is based on a synthesis of techniques in which the quantum approach is

supplemented by the classical picture of precessional motion. We already know that
we can account for VSI by computing the expectation value in a state nZ,-, where j
and m are good quantum numbers. Our plan is to use the wave function ^„^ )m for
(VM ) as well.
The problem is difficult because a mismatch exists between the interaction and the
state. The interaction pertains to the total magnetic moment \i = —(n B /h)(L + 2S),

while the state refers to the total angular momentum J = L + S. Figure 8-32 shows
that this feature of the problem prevents the vectors |X and —J from pointing in the
 8-11 The Zeeman Effect 427

Figure 8-32

Vector diagram for the constructions

J = L + S and \i = \i
L + \i
s
. The g-f actors

g, and gs are not equal, and so the vectors \i

and J are not collinear.

same direction. The component of \i along J is given by

M7
=!-r- :

-tt(l + 2S)-(l + s)
J hj

= - —
Mb
(L 2
+ 2S 2 + 3S-L).

We relate S • L toy 2 L 2 and , , S2 as before and find

Mb
M/ L 2 + 2S 2 + -(J 2 - I - 2
S2)

My
= ~—(3JJ y
2
+ S2 -L 2 '

(8-47)
2hJ

We realize, however, that the desired quantity is not jx

/
but /n,, the component of [i

along the direction of B.

Figure 8-33 indicates how \i, and ju. are distinguished and how the one can be
found from the other. We introduce the three vectors fi ,, \i
± f and \i ±B according to
,

the figure and write

M, = \V-j + V-±j + \l
±b \cos6, (8-48)

where 6 is defined such that

J* =Jcos
428 Spin and Magnetic Interactions

Figure 8-33

Construction of fi. from ji,.

Precession around B

Our construction of ju. identifies \i

± j
and \i
± H as vectors perpendicular to J and B,
respectively. Our objective is to determine the expectation value of ju. by the following
argument based on the dynamics of precessional motion. The effect of spin-orbit

coupling is represented by a precession of L and S about J, as introduced in Figure

8-27, while the effect of the magnetic interaction is represented by another simulta-
neous precession of J about B. Figure 8-33 shows how \i
± /
rotates around the
direction of J while \i ± B rotates around the direction of B during these two
precessions. When we take the expectation value in the given state, we perform an

average over the two periodic motions and obtain vanishing results for both vectors |i ± ,

and |j.
± H.This argument implies that Equation (8-48) can be replaced by the simpler
expression

M.-

with the understanding that the expectation value must be taken

-» M/ cos 6 7
V if
(8-49)

the replacement is

to have the status of an equality.

Let us now combine Equations (8-47) and (8-49) and complete the determination
of (/*.). We proceed by calculating the expectation value of fi z J instead:

2
(m,7 > = (JJiij)

OAV 2
+ s2 -l 2
)).
2h
 811 The Zeeman Efleet 429

The two sides of this equality are to be evaluated for a level nL-, where eigenvalues
are specified for the observables J
2
, L 2 and S 2
, . We use these eigenvalue properties to
substitute

on the left side of the equation and

(JAV +
2
S
2
- L 2 )) = h
2
[3j(j + 1) + s(s + 1) - t(/+ l)](Ja )

on the right side. The resulting equality can then be rearranged to read

3j(j+l) + s(s+l)-S(t!+l)
<^>--2*
, x
ii B
JJTT) a >

= -EHb^t-, (
8 - 5 °)
n

where

j(j + i) + s(s+\)-n/+i) . .

2jU + U

This last coefficient in the final expression for (ju.) is called the Lande g-factor after A.
Lande, a pioneer in the period of the old quantum theory. We take note of the fact
that the spin g-factor has been explicitly written as g s = 2 from the beginning of the
calculation.
Equation (8-50) takes the place of Equation (8-10) in all applications of the
magnetic moment. The revised formula is more involved since the Lande g-factor is

not just a constant like g L or g s . We get g = 1 from Equation (8-51) and thus
reproduce the orbital g-factor g L if we arbitrarily , set s = and let J and L become
identical. Of course, we must take s = ~ and write

j(j+l)-t(t+l) + *

s= l + 8 " 52 )
2j(j + n
oY <
1)

in the case of the one-electron atom. This expression reproduces the spin g-factor
g s = 2 if the given state has quantum numbers /= and J
= L
,. Equation (8-50) can
be recast in vector form as

<H>=--/<J>^ (8-53)

since only the z component can have a nonvanishing expectation value in the state

^nfjmj- This result tells us that the observable magnetic dipole moment vector is

directly proportional to the total angular momentum, the only vector available to
characterize the state of the atom.
The Zeeman energy shift is deduced directly from Equation (8-50). We evaluate
the expression
430 Spin and Magnetic Interactions

in the state ^„^„, and use the fact that the wave function is an eigenfunction of J. to
write

a> = k-
The conclusion follows at once:

( vm) = g^B Bm r (8-54)

a result to be compared with Equation (8-12) for the fictitious normal Zeeman energy
shift. The actual situation pertains to a typical level nL
]
whose 2j + 1 magnetic
substates have the same energy E n) in the absence of an external magnetic field.
Equation (8-54) represents an energy shift due to the application of the field, causing
the magnetic substates to split apart and acquire different energies for each value of
the quantum number m . These Zeeman splittings differ from one nL to another
because of the variation of the Lande g-factor with £ and j. We therefore predict more
than three different transition energies for the various transitions allowed by the electric

dipole selection rules. The anomalous pattern of Zeeman spectral lines is observed as a
result, instead of the normal Lorentz triplet. The following illustration demonstrates
this effect.

Example

Let us look at the Lyman a transitions of Figure 8-30 in the presence of an

applied B field. The transitions of interest are

2P 3/2 15 1/2 and 2/ 1/2 >

\S
1/2 >

where each level nL- is split into its 2} + 1 magnetic sublevels. The Lande
g-factors and Zeeman energy shifts are given by Equations (8-52) and (8-54)
according to the values of m- as follows:

in the 2/^/2 state g = 1 +

and (VM ) = \li B B

in the 2P W2 state g = 1 4-

and ( vm) = iv-B B

in the l-S 1/2 state g = 1 + = 1 + 1=2

1/2
and (VM ) = 2n B B
-1/2

The resulting sets of split levels are shown in Figure 8-34. Note that the Zeeman
 812 Hypertine Structure 431

Figure 8-34

Zeeman splitting in the ground state and first excited states of hydrogen. An applied magnetic
field splits the levels for the various values of w ;
. The Lyman a fine structure transitions

IP.3/2 lS l/2 and IP I 2

15./., result in six and four distinct spectral lines.

™ 3

2P %: 2 1

2
3
2
1
2Si 2/»i
2

W V
_i
lSi 2 Mfi B W V W
I ZP 3/2
- IS i 2Py2 -lS 1

6 lines 4 lines

splitting for the 2S {

,
2
states is identical to that for the lS l/2 states. Electric
dipole transitions occur from 2P 3/2 an d 2/3 1/2 to ^i/2> provided the initial and
final m values obey the selection rule

krrij = or + 1

asshown in the figure. It is apparent that all the transition energies are different
and that the fine structure doublet of Figure 8-30 turns into six-plus-four distinct
Zeeman lines.

8-12 Hyperfine Structure

The proton is a spin-^ particle, like the electron, with its own magnetic moment due
to spin. In fact, every atomic nucleus with spin is likewise endowed with intrinsic
magnetization determined by the distribution of constituents in the nuclear system.
The implications for the one-electron atom are that the nuclear magnetic moment sets
up a permanent magnetic field inside the atom, and the electron magnetic moment
432 Spin and Magnetic Interactions

experiences a weak Zeeman interaction with the internal field. This additional
magnetic atom is known as the hyperfine interaction. Its
effect within the influence is

detectable in measurements of energy-level splittings that are orders of magnitude

smaller than the splittings due to spin-orbit coupling. We focus our discussion on the
f— states of the one-electron atom and finally concentrate on the ground state of
hydrogen. Our first objective is to describe the hyperfine interaction in terms of a
spin- spin coupling between the nucleus and the electron.
The nucleus has a nuclear spin I with quantum behavior like that of an angular
momentum vector. Every nucleus is assigned a nuclear spin quantum number from the
i

list of allowed integral or half-integral values

x 1
2

such that the magnitude of the nuclear spin is given by the eigenvalue property

I
2
= h
2
i(i+ 1). (8-55)

The assignment of the quantum number i depends on the particular quantum state of
the given nuclear species. A magnetic moment can be defined for any nucleus by
analogy with Equation (8-20), the formula for the magnetic moment due to electron
spin. First, we reverse the sign of the charge and alter the mass scale of the Bohr
magneton in the equation. These steps replace the factor — fi B by the nuclear magneton

eh m
M" =
^ =
JT/''
(8 " 56)

The magnetic moment and the nuclear spin are then related by the vector equality

V-l
= + gifl NT- ( 8 " 57 )

This equation introduces the nuclear g-faclor g t as an experimentally measurable

numerical quantity. We assume a point-like nucleus described solely by the parame-
ters Z, i, and g,, and we use the values Z= 1 and / = \ in the special case of the
proton. We also use the notation

— = 2.792847386
2

to express the measured value of the proton g-factor.

The hyperfine spin-spin interaction involves a coupling between the spin magnetic
moments of the electron and the nucleus. We sketch some of the details of this
interaction at the end of the section and obtain the following result for an atom in an
/= state:

12 2
1

-.
Vss= 7 zT^'M-zV (8-58)
4i7e c 5 r

The two spin vectors appear in the formula when Equations (8-20) and (8-57) are
inserted:

2
1 2 / e m r
1
= \
^—\ M S Iv
*
2oSsgi\
~~a4tt£ c* 3 \ 2m TT r
•

q f j p
 812 Hyper fine Structure 433

Note that Equations (8-7) and (8-56) are also employed to eliminate the magneton
factors in favor of fundamental constants.
The treatment of S • I in the expression for Vss parallels the technique applied to

S • L in the problem of spin-orbit coupling. A grand total atomic angular momentum

vector F is defined to include the nuclear spin I along with the usual contributions L
and S. This definition reduces to the two terms

F = S + I (8-59)

in the €= case. We then use the relation

F2 = S 2 + I 2 + 2S • I

to rewrite the formula for the hyperfine interaction:

2
? t ?, rn,
Vss --- 1 / e \
2
-S 2 -t 2 )V 2 --
1

4ire () c 2^nU-
lm 3 \ £ J
TT(F
M p
r
(8-60)

The hyperfine energy shift in any ^=0 state is determined by computing the
expectation value of this expression. The state in question has a grand total quantum
number / associated with the angular momentum behavior of the vector F, such that
quantized values of F2 are given in terms of / by the eigenvalue property

F2 = h
2
f(f+ 1). (8-61)

We also specify the state by the familiar principal quantum number n, orbital
quantum number £ = 0, and total angular momentum quantum number j '
= s = l
,.

The addition of spin vectors in Equation (8-59) takes the form

i +i

and yields two allowed values for the grand total quantum number:

f= + i £or z- \. (8-62)

These two / values refer to two different states of the atom with two different energies,
split by the small effect of the hyperfine interaction. This splitting is present in every

nS x/2 energy level and is of greatest interest in the \S 2 ground level of the hydrogen X
,

atom.
We calculate (Vss ) in an (= state with quantum numbers n and / by first

identifying definite values for the angular momentum factor in Equation (8-60):

F 2 -S 2 - I
2
= h
2
[F(f+ 1) - f
- i(i+ 1)]. (8-63)

The expectation value of Vss also requires an evaluation of the remaining factor
V '( 1 /r ). We examine this last detail at the end of the section and deduce a
prescription in terms of the radial portion of the wave function, evaluated at the
origin:

V -j = -\RJ0)\\
2
(8-64)

These two contributions are combined to produce the general formula for the ^=0
 M

434 Spin and Magnetic Interactions

hyperfine energy shift:

f gsSi
<Vss) = /(/+ i)- " -i'(*+ i; RJ0)\~. (8-65)
477e 3 \ 2m e
c j M p

Let us specialize to the n = 1 case and consider the hyperfine splitting of the ground
level. We consult Table 7-1 to find R 10(0), and we also express the Bohr radius in
terms of the fine structure constant a to obtain

Zam,
|* 10 (0)| = -j =4

Equation (8-65) can then be rewritten in powers of a:

SsSi Zamx
= ahc /(/+ 1)- - -i(i+ 1)
(V.ss)
2m,c J M
= Z a — in /(/+1) i(i+l) (8-66)
M
i

3 k

This final result is valid in the /= ground level of the one-electron atom for any
given nucleus.
The hyperfine energy shift depends on the value of the grand total quantum
number /. Two possibilities appear in the bracketed factor in Equation (8-66):

i for f= + i

/(/+ 1)- \ -i{i+ 1)

—
—i — \ for /= i

We see that the state with the larger energy is the one with the larger value of /. The
difference in energy between the two states determines the hyperfine splitting

8Ey «4 -^/(2i+
M 3
1). (8-67)

The combination of factors a* (m e / )m e c 2 should be compared with the analogous

p
2
combination a^m e
c in Equation (8-40) for the fine structure splitting. It is clear that
the electron-proton mass ratio suppresses spin-spin coupling in the atom relative to
spin-orbit coupling by some three orders of magnitude.
The lSl/2 ground level of hydrogen has /= 1 and /= states. We find the

splitting of these states by taking Z = 1, i = \, and g{ = gp in Equation (8-67):

2 m e
8E, (8-68)

Transitions between the lS 1/2 hyperfine levels of hydrogen have been observed in the
laboratory in the radio range of photon frequencies. The measured frequency is
 812 Hyper fine Structure 435

perhaps the most accurately determined quantity in physics:

v.'= = 1.420405751800 GHz,

corresponding to approximately 21 cm in wavelength. We can visualize the transition

as a spin-flip phenomenon, where the electron and proton have parallel spins in the
initial / = 1 state and antiparallel spins in the final / = state. This effect does not

change the orbital quantum number ( and does not have the behavior of a radiating
electric dipole. The probability for the transition is severely suppressed because of
these considerations.
The famous 21 cm line has played an important role in radio astronomy ever since
its is detectable in the radio spectrum of galactic
discovery in 1951. This radiation
hydrogen clouds, despite the extreme suppression of the transition probability. Detec-
tion is made possible by the appreciable abundance of hydrogen atoms in the galaxy
and by the inappreciable attenuation of radio waves by interstellar dust. Observations
of the intensity of these 21 cm emissions are employed to map the distributions of
hydrogen in the galaxy, and measurements of the Doppler-shifted wavelengths are
used to determine the radial motion of the emitting sources. Such techniques are in
current use in the investigation of galactic structures.

Detail

Let us outline the steps leading to the formula for the hyperfine spin-spin
interaction. We turn to Problems 2 and 3 at the end of the chapter and use the
relation ju. £ £
2
= 1 to find the magnetic field due to the nuclear magnetic
moment ji
7
:

1 '

B = -
4tte c
^v x U,xv-
/

r
\

I T 1 / 1

2
fX/V" V U,'V-
47re c

This internal B field interacts with the spin of the electron in an (= state
through the spin magnetic-moment interaction

vss = -V-s'K = -.

4ire c-
2 {v-s'V-F
2

r
(|i. s ' V) hi/* V- r
{ \

We reexpress the interaction in the form

1 2
Vss= ~.
j{ TV-s' V-F
-

^v-s'v-N - iv-s'^ I
v-r v-

and remark without proof that the expectation value of the terms in square
brackets vanishes in any ( = state. The remaining portion of V
ss is quoted in
the text as Equation (8-58).
436 Spin and Magnetic Interactions

Detail

The calculation of (Vss ) calls for the expectation value of V 2

(l/r) in a state
whose (* = spatial eigenfunction is given as

,
= *.o(0
^ nr-

We differentiate \/r away from the point r = and find

V '- =
1
— —d1

r
1
d 1
= 0.
r r~ dr dr r

We also note that the expectation value of V2 ( 1 /r ) picks up a nonzero

contribution in an infinitesimal spherical neighborhood of the origin:

/ \ c 1 1 t [ \ d d \\
V - = Jl**V -VdT=
2 2
/ xP*\——r' U4wr"-'<fr
\ r / r •'r-o \ r~ dr dr r
j

.,
r
Id d \\

2
-I^0)|'(,^i) = -|*.o(0)| .

r =

This result appears in the text as Equation (8-64).

Example

The following numerical exercises illustrate the orders of magnitude involved in

the analysis of hyperfine structure. First, we note that the nuclear magneton is

three orders smaller than the Bohr magneton:

rri 5.788 X 10" 9 eV/G

12
/^=TT/^=- -r^r- - =3.152 X 10- eV/G.
M p
1836

We can compare the hyperfine splitting in hydrogen to the Bohr energy by

inserting the relation E = {<x
2
/2)m f
c
l
in Equation (8-68):

Kf = 3
« 2g S gpJfEo-

We find the transition frequency to be

19
4 (2)(2)(2.79) 13.6 eV 1.60 X lO" J/eV 9
Vu, = J4
= 1.42 X 10 Hz,
J
3 (i37) 1836 6.63 X 10 J •
s
 Problems 437

and so we obtain

8
3 X 10 m/s
K= 1.42 X 10
9
Hz
= 0.211 m

for the wavelength of the 21 cm spectral line.

Problems

1. Obtain the formula for the magnetic field due to a circular current loop and for the

electric field due to a pair of opposite charges, in each case at a location on the axis a
distance z from the origin. Show that for large z the two results are of identical dipole

form.

1
i

2. The general formula for the magnetic field due to a magnetic dipole moment \i is

Mo I

-V
477
X /

\
p. x v- r

Let \i = fiz and show that at the axial point (0,0, z) this expression reproduces the large--

result obtained in Problem 1

3. Prove the vector-calculus identity

V X (C X v/) =c(v •
V/) - V(C- V/),

where C is a constant vector and / is a scalar function. Apply this identity to the
magnetic dipole formula in Problem 2, and reduce the form of the result.

4. A uniform solid cylinder of mass M and total charge Q rotates about its axis. Determine
the g-factors relating the magnetic moment and the angular momentum, assuming that
the charge is uniformly distributed in two ways: (a) over the cylindrical surface and (b)
through the cylindrical volume.
5. A rectangular current loop is oriented with respect to a uniform applied B field so that the

magnetic moment p, makes an angle 6 with B. Show that the loop experiences a torque
given by \i X B, and use this result to determine the work required in order to increase the
angle between \i and B by an amount dO.
6. The Paschen a line in the hydrogen spectrum is due to the transition n = 4 —* n = 3.

Sketch the normal Zeeman splitting for the 4p and 3d energy levels of the hydrogen
atom, and compute the magnitude of the splitting in a 2 T applied magnetic field.
438 Spin and Magnetic Interactions

Identify the allowed Ap —* 3d transitions and determine the shift of the Paschen a
wavelength for each case.

7. Consider a classical model of a spinning electron in terms of a uniformly dense rotating

sphere of mass m r
and radius re . Estimate r
t
by identifying the rest energy with the
electrostatic energy e~ /A"ne {) rr . Obtain an expression for the classical angular momentum
and equate this quantity to h/2. Use the result to solve for the speed v of an equatorial
point on the surface of the rotating sphere, and show that v Is considerably larger than the
speed of light.

8. In a Stern-Gerlach experiment, a hydrogen beam from a 500 K oven traverses a 20 T/m

field gradient along a half-meter of beam length. Calculate the separation between the

deflected beams upon emergence from the magnetic field. Why is it valid to assume that
the hydrogen atoms are in the ground state?

9. A magnetic- resonance experiment is conducted using a beam of hydrogen atoms in the

ground state. A constant field B splits the magnetic energy levels of the atoms, and an
oscillating field Bu is tuned to the frequency corresponding to transitions between these
levels. Calculate the value of the resonance frequency for a field B = 2000 G.

10. A beam of hydrogen atoms in the ground state passes through two coaxial Stern-Gerlach
filters in series. The analyzing filter makes an angle B with the polarizing filter, as shown
in Figure 8-20. Let the polarizer transmit atoms in the spin-up state with respect to the z
axis defined by this first filter. Deduce the probability that any such atom is then detected
in the spin-up state with respect to the z' axis defined by the analyzer.
11. An electron is known to have spin down along a certain direction Z. Calculate the
probability of finding the electron to have spin up along another direction Z' at a 60°
angle with Z. What is the probability of finding spin down along Z'? Repeat the

calculations for the case of a 30° angle between Z' and Z.

12. Consider two of the /= 2 states of the one-electron atom in which the L. and &, quantum
numbers are given as (m^= 2, m = — s £) an<^ ("V= 1, "*, =
|). What two values of j

are possible for these tn-= \ states? Draw sketches to show how L and S may be added in
the two given states in order to produce the allowed values of j.

13. The vector-addition formula J = L + S implies that the inequalities

IJI > |L| - |S|

must hold for £= 1,2,3,... . Prove (using a suitable graph) that, out of the range of
possibilities

only the £ + \ and (— \ cases satisfy the inequality for every integer (> 0.

14. Choose a 3D state of the one-electron atom and carry out the explicit integration required

to obtain the expectation value of l/r

!
. Compare the answer with the general formula

<l/r 3 ) = 2/a 3 nV(Y+ l)(2<f+ 1).

15. The n = 3 level of the one-electron atom comprises the states 35, /2 3/5 1/2 , , 3P 3/2 3D 3/2
, ,

and 3Z)r)/2 . These states are degenerate if relativistic effects are ignored. Evaluate the
spin-orbit energy shifts for the 3P and 3D states, and calculate the spin-orbit splittings

of the 3P and 3D levels in hydrogen.

16. How many AF states of hydrogen have the same Bohr energy £4 in the absence of fine
structure effects? Evaluate the spin-orbit energy shifts for the two possible values of j at
the AF level. Identify the degeneracy that remains among the 4F states after this splitting

is taken into account.

 Problems 439

17. Prove that the energy shifts owing to the spin-orbit interaction and the relativistic

correction to the electron kinetic energy combine to give

ZV / 2 3
\ SL/ rel/ i
\
2n
'
^ 2> + 1 An

The formulas in the text are derived for £+ states; however, the final result is valid for

any nL state.

18. Identify all the electric dipole transitions that contribute to the Balmer a line in the

hydrogen spectrum. Determine the fine structure shifts for each of the n = 2 and n = 3

states, and calculate all the different Balmer a transition energies.

19. Use the value of the Lamb-shift frequency, quoted in Figure 8-31, to compute the
difference in energy between the 25,,,, and 2P, ,
2
levels in hydrogen. Compare this result

with the fine structure splitting between the 2P {

,
2
ar>d 2i>3 /
2
states.

20. The 3D level of the one-electron atom comprises ten states whose energies are equal if

relativistic effects are ignored and if no magnetic field is applied. Let an external B field

be introduced, and consider the case in which the strength of B greatly exceeds the
internal magnetic field responsible for spin-orbit coupling. Determine the energy shift for

each magnetic substate at the 3D level, and draw an energy level diagram in which the
split levels are labeled by the quantum numbers of the states. Is the tenfold degeneracy of

these 3D states completely broken by this effect?

21. Reconsider the atom of Problem 20 for the situation in which the applied B field is weaker
than the internal magnetic field. Determine the energy shift of the 3D states resulting

from the magnetic interaction. Draw an energy level diagram indicating the quantum
numbers of the states and the magnitude of the splittings. Is the tenfold degeneracy at the

3D level completely removed in this case?

22. Let the atom of Problem 20 have the fictitious g-factor gs = 1 (instead of g s = 2) for the

spin magnetic moment, and consider the effect of a weak applied B field. Derive an
expression for the Zeeman energy shifts at the 3D level in terms of the quantum numbers
of the 3D states. Draw an energy level diagram labeled by these quantum numbers. Is the
tenfold degeneracy at the 3D level completely removed under these circumstances?

23. Calculate the fine structure splitting at the AF energy level of the hydrogen atom.
Determine the magnetic splitting of the 4F states when a weak B field is applied to the
atom, and calculate the value of the magnetic energy shifts in a 5 G field. Draw a
diagram of the final 4F array of energy levels, identifying the quantum numbers of each
state.
 NINE
COMPLEX
ATOMS

/he evolution of quantum physics has been

guided from the beginning by discoveries in atomic spectroscopy. These observations

of atomic structure furnish the background for the Bohr theory of the atom, the
concept of electron spin, and the Schrddinger theory of quantum mechanics. The
primitive atom with one electron has provided our first opportunity to test the
predictions of the quantum theory. The complex atom with many electrons is our next
system to analyze for further evidence of quantum structure. We find that the analysis
is complicated by the large number of degrees of freedom and that an exact solution is

out of the question for any atom with more than one electron. must approximateWe
the many-particle dynamical problem, and so we obtain a less-quantitative body of
predictions as a result. Our main goal is to understand the complex atom in terms of a
set of quantized energy states with a suitable assignment of quantum numbers. The

spectroscopic consequences are examined for guidance throughout the investigation.

We encounter a new principle when we consider the atom with several electrons as
a system of identical quantum particles. The principle identifies a notion of identical-
particle symmetry and associates a corresponding quantum property with the half-
integral spin of the electron. These ideas constitute the decisive contribution of Pauli
to the theory of atoms. We devote a large portion of the chapter to the remarkable
implications of this principle.
The complex atoms are organized by the periodic table of the elements. Only a
minimum of new quantum physics is needed for an understanding of this organiza-
tional scheme. We construct these arguments in the first few sections of the chapter.

We then turn to a more detailed picture of the complex atom based on further
considerations of quantum mechanics.

9-1 The Central-Field Model

We concentrate on the neutral atom and use the atomic number Z to locate the species
in the periodic table. The corresponding system consists of Z electrons bound to a
nucleus of charge Ze, assumed to be at rest. We must approximate a certain essential

440
 9- 1 The Central-Field Model 441

Wolfgang Pauli

aspect of this problem, and so we regard any allowance for nuclear motion as an
unwarranted correction.
It is instructive to return to the hydrogen atom for purposes of reference. The
Coulomb potential energy and the stationary-state wave functions are given by the
well-known expressions

Ej/h
V= and ^ / = ib / (r)e
lE "

Attest

We recall that the angle independence of V makes possible the separation of radial
and angular variables in the eigenfunction nfm m (r). The results for the energy
i^

eigenvalue En are found in Figure 7-2 and are transferred to Figure 9-1. Note that the
scale of energy is shifted in the new figure so that the excited levels are displayed
relative to the position of the ground state. The figure shows the familiar n /-orbital
labels for the single-electron configurations as well as the spectroscopic notation for
the states.A left superscript is added to these designations to indicate the doublet
property of the states nL- with j values equal to either t° + L or c* — ~ (The states of
, . .r

the one-electron system are labeled as ~S doublets, even though j = \ is the only '

possible choice. This usage anticipates a development yet to come.) The figure also
shows transitions allowed by the electric dipole selection rule t\( = ±1 and includes a
scale of energy in inverse nanometers along with the usual electron volts. We relate
these units with the aid of the Rydberg definition in Equation (3-59),

R,
he
442 Complex Atoms

Figure 9-1

Grotrian diagram for the hydrogen atom. The fine structure of the doublet levels is too small to
be seen on this scale. Electric dipole transitions are labeled by the emitted wavelengths in
nanometers.
.
R +e
2
S 2p 2
D 2
F

and note that 13.61 eV is equivalent to 0.01097 nm" 1

. Figures containing this sort of
information for the various atoms are called Grotrian diagrams, after the German
astronomer W. R. W. Grotrian.
The exact Schrodinger treatment of the atom becomes much more complicated
when there are two or more electrons to consider. We can appreciate the problem if
we examine the helium atom and allow for all the interactions, as indicated in Figure
9-2. The Coulomb potential energy for the Z = 2 system contains two terms corre-
sponding to electron-nucleus attraction and a third term describing electron-electron
repulsion:

2e< 2e<
K= -
—
(9-1
477£ r, 4:ire Q r2 477£ |r, r2 |
 9- I The Central-Field Model 443

Figure 9-2

Coulomb interactions in the helium atom. The

attractive force between electron and nucleus
is central, while the repulsive force between
electrons is noncentral.

The two-electron eigenfunction i//(r 1} r 2 ) for energy E obeys the time-independent

equation
*2
-— (V, 2
+ V 2 )^+
2
V+ = E$, (9-2)

in which the differential operators V{ and V 2 " refer to the two sets of coordinate
variables (r,, #,, <£,) and (r2 , #,, <£>.-,). We observe that the electron-nucleus contribu-
tions to V have the familiar central form and do not complicate the solution for »//.

Unfortunately, the electron-electron piece of the potential energy is noncentral, and so

the method of separation of variables is not applicable to an exact solution. In fact, it

is clear at the outset that the third term in Equation (9-1) prevents the separation of
the one coordinate from the other.
We are faced with a worsening situation when we consider atoms with larger values
of Z. The general Z-electron problem involves an eigenfunction ^(r,, . .
.
, rz ) depend-
ing on Z independent coordinate vectors. The eigenfunction for energy E satisfies the

differential equation

+ Vj)^+ Vxp = E+, (9-3)

Im,

where the Coulomb potential energy contains central-attractive and noncentral-repul-

sive terms for all the electrons:

2
Ze
V=
I 1

+ —1

47re r
\ >

2
e
+ + -
477E IM r > l
z-i
\

Ze
2 z 1
z

477e
I
4™ .<.._, |r, - r ;l
(9-4)
,= 1

The complicating noncentral part of V consists of Z( Z— 1 )/2 distinct contributions

from all pairwise combinations of independent coordinate vectors. It is obvious that
 .

444 Complex Atoms

we must adopt a simplifying model of the atom if we are to make any progress toward
a solution of this problem.
Let us suppose for the moment that electron-electron repulsion can be regarded as
a secondary correction so that the eigenfunction ip and the eigenvalue E can be
obtained in first approximation from electron -nucleus attraction alone. This proce-
dure decouples the electrons from one another and treats each electron independently,
with its own central Coulomb potential energy for every independent coordinate
vector r,. The approach allows the application of separation of variables and produces

a solution in which the eigenfunctions for the one-electron atom are used to describe
each of the Z Of course, the approach is valid only if the noncentral
electrons.
Coulomb enough to be ignored. It is clear that the attractive potential
forces are small
energy between the nucleus and the electrons is the main effect since the binding of
the electrons is the net result. Equation (9-4) represents a competitive situation where
a given electron makes a central-attractive contribution with an enhancing factor of Z
and also makes Z — 1 noncentral-repulsive contributions to offset the binding effect.
The repulsive terms add up to an appreciable correction whose order of magnitude is
not much smaller than that of the overall nuclear attraction.
It is possible to improve the approximation and still retain the independent-particle
approach. We observe that each atomic electron is shielded from the nucleus by the
other Z— 1 electrons, and we argue that every independent electron experiences a
screened nuclear attraction attributed to an effective nuclear charge smaller than Ze. This
screening of the nucleus is expected to vary with the radial distance to the given
electron and is be representable on the average by a spherically
supposed to

symmetric potential energy function. Thus, our improved first approximation to the
eigenfunction for the atom is based on an independent-electron model in which every
electron interacts with a central field and has a potential energy V (r) with
c
the limiting
behavior
2
Ze
as r —»
4wc r

K(r)
as r -> oo
I

477£ n r

We introduce an effective screened nuclear charge as a function of r by writing

K(r)= --^—ZeH (r), (9-5)

and we observe that Z eff

approaches Z near the nucleus and tends to unity at large
distance.
A coordinate vector r ;
is defined with spherical coordinates (r„ #,,<#>,) for each
independent electron. The dynamics of the electron is governed by the central
potential energy V (r ), and so an independent state of the particle is determined by
c :

solving the differential equation

2
h
-T- V.V.-r VXrM, = E,^, (9-6)
2m f

to obtain an eigenfunction ^,(r, ) with energy £,. We let the index i run over all Z
 9-1 The Central-Field Model 445

electrons and express the total potential energy of the system by the sum of terms

V=tv c
{ri ). (9-7)

We can then prove that Equation (9-3) is satisfied by an atomic eigenfunction of

product form,

^(r,,...,rz )
= ^ 1
(r,)--- * z (rz ), (9-8)

whose total energy eigenvalue is given by the sum of electron energies

i=i

The product construction for the eigenfunction of the atom in Equation (9-8) is the
basic feature of the independent-particle model.
The Vc is central, and so the single-particle eigenfunction ^,( r ) is
potential energy ,

separable in and angular variables. The solution of Equation (9-6) can

its radial
therefore be patterned after the wave function found in Equation (8-18). We intro-
duce a single Greek index a as a convenient shorthand to denote the complete set of
single-particle quantum numbers {nc"m^m ) and represent the desired eigenfunctions
s

for each particle by expressions of the form

iUr) = /UOF,„v (0,4>)(? or |). (9-9)

Tnis solution of Equation (9-6) for a single electron is called a spin orbital. The
eigenfunction for the entire atom is then constructed as a product of Z such factors in
themanner of Equation (9-8). The familiar spherical harmonics appear in \p a with
indices { and m r bearing the usual angular momentum interpretation. The assign-
ment of a unique angular momentum to each individual electron is a consequence of
the central-field property of the independent-electron model. Equation (9-7) conveys
this dynamical property by excluding any explicit coupling between the electrons. The
radial function R n/P (r) obeys a differential equation like the one for the hydrogen
atom, except that the purely Coulombic potential energy is replaced by the central-field
function V (r):
c

2
h ac*+ 1)
VR nS + K(r)+ ,
R nf =E nf R nf . (9-10)
2m r dr" Im.r

Thus, the eigenfunctions of the independent-electron model exhibit the familiar

correspondence between radial functions R n( (r) and energy eigenvalues Enf These .

quantities cannot depend on the quantum number m( according to the usual

spherical-symmetry arguments, and cannot depend on the spin quantum number m s

either since spin effects are not included in the potential energy of the atom. This
procedure is expected to result in single-electron functions and energies different from

the analogous solutions for the hydrogen atom because of the non-Coulombic nature
of Vc .

We are concerned with a determination of the eigenfunction \p based on a model

for the single-electron potential energy Vc(
r ). A successful approach to the solution of
446 Complex Moms

this problem exists in the form of a method, originally proposed by D. R. Hartree and
eventually improved by V. Fock and J. C. Slater. Their solution treats the average
behavior of each atomic electron and also incorporates the identical-particle symmetry
of the multielectron system. The whole procedure is supposed to be self-consistent,

since the central potential energy V (r)

c
for any given electron depends on the
eigenfunctions determined from V c(
r ) for every other electron. Many useful predictions
can be made by this approach to the structure of complex- atoms.

Example

The ground state of the helium atom has energy — 79.0 eV (on an energy level
diagram where the zero level refers to a He + + ion plus two electrons, all at rest
with infinite separation). Let us make a primitive attempt to understand this
number. The crudest approximation to the He eigenfunction is found from
Equation (9-2) by retaining only the first two terms from the potential energy in
Equation (9-1). The resulting ground state is described by the product of two
hydrogen-like n = 1 eigenfunctions,

- (r, + r2 )/<z
g
rp(r ,r 2 t )
= i//
1(l0
(r, )<//„,„( r,) = ,

ita

in which the spins of the two electrons are left unspecified and the radius
parameter is given by a = a /2 for Z= 2. The ground-state energy in first

approximation is the sum of the Bohr energies of the electrons:

E = 2E = -2Z 2E = X
-8(13.6 eV) = - 108.8 eV.

We should not expect this result to be close to the correct answer since we have
ignored the repulsion of the two electrons. Let us estimate the repulsive
contribution by making a gross classical calculation. If we replace the electron
separation |r, — r2 |
in the neglected term of Equation (9-1) by the constant
value 2a = a , we find

477e a
e
2

= ahc —- =
am.c
a2m c
2
= 2E n = 27.2 eV.

The sum of the two numbers — 108.8 and 27.2 yields —81.6 eV as an estimate
for the ground-state energy. This computation is inadequate for a quantum
system and serves only to suggest the relative sizes of the two competing effects.

9-2 The Exclusion Principle

Electron spin has proved to be essential for the understanding of multiplet structure
and Zeeman splitting in the one-electron atom. Complex atoms also reveal the
influence of the spin quantum number, particularly in the periodic table of the
elements. This revelation of a special role for electron spin in many-electron atoms is

an indication of a new kind of symmetry in systems of identical particles. The

 9-2 The Exclusion Principle 447

deduction of the spin degree of freedom originates in these observations, and the
exclusion principle provides the underlying deductive framework.
The exclusion principle is a statement, due to Pauli, about the assignment of
electron quantum numbers in the complex atom:

No more than one electron is allowed to occupy a given quantum state specified
by the complete set of single-particle quantum numbers (n^m f m s ).

This prohibitive rule acts as a constraint to exclude the existence of certain states in

the many-electron system. The constraint is an additional quantum condition imposed

on solutions of the Schrodinger equation for the many-particle problem, in the special
circumstance where the particles are identical. When the principle is applied to the
construction of the ground states of atoms, the result is the organization of the periodic
table.
Regularities among the elements are presented in the periodic table according to
values of the atomic number Z. The periodicity of such characteristics as chemical
valence and binding energy is evidence for a periodicity in the structure of the atoms.
The cycling of properties with increasing Z is explained by distributing the electrons
in a succession of "energy shells" and requiring a given shell to be fully occupied for a
certain number of electrons. These closed shells occur in the ground states of the
noble-gas atoms helium, neon,... at Z= 2, 10, ... . The occupation of succeeding
shells then continues with the ground states of the alkali atoms lithium, sodium, ... at

Z= 3,11,... .

The theory of atomic shell structure is supported by observations of the optical

spectra of the elements. These spectral lines in the visible range of wavelengths are
generally associated with the excitations of loosely bound electrons in the outer shells.
The alkali elements are especially interesting because their optical spectra contain
doublets of lines like those found in the spectrum of hydrogen. This behavior is

explained by attributing the radiative transitions to a single optical electron, whose

initial and final energy shells lie outside an inert core of closed shells.
Optical spectra are not the only sources of information about the shell structure of
atoms. The excitations of tightly bound electrons in the inner shells are also detectable
as higher-energy x-ray transitions. Characteristic x-ray lines in the various series
K, L,. . . are interpreted in terms of electron transitions to inner atomic shells denoted
by the same letters K, L,. . . . Optical and x-ray emission processes are represented
schematically as complementary forms of outer- and inner-electron activity in Figure
9-3.
A link exists between spectra and shell structure on the one hand, and the spin of
the electron and the exclusion principle on the other. The following brief history
describes the discovery of this connection.
A shell picture of the atom has been in force since the time of the old quantum
theory. In fact, the exclusion principle emerged along with spin to explain the picture
before the coming of quantum mechanics. The energy shells were originally defined to
be the quantized electron orbits of Bohr's model, adapted to include three empirical
quantum numbers and extended to apply to atoms with many electrons. The electrons
were assumed occupy the various energy
to shells on the basis of assignments of the
three quantum numbers. Moseley used this orbit model to analyze the characteristic
x rays of many elements and demonstrated the connection between the atomic
number and the nuclear charge. No theoretical argument was put forward, however,
to account for the idea of shell closure. The model failed especially to say why all the
448 Complex Atoms

Figure 9-3

Transitions of outer- and inner-shell electrons in optical and x-ray spectra. The excitation of the
atom is by electron collision in each case.

Optical transition

Excitation Deexcitation

ition

electrons in the ground state of a given atom were not simply assigned to the
innermost shell of minimum energy.
Pauli was an ardent advocate of the notion of closed shells. He argued that these
distributions of electrons did not participate in the optical properties of the atom
because the closed shells did not contribute to the total angular momentum and
magnetic moment. His argument drew only on the Bohr model and therefore did not
address the basic question of shell closure.
Another problem with Bohr's model was its failure to predict all the lines observed
in the x-ray spectra of the atoms. This defect was remedied by E. C. Stoner, who
suggested on empirical grounds that a fully occupied shell should contain twice the
number of electrons deduced on the basis of Bohr's three quantum numbers. The
suggestion influenced Pauli to propose that the doublet structure of the alkali spectra
and the anomalous Zeeman effect could be explained if a nonclassical two-valued
degree of freedom was associated with the electron. The new variable turned out to be
the spin quantum number and the new idea proved to be the inspiration for electron
spin.
Pauli went on to observe that four quantum numbers were needed to specify a state
for each electron in the atom. He then showed that the shell structure of the atom
followed as a natural consequence if no more than one electron occupied any given
single-particle state in the many-electron system. His proposition of the exclusion
principle resolved the problem of shell closure and explained the organization of the
periodic table. The original statement of the principle was put forward in 1925.
Pauli's idea was later recast in more general quantum mechanical language and
became one of the cornerstones of quantum mechanics.
 9-3 The Ground Slates of Atoms and the Periodic Table 449

9-3 The Ground States of Atoms and the Periodic Table

The ground state of an atom with atomic number Z is the minimum-energy

configuration for the bound system of Z electrons. We proceed to construct such a
state in the central-field model by letting each electron have a set of independent
states denoted by the four quantum numbers {n^m^m^. We can obtain these
single-particle states from Equation (9-10) by solving for the set of energy eigenvalues
E nf The solution
. provides an ordered sequence of energy levels for any electron in the
Z-electron system.
The atom is not a pure Coulomb field. The single-par-
central field in the complex
ticle depend on both quantum numbers n and /, unlike the
energies should therefore
situation for the hydrogen atom. These energies must not depend on m e and m i

because the potential energy of each electron is spherically symmetric and spin
independent. Hence, there are 2(2/+ 1) degenerate states with the same energy En( ,

corresponding to the two possible values of m s and the 2/+ 1 possible values of m t .

This group of 2(2/4- 1) spin-orbital states constitutes an atomic subshell at energy E nf

for each pair of quantum numbers n and /.
We distribute electrons into subshells and define an electron configuration in terms of
the resulting inventory of n/ assignments for all Z electrons. We must observe the
exclusion principle and assign electrons to spin-orbital states so that no two electrons
have the same values of the four quantum numbers (n£m f m s ). This stipulation limits
a given subshell to a maximum occupancy of 2(2/4 1) electrons with the same energy
E nf The minimum-energy configuration of the atom is then found by allocating the Z
.

electrons to the subshells of least energy, subject to this constraint.

We have noted that the energy levels of a single electron depend on / as well as n
and that the degeneracy of states for fixed n and different / is a special property of
the Coulomb potential energy. A principal quantum number is identified for the
electron in the central-field model so that a close parallel is maintained with the
solutions in the case of hydrogen. We select a value of / and consider solutions of
Equation (9-10) with potential energy V.{r). The solutions comprise a sequence of
radial functions whose nodes increase in number with increasing values of the energy
level. We then define the principal quantum number n as a label for R nir(r) and E nf
by taking n — /— 1 as the number of nodes of R nf (r) in the interval < r < oo.

This definition of n agrees with the radial-node properties of the hydrogen solutions
found in Section 7-2.

Each value of n determines an electron shell for a given atom. A shell consists of n
subshells labeled by n and /, as/ ranges from to n — 1, and every «/ subshell
contains 2(2/4 1) spin-orbital states as observed above. Thus, the single-electron
energies in the central field depend on / and n according to a scheme in which the
principal quantum number retains the same meaning for all atoms. The radial
functions and probability distributions for a single electron can therefore be given the
same interpretation from one atom to another, in the manner of Figures 7-1 and 7-4.
We wish to know the ordering of the energies Enf so that we can assign electrons to
subshells of increasing energy. The determination of these single-electron energies is a
technical problem that must be solved anew for every choice of Z. A representative
sample of the energy levels for a particular Z might resemble the diagram shown in
Figure 9-4. we compare this picture with
If the analogous diagram for hydrogen in
Figures 7-2 and 8-13, we can observe certain points of similar and dissimilar behavior.
The energy E nf increases (becomes less negative) with n for fixed /, reflecting the
usual relation between the energy eigenvalue and the number of nodes of the radial
function. The energy also increases with / for n fixed in a given shell. We can
450 Complex Atoms

Figure 9-4

Energy levels and subshells for a single electron in a non-Coulombic central field. The number
of spin-orbital states is given in parentheses for each of the nf subshells.
(=0 ( = 1 e = 2 ( = 3

Ebp E, 4/
Ess d 5p
5s (6)
•43 (14)
(2) 4p (10)
E*s Eid '

4s (6) 3d
(?) (10)
Eip
(6)
3s
(2)

-.7> 2p
ib)

2s
(2)

Eu
(2)

understand this new feature by considering the following arguments. The smaller

values of ( give larger probabilities for finding the electron near r = 0, as a

consequence of Equation (6-51). In these states the electron is less effectively screened
from the nucleus and therefore experiences a greater share of the nuclear attraction.
The larger values of / refer to states in which there are larger probabilities for finding
the electron farther from the nucleus where the nuclear charge is more fully screened.
In these states the effective nuclear charge is more like that seen by the electron in the
hydrogen atom. Thus, we observe a distribution in energy for subshells in a given shell
where the subshell of maximum / lies near the analogous level in hydrogen while the
subshell of minimum / occurs at a substantially lower level.
We have remarked that the central-field model must be reconstructed for every
atomic number Z. The self-consistency of the model complicates the procedure by
which Vc (r), R n/-(r), and Enf are determined. We are supposed to make a starting
hypothesis regarding Zeff (r) in Equation (9-5) and use this assumption for Vc (r) to
 9-3 The Ground Slates of Atoms and the Periodic Table 451

find eigensolutions R n f{r) and Enf from Equation (9-10). We must then assemble the
state of the given atom by invoking the exclusion principle and assigning the collection
of Z electrons to the single-particle energy levels. The resulting probability distribu-
tion for the system of particles determines an electron charge density from which a
classical electrostatic potential can be computed. The potential determines a potential
energy for each electron, and the average of this result over the state of the atom
generates a predicted central potential energy Vc {r), to be compared with the
hypothesized quantity at the beginning of the cycle of calculations. Self-consistency is

achieved when satisfactory agreement is obtained between the input and output
versions of V( r ). This procedure summarizes the technique developed by Hartree.
The subsequent modification of the method by Fock and Slater incorporates the
properties of identical-particle symmetry to produce the best possible eigenfunctions
for the atom.
Figure 9-5 contains a few graphs of the single-electron energy E nf versus Z, taken
from calculations based on the self-consistent method. We can use this sort of
information to and construct an energy level diagram like
order the subshell energies

the one in Figure 9-4. The exclusion principle allows no more than 2(2/+ 1 electrons )

in each subshell, as noted by the numbers in parentheses at each of the indicated

energy levels. The ordering of subshells is difficult to ascertain whenever the energies
at two or more levels are nearly equal. Figures 9-4 and 9-5 suggest, for example, that
the 3d and 4s subshells are sufficiently close together to compete in the allocation of
electrons to the lowest unoccupied states. The lesser degree of screening in the case of
the As electron implies a greater degree of attraction in that state, and so the
competition favors As over 3d for values of Z within a certain range. A similar
conclusion holds for the 5.r and Ad levels in Figure 9-4, and for other groups of

competing subshells at higher energy. Let us summarize the solution of the ordering
problem by listing the subshells with increasing energy as follows, noting by parenthe-
ses the subshells of nearly equal energy:

Is 2s 2p 3s 3p {As 3d) Ap {5s Ad) 5p {6s Af 5d) 6p . .

We can use this list to build up the ground-state configuration for any atom in the
periodic table.
The lowest Is subshell is occupied by as many as two electrons to account for the
elements hydrogen and helium ( Z= 1 and 2). We describe the electron configurations
of these atoms by the following notation:

H He
2
Is Is

A right superscript is introduced to denote the occupation number whenever a

2
particular subshell is occupied by more than one electron. The Is configuration of
the He atom defines a fully occupied subshell and closes the K shell. It is convenient
to visualize this system in terms of two \s electrons with spins up and down.
The 2s subshell is the next to be filled by as many as two more electrons. The
corresponding two elements in the periodic table are lithium and beryllium ( Z= 3
and 4), with the following configurations:

Li Be Li Be
2 2 2
°r 2
\s 2s ls 2s 2 [He] 2s ...2s
452 Complex Atoms

Figure 9-5

One-electron energy En( versus atomic number Z for the lower subshells. The energies are
expressed on a logarithmic scale in terms of the hydrogen-atom ground-state energy. The data
are taken from tables compiled by F. Herman and S. Skillman.

100

£i,(l)

Note that the symbol [He] refers to an inner helium-like closed shell in the structure of

each atom. It should also be noted that the Be configuration constitutes a filled

subshell but not a closed shell. The 2p subshell follows with a maximum occupancy of
six electrons. We fill these states by adding one electron at a time to generate the
configurations of the next six atoms from boron to neon (Z = 5 to 10):

B C N O F Ne
2 2 2 2 :i 2 4 2 5 2 6
\He]2s 2p ...2s 2p ...2s 2p ...2s 2p ...2s 2p ...2s 2p
 9-3 The Ground Stales of Atoms and the Periodic Table 453

Each of these structures contains an inner closed [He] and an inner filled 2s 2
shell

subshell. The Ne configuration at Z= 10 closes the L shell, and the eight L-shell
atoms from Z = 3 to 10 make up the second row in the periodic table.
The 3s and 2>p subshells are filled in similar fashion by two and six additional
electrons. This construction produces the ground states of the eight atoms from sodium
to argon (Z = 11 to 18), corresponding to the eight elements in the third row of the
periodic table. The configurations of these atoms are listed in Table 9-1, along with
other pertinent information for all the ground states through atomic number 54. Note
that the second and third fully occupied configurations at Z= 10 and 18 are
abbreviated in the table by the symbols [Ne] and [Ar]. We use these abbreviations
when we fill the succeeding subshells beginning at Z = 11 and 19.
The Ar atom closes the third family of subshells, even though the 3d subshell
remains unoccupied. This type of closure is akin to the closing of the K and L shells

by the He and Ne atoms. An explanation is suggested in Figure 9-5 by the existence of

a substantial energy gap between the 3p level and the (4^ 3d) pair of levels. This gap

is just like the two previous gaps at the Is and 2p levels where the K- and L-shell
closures occur. The 4s subshell is actually the next to be filled after 3p because the
screening effect of the [Ar] core tends to favor As over 3d for atoms in this region of
the periodic table. We
from Table 9-1 that the fourth family of subshells opens
see
with the beginning of the As subshell by the K atom at Z = 19 and closes with the
filling of the 4/> subshell by the Kr atom at Z = 36. The 3d subshell is occupied in

ten steps along the way, at interior values of Z in the fourth row of the periodic table.
Notice that this resolution of the (4s 3d) ambiguity undergoes a reversal at Z = 24
and again at Z= 29. In these special cases the Cr and Cu ground states prefer to
keep only one 4s electron and add two more 3d electrons instead.
The same pattern of subshell formation is reenacted in the fifth row of the periodic
table. The 5s subshell is opened by Rb at Z = 37, and the 5p subshell is closed by Xe
at Z = 54. Occupation of the 4d subshell occurs at interior values of Z, and several
reversals in the resolution of the (5^ 4d) ambiguity take place along the way.
The periodic table unifies these observations about the filling of subshells. Figure
9-6 shows how the shell structure of the ground-state atoms is organized by rows in the
table and how the various rows are subdivided according to the occupation of the
successive subshells. Closures occur at the ends of rows, at the noble-gas locations

Z= 2,10,18,36,54

These special atoms are characterized by the closing of a p subshell (except in the case
of He), followed invariably by the opening of an s subshell in a shell of higher n.
Each successive row in the table refers to states of electrons assigned to lie outside closed
subshells. These assignments of n and c* determine the outer electrons of each atom

because the corresponding spin orbitals give weight to the larger distances between
electron and nucleus. Columns of the periodic table contain different atomic species
with the same numbers of electrons outside closed subshells. These atoms are expected
to have similar physical properties since their electron configurations have similar
patterns ofquantum numbers. The alkali elements in the first column are prime
examples. The common properties of these atoms are clearly demonstrated in their
hydrogen-like optical spectra.
Table 9-1 includes a list of experimental values of the ionization energy for each
neutral atom Z. This quantity is defined as the negative of the ground-state energy on
an energy level diagram in which the zero level denotes an ionized system consisting of
 454 Complex Atoms

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-ft, "Vi^ "*<, "*"V| "^t, "^"**
"*"S
^* TJ^ ^7^ Tj* ^^* ^* io lo in in in io

- c - "S3 "S3 "S3 "S3 "S3 ~« "S3

5 "S3 "S3 „£ "S3 "S3 O 2 •* rf Tt< Tf TJH Tf Tf
M -j ?*"; -i -j ~i cm cm cm cm
-= —^t —^i —^l
= *T* "T*
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 9-3 The Ground Stales ol Atoms and the Periodic Table 455

Figure 9-6

Periodic table of the elements from Z = 1 to 54. Atoms in the same column have similar
physical and chemical properties. The rows are divided into blocks of atoms whose outer
electrons occupy the indicated subshells.

Is

1
2

H II.

2s 'ip

3 4 5 6 7 8 9 10

Li Be B C N O F Ne

3s 3p

11 12 13 14 15 16 17 18

Na Mg Al Si P S CI Ar

4s 3d If,

19 20 21 22 23 24 25 26 J 7 28 29 10 31 i2 !3 !4 35 36
K Ca s, Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

bs u< <P

37 38 39 41 12 43 11 15 In 47 48 19 JO il i2 1

Kl> Sr Y Zr Nb Mo Tc Ru Pd Ag Cd In Sn SI, Te 1 V

an electron at rest farfrom a ground-state Z" ion also at rest. In practical terms, the
ionization energy represents the minimum photon energy that the atom must absorb
in order to free a bound electron. We plot the tabulated energies against the atomic
number in Figure 9-7 so that we can display the evidence of periodic shell structure.
The largest values of the ionization energy are observed for the noble gases, while the
smallest values are found for the alkalis at the opening of each succeeding shell. We
can understand this behavior if we recall how the screening effect operates. Electrons
in the same subshell tend not to be screened by each other since their spatial
distributions are equivalent. Consequently, their binding is governed by an effective
nuclear charge that grows with Z to a maximum at the noble-gas closure. The next
electron must be added with a larger n assignment, implying a larger average distance
from the nucleus. The result is an abrupt rise in screening accompanied by an abrupt
fall in nuclear attraction for the added electron, as seen in the figure. Hence, we
identify a closure to be the most tightly bound structure, and we recognize a single
electron beyond a closure to be the least tightly bound constituent.
Electrons in unfilled outer subshells are called valence electrons. These weakly
bound particles control the chemical properties of the atom and determine the
interaction of one atom with another. The noble gases have no unfilled subshells in the
ground state, and so these elements tend to be chemically inert. On the other hand,
the alkalis are chemically active because their ground-state configurations contain a
456 Complex Atoms

Figure 9-7

Ionization energy versus atomic number up to Z= 54. Extreme values of the ionization energy
occur as indicated for the noble gases and the alkali elements.
Ionization energy (eV)

He

Ne
,'(!

At

Kr

.«:,-

10

Li Ne
Rb

10 20 30 40 50

single weakly bound valence electron. These atoms are easily ionized and readily give
up their lone valence electron in the formation of molecules. The chemical characteris-
tics of the elements recur across the periodic table in a columnwise pattern of
regularities, as discovered originally in the design of Mendeleev's table. This pattern is

attributable to the recurrence of quantum properties in the assignment of electrons to

the succession of atomic subshells. The comprehension of the whole scheme of
regularities is only one of the remarkable consequences of Pauli's exclusion principle.

Example

It would be grossly inaccurate to represent the single outer electron of an alkali

atom by an ordinary hydrogen eigenfunction, even though the one-electron

behavior of the atom is observed to be hydrogen-like. To illustrate, let us assume
maximal screening and set Z = 1 for the outer electron in each alkali atom.
(
.
ff

The ionization energy is then given by E /n 2 the Bohr expression for hydrogen, ,

with principal quantum numbers n = 2 for Li, n = 3 for Na, n = 4 for K, and
so on. The resulting energies are

——
eV
13.6
= 3.40 eV, 1 .51 eV, and 0.85 eV for n = 2, 3, and 4.
//

These predictions are not close to the actual values 5.39, 5.14, and 4.34 eV listed
for Li, Na, and K in Table 9-1. It is obvious that a better model is needed to
include the screening effect.
 94 XRay Spectra 457

Example

Oxygen, sulfur, and selenium occur in the same column of the periodic table at

Z= 8, 16, and 34. The ground-state configurations describe an unfilled p

subshell with two electron vacancies in each case:

O Se
2 4 2 4 2 I0 4
[He]2/ 2/> [Ne]3j 3/> ;Ar]4j 3rf 4/>

These elements can fill their vacancies by accepting electrons from two hydrogen
atoms to form the molecules H_,0, H.,S, and H 2 Se. The two vacant sites in O, S,
and Se have angular probability distributions characteristic of an /= 1 subshell.
We can interpret the three m f assignments for £ = 1 in terms of large distribu-
tions of probability along three perpendicular directions. Therefore, we expect to
find right-angle shapes when we attach two H atoms to O, S, and Se to make
the three triatomic molecules. This expectation is borne out since the hydrogen
bonds are at angles of 105°, 93°, and 90° in H.,0, H >S, and H ,Se. (The angle
tends to exceed 90° because of Coulomb repulsion between the two hydrogens
and approaches 90° in the largest molecule where the repulsion is weakest.)

9-4 XRay Spectra

The periodic table organizes the states of electrons outside closed subshells as the basis
for the low-energy regularities of atoms. The underlying shell theory also governs the
inner shells of the atom where the electrons engage in higher-energy processes such as
the emission of x rays. This inner-shell behavior can be examined in a given atom by
analyzing an x-ray spectrum like the one shown in Figure 9-8. We have discussed the
production of x rays in Section 2-6, and we have taken a preliminary look at
characteristic x rays as a source of inner-electron information in Section 3-7. We now
return to the study of x-ray spectra with a proper quantum theory at our disposal and
find that the independent-electron model provides an especially suitable approach.
Let us reconsider our previous picture of x-ray emission in Figure 9-3 and visualize

the excitation and deexcitation of the system from the viewpoint presented in Figure
9-9. The revised picture describes these processes in terms of the single-electron energy
levels in the central-field model. We represent the collisional excitation of the atom by
the creation of a vacancy, or hole, in one of the fully occupied inner subshells. The

Figure 9-8

X-ray lines in the K and L series of tungsten. The heights of the lines are indicative of the
observed intensities. The Ka line at 0.0209100 nm is used to define an x-rav wavelength
]

standard.
<>

K series L series

002 004 006 0.08 10 0.12 0.14

K (nm)
458 Complex Atoms

Figure 9-9

Excitation and deexcitation processes associated with x-ray emission.

Atom Ion in transition E — E2

x

resultis the formation of a highly excited ionic state with initial energy E
v then We
represent the radiative deexcitation of the system by letting an electron from a higher
subshell fill the hole and emit an x-ray photon. The emitted photon has energy

hv = E - E2 x ,
(9-11)

where E2 is the energy of the excited final state in which the vacancy appears in the
higher subshell. Observe from the figure that the x-ray transition occurs in the ion

containing Z— 1 electrons. Note especially that a vacancy in a higher-energy subshell

corresponds to a lower energy state of the ion, so that a hole stands for an absence of
energy, as well as charge, in the overall electron system.

Let us also consider the related quantum phenomenon of x-ray absorption. This
process is an example where the absorption of an
of the familiar photoelectric effect,
x-ray photon excites the atom above and ejects a bound electron. A
its ionization level
quantum mechanical probability can be introduced to describe the photon-atom
interaction, and an absorption cross section can be defined to account for the behavior
of a beam of x rays incident on the atoms in a sample of matter. We measure
absorption in the laboratory by observing the attenuation of an x-ray beam in its
passage through a thickness of material. The fractional decrease in intensity — dl/I is
related to the element of thickness dx by the proportionality

dl
= u x dx,
I *

where the constant jx

x
defines the absorption coefficient of the material. This expres-
sion is easily integrated to give the intensity as a function of distance x through the
sample, starting with incident intensity / :

dl
,,

Jr
-=- r
,

ii x dx =* ln-=-/x^
I
=>
/=V" M ' X
.

I Jo I

The absorption coefficient varies with the material and depends on the wavelength of
the x rays. We can use measurements of the attenuation to determine this dependence,
and we can then infer the related behavior of the absorption cross section for the given
element.
 94 X-Ray Spectra 459

Figure 9-10

K and L absorption edges of lead. The wavelength thresholds occur where the x-ray photon
energy becomes insufficient to eject a K- or L-shell electron. Emission lines of lead in the K and
L series are also shown.

Absorption
coefficient

k (nm)

K series

Figure 9-10 shows a typical graph of ju

r
as a function of the wavelength A. We
observe zero absorption in the limit A — > 0. This observation tells us that the
absorbing medium is transparent to x rays when the beam energy is very large. We
then observe a steady growth in absorption as the photon energy decreases from large
values and as A increases from zero, until we reach a sharp value of A where the
medium suddenly becomes transparent again. This feature of the graph is called an
absorption edge, the first of several to appear with increasing A in the figure. The
indicated A* absorption edge occurs at wavelength X K where the photon energy is the ,

minimum needed to ionize the atom and leave a vacancy in the shell. When A K
becomes larger than A K the x-ray photon energy becomes too small to free a A'-shell
,

electron but remains large enough to eject an electron from an L (or higher) shell. We
again observe a steady growth in absorption as the wavelength continues to increase
until we reach one of the indicated L absorption edges. The various absorption
thresholds are tabulated along with the characteristic x-ray emission lines. Both
features provide a signature of the particular atom, and both give an indication of the
energy levels of the system. We include the emission lines of the K and L series in the
figure so that we can note the positions of these spectral lines relative to the absorption
edges.
X-ray absorption can be interpreted with the aid of our representation of the atom
as a collection of occupied subshells. Figure 9-1 1 describes the process in these terms at
two different wavelength thresholds. The wavelengths A, and A., correspond to
photons whose energies just suffice to eject an electron with no kinetic energy from the
particular subshells shown in the figure. We leave the excited ion in states of energy E x

and E2 in the two cases, and we note the relation

E > E2
x
for A, < A ->•
 1

460 Complex Atoms

Figure 9-1

X-ray absorption processes at two different absorption edges.

Atom Ion in state E,

Atom Ion In state E

The figure tells us that the wavelengths and energies obey the formulas

hi k
E ~
\ ^atom and E, - E» (9-12)
A, A,

where EaUm denotes the energy of the initial atom. If we compare Figures 9-9 and
9-11, we see that the two ionic energies are the same as the energies E x
and E., in

Equation (9-11). If we combine Equations (9-11) and (9-12), we establish the

following connection between x-ray absorption and x-ray emission:

hv (9-13)
A, A

This formula relates the wavelengths for two absorption edges to the frequency for a
certain emission line in the spectrum of a given element. The equality implies an
inequality of the form

he ht
or A > A,
A

for an emitted x ray of wavelength A = c/v. This observation explains why the lines
in a given series have wavelengths above the corresponding absorption edge, as
indicated in Figure 9-10.
The absorption and emission of x rays reveal a new problem that requires an
amendment to the central-field model. Figure 9-10 shows the existence of three L
absorption edges instead of the two expected for the 2s and 2p subshells in the L
shell. This behavior is a clear indication that the nc° assignments of the model are not

adequate to describe the energy levels of the independent electrons. The effect is

reminiscent of the multiplet structure of the one-electron atom and is attributable to a

 9-4 XRay Spectra 461

Figure 9-12 Figure 9-13

Single-electron subshells including the effect X-ray emission associated with the transition
A' —> L lu An electron in the L
of spin-orbit coupling. .
m subshell fills
Electron a vacancy in the K shell while the hole makes
n( occupancy j Subshell a transition from A' to L m The standard .

Ka t
line of tungsten corresponds to this

transition.
5
M\V
3rf<T 2
3
3
2
Z
Mlv !° n

3p^ '
' '
'
2 i
Mm
—
: ; ~ i 2 m„
3s 2 M,

2p< ^
^
— «—
I
1
*m
L\\
^^l!^
7
Hole transition
2s ~ 1
" i!

l.s

spin-orbit coupling experienced by each electron in addition to its interaction with the
central field. We discuss some of the details of this coupling at the end of the section.

Figure 9-12 shows how these considerations alter the independent-electron picture
of the atom by the introduction of the quantum number j. We let each energy level
with subshell quantum numbers n and ( be split for /# in the manner of Figure
8-28, and we recall the familiar quantum numbers (nfjm^ to specify the new
single-electron states. We also label the energy levels by the x-ray spectroscopic notation

K L LnLm
x
M Mu M m M M
x lv x

according to the tabulation given in the figure. The exclusion principle is built into
thisnew scheme of states by stipulating that no two electrons are allowed to have the
same four quantum numbers (nt*jm Hence, each of the split nc"j subshells has a
).

maximum occupancy equal to 2j + corresponding to the number of degenerate m ]

1 ,

states for the given value of j. (We note in passing that the figure orders the energies
of the inner subshells in ascending fashion as

Is 2s 2p 3s2p3d ....
462 Complex Atoms

This ordering of values of Enf holds for the inner electrons of a large-Z atom.) We
note especially that the occurrence of the three split L subshells in Figure 9-12 is

directly correlated with the existence of the three L absorption edges in Figure 9-10.
Let us now return to our picture of x-ray emission in Figure 9-9 and revise the
diagrams to account for the splitting of the subshells. We illustrate the result in Figure
9-13 in terms of a particular x-ray transition. The indicated process shows the filling
of an inner-shell hole by an electron from a higher subshell, along with the corre-
sponding transition of the hole in the opposite direction. Since the initial and final
states of the ion are associated with the location of the hole, it is conventional to
represent the process as a hole transition. The convention employs an energy level

diagram which the highest energy state refers to a hole in the K shell, and in which
in

the zero level refers to the ionic ground state where the hole occurs just beyond all the
electron subshells. This presentation of the energy states of the ion inverts our view of
the levels found in Figure 9-12 and produces an x-ray level shown
diagram of the kind
in Figure 9-14. The figure lists the values of the hole quantum numbers (n£j) and
indicates the allowed hole transitions. These radiative processes are governed by the
electric dipole selection rules, so that the single-particle quantum numbers are

Figure 9 14

X-ray levels of lead and transitions allowed by the electric dipole selection rules. The energies
are plotted on a logarithmic scale.

Energy (eV)

Pb (Z= 82)
10 5 -
K series
n= 1 f =
i=2

.
L series ( = >=\ 1
1
hi n = 2 3 2
^III 2

Hr

...

'

'
'

'

!-
 94 XRay Spectra 463

supposed to change according to the conditions

A/ = ±1 and Aj = Oor ±1 (butO 7* 0),

as Equations (8-42) and (8-43). The various transitions are organized in the
in
diagram into the different series of emission lines. We can employ this same general
scheme whenever we wish to analyze the x-ray spectrum of any element.

Detail

We can formulate the spin-orbit interaction for an electron in a complex atom

by constructing a parallel with the expression for the one-electron atom. Let us
return to Equation (8-32) and rewrite the expression in terms of a derivative of
the Coulomb potential energy:

S • L \ dV
VSL
2m e
c r dr

/here
2
Ze 1 dV Ze 2
V = and =
3
47re r r dr 477e n r

An electron in the central-field model has central potential energy V( r ), and so

the spin-orbit interaction of the electron in the complex atom must have the
form
VSL = S-U (r) e

in which
1 1 dV
Lm f
c r dr

The function V {r)

c
contains the nuclear screening factor Z cif
(r). This quantity
varies between the value Z at small r and the value unity at large r, so that
spin-orbit coupling becomes stronger with increasing Z, especially in states
where r has a small average value. We know from Section 8-9 how the
interaction VSL perturbs the energy states in a central field. Let us consider an
independent electron in an nc* subshell and describe the electron states by means
of the quantum numbers (nt°jm ) instead of the spin-orbital set (n^m^m s
). We
use the eigenfunction ^ n( *
;m as before to calculate the expectation value of VSL ,

and we obtain the following results:

J -L -
2 2
s-
<ySL ) = uo
2
h
j(j+ 1)-/{S+ 1)- - <U0>
2 4
2
h for j"
= t+ \
= y<€c(0>
-{- 1 (orj = + /- \.

This energy shift affects the energy level of an electron in an r\{ subshell
according to the value of j and causes a splitting in every subshell with /# 0.
464 Complex Atoms

Example

The K and L m absorption edges of lead in Figure 9-10 are observed at 0.01408
and 0.09511 nm. Let us consult Equation (9-13) and use these numbers to

X(KL m )
1111
compute the wavelength emitted in the K —» L lu transition:

\K \ Lm 0.01408 nm 0.09511
1

nm 0.01653
1

nm
'

This emission line can also be predicted from the energies of the K and L m
x-ray levels of lead. We use the tabulated values EK = 88.00 keV and EL =
13.03 keV, and we find

he 1.240 keV-nm
A( KL m = 1,1 )
= = 0.01654 nm.
'
E K -E. 74.97 keV

Both calculations agree with the wavelength listed in the tables for the KL m line
of lead.The line and the transition are included among the information given in
Figures 9-10 and 9-14.

9-5 Electron Antisymmetry

We have been able to implement the exclusion principle and explain the periodic
table with only minimal use of quantum mechanics. The exclusion principle itself has
been expressed in a limited context, based entirely on the assignment of electron
quantum numbers in the central-field model. We now want to examine the fundamen-
tal quantum nature of Pauli's principle from the viewpoint of electron indistinguishabihty

and develop the broader concept of identical-particle symmetry. We we have

recall that
already introduced this notion in the framework of one-dimensional quantum me-
chanics in Section 5-10.
Let us begin with the two-electron system and identify the degrees of freedom to be
the pair of spatial coordinates and spin orientations

(r,,5 u ) and (r.,,S,,J.

It is convenient to symbolize these variables in the wave function by adopting the

abbreviated notation

*(r ly S l
„r2 ,S2 „t) = *(l,2,t).

We then determine the probability of finding the two particles in two volume elements
c/t, and dr.) at time t by evaluating the expression

2
|^(l,2, t)\ dTydT2 .

The electrons in the system have identical physical attributes of charge —e, mass m e,

and spin s — \. It is not meaningful to refer to these particles as electron 1 and

electron 2 because the notation implies that the two electrons can always be dis-
tinguished in any state. The intrinsic indistinguishabihty of identical quantum par-
 9-5 Electron Antisymmetry 465

Figure 9-15

Distinguishable orbits of two identical classical

particles.

O^

tides has been discussed previously in Section 5-10. We are reminded in Figure 9-15
that any pair of classical particles can always be analyzed in terms of distinguishable
particle orbits, but we recognize that such a treatment violates the uncertainty
principle in the case of identical quantum particles. Since the two particles in the
figure are identical, their indistinguishability allows us to prepare a state of separately
identified colliding particles but prevents us from ascertaining the identity of the
detected particles after the collision. We build this property of electrons into the
probability density by imposing the requirement of identical-particle symmetry:

|*(1,2,0|' = |¥(2,1,0|'- (9-14)

This statement follows Equation (5-90) and says that 1*1" is not altered by tin-

exchange of the two sets of space and spin variables in the wave function.
The exchange symmetry of |¥|" can be realized in two independent ways. These
alternatives correspond to mutually exclusive symmetry properties of the wave func-
tion itself. The two-particle state may satisfy either the exchange-symmetric condition

¥(1,2,0 = +¥(2,1,0 (9-15)

or the exchange-antisymmetric condition

¥(1,2,0 = -¥(2,1,/). (9-16)

A system containing more than two identical particles obeys a similar relation with
regard to the exchange of any two sets of degrees of freedom in the many-variable
wave function. We emphasize that the symmetry or antisymmetry of ¥ is an
additional quantum property to be applied to solutions of the Schrodinger equation
and that the choice of sign + for symmetry or — for antisymmetry) is not meant to
(

be taken arbitrarily. Either symmetry or antisymmetry is imposed on the constituents

of a system as a law of nature. Two identical particles are called bosons if Equation
(9-15) holds, or fermions if Equation (9-16) holds, and all particles observed in nature
are classified as either bosons or fermions. (The classification is named after S. N. Bose
and E. Fermi for their part in the development of statistical laws governing thermal
distributions of the two types of particle.)
466 Complex Atoms

The exclusion principle can now be reexpressed in terms of exchange behavior in

the space and spin variables of the wave function. This more general version of Pauli's
rule is known as the Pauli principle. The application of the rule to electrons classifies

these particles as fermions by the following assertion:

The wave function for a system of electrons must be antisymmetric with

respect to the exchange of any two sets of space arid spin variables.

Pauli's original exclusion principle follows directly from this statement by arguments
to be demonstrated below. The Pauli principle more comprehensive because its is

implementation is not tied to any specific treatment of the electron system, and
especially because its implications are immediately applicable to any particles certified
as fermions. Thus, the shell structure of atoms is only one indication of the influence of
this new quantum property.
Let us see how the exclusion principle is contained in the statement of antisymme-
try by looking first at the case of the two-electron atom. We consider a stationary-state
wave function of the form

fi// *
¥(1,2,0 =^(l,2)«-'

and note that the Pauli principle requires the eigenfunction ^(1,2) to be antisymmet-
ric under the exchange of variables 1 «-» 2. We determine \p from Equation (9-2) by
applying the central-field model to the pair of independent electrons. We know from
Section 9-1 that solutions for \p exist as products of two single-particle eigenfunctions,
each having the spin-orbital form

(Recall that we are using a single Greek index to represent a complete set of four
spin-orbital quantum numbers for a single particle.) Thus, if a and /? denote any two
spin-orbital states, it is clear that

^(1)^(2) and ^(1)^„(2)

are degenerate solutions of Equation (9-2) since both product expressions have the
same energy eigenvalue Ea + En. Any linear combination of the two expressions is

also a solution with the same energy, and so the requirement of antisymmetry can be
met by constructing the particular combination

*(1,2) = ^(^(1)^(2) - ^(1H„(2)). (9-17)

This two-electron eigenfunction has the desired antisymmetric behavior under the
exchange of variables 1 <-> 2:

^(2,1) = -^(^(2)^0) - ^(2)^„(0) = -*(1,2).

/2

(We include the factor l/v2 to secure the normalization of \p. This point
 9-5 Electron Antisymmetry 467

investigated in the first example below.) It an immediate consequence of the

is

antisymmetry of Equation (9-17) that \p vanishes whenever a and /? refer to the same
quantum numbers. We
set of single-particle conclude that no such two-electron state
and we thus affirm the outcome of the exclusion principle.
exists,

These arguments are readily extended beyond the case of the Z = 2 atom. We
observe that Equation (9-17) has the structure of a determinant, and we write

*(1,2) =
*«(2) *,(2)

An obvious generalization gives

1
* o 0) M M1
)
1
)

*(1,2,3) = * a (2) ^(2) *y(2) (9-18)

* a (3) ^(3) * Y (3)

for the three-electron atom, and ultimately gives

MO
*«(2) *„(2) ^(2)
^(1,2, Z) = (9-19)
lz\

Mz )

for the Z-electron atom. These expressions for the eigenfunctions are known as Slater
determinants. The general algebraic properties of determinants imply that the expres-
sions change sign when any two variables are exchanged and vanish when any two
spin-orbital indices denote the same state. Consequently, Slater determinants auto-
matically satisfy the Pauli principle and furnish the basic solutions for use in the
Hartree-Fock self-consistent procedure.
We have discovered the joint concepts of spin and fermion antisymmetry as new
quantum mechanical properties associated with the behavior of electrons. It is

intriguing to suppose that these two intrinsic characteristics of particles might be

somehow interrelated, a possibility originally explored by Pauli. The possibility has
indeed been realized in nature since the following observations have been established
by experiment:

Particles with half-integral spin behave as fermions,

and
particles with integral spin behave as bosons.

The interrelations apply to all known and suggest a profound underlying

particles
idea worthy of purely theoretical investigation. The connection between spin and
identical-particle symmetry has in fact been proved under certain general hypotheses
in the so-called spin-statistics theorem.
 .

468 Complex Atoms

Example

We can verify the normalization of the stationary-state eigenfunction in Equa-

tion (9-17) by the following computation:

jdT jdT2 \^{\,2)\

x

= -jdT jdT2 \^ a {\)^ p {2) - ^0)^(2)

x
2

-
-fdrJdr^lUDfl V2)T' " ^(1)^(1)^(2)^(2)
2
-^(1)^(1)^(2)^(2) +|^(1)| |^(2)
= \ {
1 -0-0+ 1}.

The single-particle eigenfunctions are normalized to satisfy

/ I
^«( 1 ) |
dt\ = 1 and similarly for \pp

The functions also obey the orthogonality condition in Equation (6-63):

/^(1)^(1)«/T, =0 if a *fi.

Both formulas have been used to complete the above calculation.

Example

Antisymmetrization is required, but may not always be essential, for a descrip-

tion of electrons. To illustrate, let us suppose that independent-electron states are
defined for two particles e and e in terms of the single-particle eigenfunctions \p

and »|/. A non-antisymmetrized eigenfunction for the system has the form

f'(l,2) =^(1)^(2)

with probability density

2 2
P4(l,2)=\f(l)\ \$(2)\ .

Equation (9-17) expresses the properly constructed eigenfunction as

*(1,2)= j=(Ul)f(2) -*(l)«f(2)).

The corresponding probability density is

2 2
P(l,2) = ±{|if(l)| |#(2)| " lf*(l)*(l)**(2)if(2)

2 2
+l^(i)l u"(2)i -r(i)j(i)r(2)t(2)\,
 96 The Helium Atom 469

as in the previous example. The probability of finding e (an electron in state i|>

in a volume At is given by the expression

2 2
P=-(
2 At
J\t
\f{l)\ drJ\$(2)\ dT2 - - f «j>(l)£(l)rfT,/ ^*(2)if(2)rfr2
J I At •'At

+
1
2

f \${2)\ drJ\t{\)\
dr
2
x
--( r(2)H2)dr.2 f ^(D^(l
At J 2 At At

Note that we restrict the region of integration to At wherever \p is involved, and

we integrate over all space in the variables of \p when there is no such
restriction. The integration coordinates are dummy variables, and so the prob-

ability can be rewritten as

P= f I^DfrfT, - ( r{\)i>^)dr ( $*{2)i(2) dr2 x

At At At

2
= f |ftl)| rfT, " [ f*(l)^(l) dT,
At At

We have used the fact that »// is a normalized single-particle eigenfunction to get
the first line of this result. Note that the orthogonality of \p and ip does not cause
the integral of the product of these functions to vanish unless At refers to all

space. If we compute the same quantity from the non-antisymmetrized probabil-

ity density P '(1,2), we obtain the simpler result

2
P*= f |^(l)|-^T,f|^(2)|^T, = ( |lf(l)| rfT,.
At J At

Thus, we see that P* is an excellent approximation to P whenever the overlap

integral

At

for the states \\/ and Such a circumstance arises when e and e are
\p is negligible.
an appreciable distance apart. The overlap
electrons in separate fields of force,
is small in this case because the eigenfunctions \p and \p do not have large

magnitudes in the same regions of space.

9-6 The Helium Atom

The Grotrian diagram for the He atom is shown in Figure 9-16. The striking feature
of these energy levels and transitions is the apparent existence of two distinct He
varieties, denoted in the figure as parahelium and orthohelium. The two species
present themselves in separate families of spectral lines since the transitions occur
within, but not between, the para and ortho systems of energy levels. This behavior
indicates the dynamical influence of a certain quantum number that distinguishes the
two forms of helium. One of our main objectives is to show how this new quantum
number arises from considerations of the Pauli principle.
470 Complex Atoms

Figure 9-16

Energy levels and electric dipole transitions of helium. Emitted wavelengths are given to the
nearest nanometer, as in Figure 9-1 All states below the ionization level have Is n rf configurations
.

denoted by the indicated n£ assignments. The levels are organized by the notation at the top of
the diagram according to total orbital and total spin quantum numbers.

He +e

ortho-He

We know from Section 9-3 that the He ground state is a closed-shell system of two
Is electrons. The higher-energy states must therefore involve configurations in which
at leastone of the electron orbitals is beyond the n = 1 shell. In fact, only one particle
can be excited beyond n = 1 since the energy required to excite both particles exceeds
the 24.6 eV ionization threshold for the ionized system He + (l.r) + e. We can therefore
classify all the discrete energy states of the bound He atom as singly excited \s n£
configurations. Accordingly, the levels in Figure 9-16 are labeled by the n^orbital
designation of the excited electron, and the energy values are given by the sum of

energies E n) + Enf in the central-field model.

It is instructive to combine the orbital angular momenta of the two electrons and
define the total orbital angular momentum of the system as

L, + L,. (9-20)
 9-6 The Helium Atom 471

A total orbital quantum number l° can then be associated with L by the usual quantization
rules. Since the one electron is never excited, it is clear that the value of ( in the He
atom is always equal to the £ value of the lone excited electron. We indicate this
assignment of the total orbital quantum number by the familiar spectroscopic label
S, P, D,. . . at the top of each column of energy levels shown in the figure.

We get to the heart of the He problem when we consider the imposition of the
Pauli principle on the two-electron system. Let us start with the ground state and
2
rewrite Equation (9-17) in the form of a Slater determinant for the Is configuration:

*u>('i)loo(0i»*i)T, *io('i)Ioo(0i»*iHi
*(1,2)
f2 Rjr 2
)Y00 (02 ,4> 2 )T 2
R [O (r2 )Ym (02 ,<t> 2 )l 2

The expanded result exhibits a separation of the space and spin dependence into a
spatial eigenf unction multiplied by a spin eigenf unction:

/ 1

*(1,2) = {(/? 10 (r 1
)K00 (« ,* 1 1 ))(/? IO (r2 )yoo (fi2 ,* 2 ))}|^-(t 1 i 2 - i , t 2 ]

(9-21)

We observe that the required antisymmetrization of i// is accomplished in a factorized

fashion. The first bracketed quantity is obviously symmetric under the exchange of the
two spatial coordinates r, *-* r2 , while the second is antisymmetric under the exchange
of the two spin orientations 1 *-» 2.

A similar factorization can be employed to obtain overall antisymmetry in any He

eigenfunction. The procedure can be followed even when the construction of the state
calls for a superposition of Slater determinants. We antisymmetrize the two-electron
eigenfunction under the exchange 1 <-> 2 by assembling a product of symmetric and
antisymmetric space and spin eigenfunctions in either of the following two ways:

U s
(r ,r 2
1 )
"
!

X (l,2)
<Ml,2) = I or (9-22)

l^(r lf i
r 2 ) X *(l,2).

The antisymmetric and symmetric spatial eigenfunctions are obtained by constructing

^(r,,r 2 ) = -^[^(r,)^(r2 ) - ^ 6 (r,)^(r 2 )] (9-23)

and
1
r

^(r„r2 ) = ^[*„(r,)* 4 (r 2 ) + ^ A
(r, )f (r 2 )]
;
(9-24)

lettingeach subscript a and b denote a set of three spatial single-particle quantum

numbers {n£m f ). The antisymmetric and symmetric spin eigenfunctions are formed in
like manner by defining

1
4
X' (l,2)= -^(t,4 2
- 1,T 2 ) (9-25)
472 Complex Atoms

and

X f(l,2) = T,t 2 ,

xg(l,2) = -^(T,l 2
+ 1,T 2 ),
v2

X-i(l,2)= i,i 2
. (9-26)

As usual, the factor 1/ v2 is included in the formulas to maintain the normalization.

We see that the exchange antisymmetry and exchange symmetry of these expressions
are in correspondence with the superscripts A and S introduced in Equations (9-22).
The four spin eigenfunctions in Equations (9-25) and (9-26) exhaust all combined
up and down orientations for the two electron spins. We have found it possible to
construct one antisymmetric and three symmetric arrangements of these orientations.
The states are designated accordingly as singlet and triplet spin eigenfunctions. We
note that the lone antisymmetric spin eigenfunction x already appears as a factor in
Equation (9-21) for the ground state. The accompanying spatial factor is a special
version of Equation (9-24) in which the indices a and b refer to the same single-par-
ticle orbital state. Other special cases of the symmetric spatial eigenfunction may also
occur, taking the form of a single product

v
f (r,,r 2 = )
^(r,)^(r 2 )

without the usual normalizing factor.

The lowest excited levels of helium belong to the \s2s electron configuration. Let us
organize the four different states in this system by the scheme described in Equations
A
(9-22). We represent the electron spins by the singlet eigenfunction x m one OI the
S
states and by the three triplet eigenfunctions \ m the other three states. Equation
(9-22) then tells us that the spatial eigenfunction must be symmetric to accompany the
singlet state and must be antisymmetric to accompany the triplet states. We use this
strategy to write the \s2s eigenfunctions as

*(1,2) - ^[(VoJ.fVJ. T+
~7j |A'*!0 / 00M A 20 / 00</2 f^A,)^,,^),]
^'Jo'lNl/l^ill'oo^l \ ^(Til2- Ma)}
~fK

(9-27)

for the singlet state and

4 /
( 1 >2) = {
-^[(#i *oo)i( #20*00)2 ~ ( #20*00 )i( #10*00)2]

T,T,

\ -7^(t,i 2
+ Ma) (9-28)

1 1 i 2

for the triplet states. (We adopt the abbreviating subscripts 1 and 2 to denote the
spatial variables r, and r 2 .) The total orbital quantum number has the value €= for

each of these eigenfunctions, and so the resulting singlet and triplet states appear in
 9-fi TAe Jfe/wm /l/om 473

3
Figure 9-16 with the assignments S and
l
S at the top of the energy level diagram.
Singlets and triplets are also indicated in the figure for other configurations and other
values of tf.

The singlet and triplet states are distinguished by their exchange properties under
the abstract concept of fermion antisymmetry. Let us attach a more concrete meaning
to the two kinds of spin eigenfunctions by recalling our interpretation of electron spin
as an angular momentum vector. The two-electron system has spins S, and S.,, and so
a total spin angular momentum can be defined by the vector sum

S = S, + &,. (9-29)

l
The individual spin vectors have the eigenvalue properties of separate spin- ,
par-
ticles, as discussed in Section 8-5:

3
2
s, = h\(s + i) = -h' S„ = /zw = + —
y

4
* - 2

and
3
sj = h%(s.2 + 1) = -ti1
4
^= /?w
'-'
= H
" 2

The total spin S is supposed to obey the same general quantization rules in terms of
the quantities S" and Sz Hence,
. there must exist a nonnegative numerical quantity s,

called the total spin quantum number, such that quantized values are given for the square
of S by the eigenvalues

2
S2 = h s(s +1). (9-30)

Each possible s then implies a set of 2.$ + 1 quantized values for the z component of
S, given by the eigenvalues

Sz = hm 3
with m = s
-s,..., s. (9-31)

These equations describe the familiar behavior of an angular momentum in which the
S vectors have definite magnitudes determined by s and discrete 2-axis projections
determined by m s
.

Equation (9-29) implies a relation among the c-component quantum numbers:

m = m + m .

It follows that m s
must be integer- valued, since m and m s are half-integral, and that s

the possible values of s must be integers. Only two possibilities exist,

5 = and s = 1

since any larger s would permit w to exceed unity, the maximum allowed (
for the sum
of m s
and m s The respective z-component quantum numbers are
.

m = s
for s = and w = —
(
1 , 0, 1 for s = 1

These four assignments of quantum numbers (smj refer precisely to the four spin
474 Complex Atoms

Figure 9-17

Vector addition of two spin-^ angular momenta. The sum S = S, + S_> is constructed, without
factors of h, for the case m %
= m %}
= h. The resulting spin state has s = 1 and m = 1
1, as
described by the symmetric spin eigenfunction x'\-

s = 1

eigenfunctions identified in Equations (9-25) and (9-26). The total spin quantum
number and the spin-exchange property are correlated such that

= A
s denotes the antisymmetric singlet \

and

s = 1 denotes the symmetric triplet xt, •

S
Note that the x' states in Equations (9-26) are already labeled by their m s
values in
anticipation of this development.
Figure 9-17 shows how the addition of two quantized spin-^ vectors S, and S 2
produces a quantized result for S. We illustrate the selected spin state xf by the sum
of two spin-up vectors, and we argue that x^ is represented by an inverted version of
i

the same picture. Any combination of spin-up and spin-down states can be taken to
A
form an m =
s
state. The particular construction x corresponds to a total S vector
of vanishing magnitude, while the Xo state describes a combination of spin up with
spin down in which the total S vector has magnitude v2 h.
The new quantum number s has dynamical as well as notational significance. We
recognize the total spin S to be a conserved angular momentum for two electrons
subject to the Coulomb interactions described in Equation (9-1). We also make a
similar claim regarding the total L vector defined in Equation (9-20). These state-
ments mean that we can regard the associated total quantum numbers (sm s ) and
{£m f ) as good quantum numbers, provided we ignore spin-orbit coupling. This
interaction is of some interest since it causes a small splitting of the helium levels with
nonzero f in Figure 9-16. If we take account of the effect we find that L, and S, are
no longer conserved, as in the one-electron problem, so that m f and m do not remain s

good. We then introduce the conserved total angular momentum

J = L + S,

and we use the corresponding quantum number j along with / and s to label the split
energy levels. The complete spectroscopic designation for a He level has the form

2j+1
L;.

This notation includes a value of n for the excited electron and assigns a superscript
 9-6 The Helium Atom 475

2s + 1 giving the spin multiplicity of the level as singlet or triplet for s = or s = 1.

2
Thus, to cite again our previous examples, we denote the Is ground state in Equation
(9-21) by

1 % with n = 1, s = 0, <f = 0, j = 0,

and we denote the \s2s excited states in Equations (9-27) and (9-28) by

2 \ with n = 2, s = 0, /= 0, j =
and

2 5,
3
with n = 2, j = 1, (= 0, j'= 1.

2i+1
Only the partial notation L is employed to classify the helium levels in Figure

9-16. Notice that the same scheme has already been adopted for the hydrogen levels in
Figure 9-1 by setting s = \ and 2s + 1 = 2 for every state in the one-electron system.
We observe from Figure 9-16 that the singlet and triplet helium levels separate into
the two varieties parahelium and orthohelium. We also note that the triplet always lies
below the singlet in a given electron configuration, except for the special case of the Is
configuration where the triplet possibility does not exist. To choose a typical example,
i
consider again the ls2s system and note that the level 2 S i
lies lower than its partner
2
X
S . We know that the solutions of the central-field model describe configurations of
degenerate spin-orbital states. We also know that the central field takes in only a part of
the noncentral interaction between electrons. The obvious conclusion is that the
separation of singlet and triplet He energies must be due to some aspect of the
interaction between the electrons, beyond the effects included in the central-field
potential energy.
The repulsive electron-electron interaction favors the triplet over the singlet as a
consequence of the Pauli principle. The two electrons in a triplet state must have a
spatial eigenfunction of antisymmetric form, as given by Equation (9-23). Such a state
vanishes when r, = r 2 , so that there is small probability for the particles to be found
near each other. Consequently, the two electrons tend to remain at a distance where
the repulsive interaction has a reduced effect. On the other hand, a symmetric spatial
eigenfunction governs the singlet state and permits the particles to be found closer
together where they undergo a greater Coulomb repulsion. Thus, electron-electron
repulsion is more effective for the singlet state in a given configuration, and so the
triplet states experience more net attraction and have lower-lying energy levels. These
arguments imply that the choice of spin state influences the spatial distribution of the
particles and simulates a sort of interaction.The effect is called an exchange force keeping
triplet-state particles apart and bringing singlet-state particles together. The coupling
of space and spin variables operates through Equation (9-22) by virtue of the Pauli
principle and generates this important nonclassical contribution to the behavior of
indistinguishable particles.
Figure 9-16 also shows that no radiative transitions occur between para and ortho
states. We understand this situation at once when we recognize that the observed
spectral lines are due solely to electric dipole transitions. These processes are associated
with the oscillations of a spatial vector, the electric dipole moment of the atom, and do
not involve the spin vectors of the electrons. The total spin quantum number s cannot
change in an electric dipole transition, and so the singlet and triplet energy levels can
only participate in transitions among themselves. The electric dipole selection rules
476 Complex Atoms

apply to the orbital quantum number of the excited electron and, therefore, to the
total orbital quantum number t We summarize the constraints on the total spin and
'.

total orbital quantum numbers by writing

A* = and l±f = ±1 (9-32)

and by noting that all the transitions in the figure obey these conditions.

Example

We have identified all the bound helium levels above the ground state with
singly excited two-electron configurations. Let us examine this claim by describ-
ing the atom in first approximation without the electron-electron interaction.
The energy of a state with independent-particle quantum numbers («, n2 ) is

then given by the Bohr formula with Z= 2:

Z2 Z 2

—E — —+—
/ 1 1 \

E(n ,n 2 )x
= E - = - (54.4 eV).
"l n2 \
n \
n 2 )

We compile the results in the following brief table:

n, n 2 1 1 1 2 1 3 1 00 22
/-."(
n,, « 2 ) ' n e^ - 108.8 -68.0 -60.4 -54.4 -27.2
E(n v n2) - £(l,l)ineV 40.8 48.4 54.4 81.6

Note that the (1 oo) level refers to the ionized system He + (1^) + e, and observe
in the third line of the table that the doubly excited energies above £(1, oo). lie

Of course, the numbers in the line cannot accurately approximate the actual
values plotted in Figure 9-16. The point of this simple calculation is that the
neglected electron -electron repulsion contributes a positive energy shift that
elevates all values of E to higher levels. The energy of the (1 oo) level is scarcely
affected by the shift since the electrons stay far apart in this state. Appreciable
upward shifts occur for levels with small n values, however, particularly in the
(11) ground state and even in the (2 2) doubly excited system. We conclude that
all doubly excited states remain higher than the ionization level after the

repulsive shift is taken into account. These systems are known as autoionizing
+
states since they transform spontaneously into the ionized atom He + e.

9-7 Alkali Atoms

The optical spectrum of an atom spans the visible range of wavelengths and reflects
the activity of the outer-shell electrons. We have illustrated the excitation and
deexcitation of these optically active electrons in Figure 9-3. This picture of optical
phenomena is clearly realized by the alkali atoms corresponding to the elements
 9-7 Alkali Atoms 477

directly below hydrogen in the periodic table. Hydrogen-like qualities appear in the
spectra of the alkali atoms and give evidence that the transitions are attributable to a
single valence electron. The one electron occupies an orbital state outside a core of
closed subshells and thus provides a simple structure to study as a testing ground for

the central-field model.

We learn from the model that the lone valence electron of an alkali atom has an
tty-orbital assignment in the ground state. In each case (lithium, sodium, potassium, . . .
)

the quantum number n opens a new shell after all available orbitals of lesser energy
are filled by the core electrons. We consult Table 9-1 and find that the ground states

of Li, Na, K, . . . have core configurations

2 2 2 6 2 2 b 2 6
Is , ls 2s 2p , \s 2s 2p 3s 3p , ...

and valence-electron assignments

2s, 3s, 4*, ....

Each core electron has its own individual orbital and spin angular momenta L and (

S Both quantities add up to zero when the sums are taken over all electrons in the
;
.

core. To understand this point we examine the quantum numbers of the core electrons
and recognize that the individual z-component quantum numbers have vanishing
sums

V.
= and Y m, = 0, (9-33)

since every available assignment of the quantum numbers is taken to assemble the
closed subshells. It follows that the overall core angular momenta

£L, and £S,

must have vanishing magnitudes, otherwise core states with nonzero ^-component
quantum numbers would also exist, in conflict with Equations (9-33).
We summarize this situation by describing a core of closed subshells as a S system l

with total orbital and total spin quantum numbers equal to zero. The result implies
that the single valence electron sees the core as a spherically symmetric distribution of
charge. We should expect the central-field potential energy V (r) to be especially good c

as an approximation for such a quasi-one-electron atom.

The energy levels and radiative transitions of lithium and sodium are plotted in
Figures 9-18 and 9-19. We appeal to the one-electron properties of these atoms
immediately and use the n ^orbital quantum numbers of the valence electron to
identify the various levels. The excited states lie above the 2s ground state in lithium
and above the 3^ ground state in sodium, as noted in our previous remarks. The
figures also show the energies, relative to the ionization level, for comparable excited
states in hydrogen. A close correspondence can be seen between alkali levels and
hydrogen levels, provided allowance is made for the non-Coulombic features of the
alkali model. We know that the central-field potential energy V (r) approaches
c
its

hydrogen-atom form and so we consider those orbital states in which the

at large r,

valence electron has large (r) and look for good agreement between the alkali and
hydrogen energies. We meet this criterion in states of maximum / for given n. The
478 Complex Atoms

Figure 9-18

Grotrian diagram for the lithium atom showing wavelengths to the nearest nanometer.
Hydrogen levels for n > 2 are taken from Figure 9-1 for comparison on the right side of the
diagram.

Li + e
2g 2p 2
D 2p
H +

n = 4

n = 3

n= 2

figures tell us that these particular alkali states are in fact quite close in energy to their
hydrogen counterparts. These observations of the lithium and sodium levels are in
keeping with our general comments in Section 9-3 about the n dependence and /
dependence of the energy eigenvalues for a non-Coulombic potential energy.
The angular momentum of an alkali atom is easy to analyze in view of the simple
properties associated with the closed-subshell core. We define the total orbital and
total spin angular momenta of the atom by the expressions

L = E L, + L r
(9-34)
core

(9-35)

where Y. e and Se refer to the valence electron. The core makes no contribution to L
and S, and so the whole atom assumes the angular momentum properties of the one
electron outside the core. Thus, each atomic state has total spin quantum number s = ^
and total orbital quantum number / given by the particular n ^orbital state of the
valence electron. The resulting spectroscopic notation for the alkali levels has the same
 9-7 Alkali Atoms 479

Figure 9-19

Grotrian diagram for the sodium atom showing spectral-line splittings of at least 1 nm. Levels
of the hydrogen atom for n > 3 are included as in the previous figure.
2
S 2p 2
D 2
F H +
Na + e e
5- -0.004

n = 4
4rf / 4/
4

-0.003
4p
s SI n= 3
3d
r& /

3- 4s /
**
*

/
/ i

-0 002 *
/
vo
f
2- 3p
/ /

-0001
1-
1/
/
-l
eV nm /
3s

doublet form as in the case of hydrogen. Therefore, the same 2 L designations appear at
the top of the energy level diagrams in Figures 9-18 and 9-19 as in Figure 9-1.
Every alkali doublet level with nonzero ( has a fine structure like that observed in
hydrogen. (The effect is not large enough to be seen on the scale of the two figures for
lithium and sodium.) This splitting of the energy levels is due to the spin-orbit
interaction of the valence electron. Spin-orbit coupling has a small effect on the levels
ofhydrogen and becomes more appreciable in complex atoms with increasing atomic
number. The interaction has already been applied to the behavior of an inner-shell
electron in our discussion of x-ray spectra. We reconsider its influence in the case of
alkali spectra and again restrict the interaction to a single particle, the valence
electron.
We express the spin-orbit interaction for a single particle in the central-field model
by the formula

1 d_K
VSL = S-U (r) c
where |,(r) =
o
lm,c
2 i
dr
(9-36)

These equations are carried over from our treatment of x-ray levels at the end of
Section 9-4. We
then introduce J, the total angular momentum of the atom, as the
sum of the quantities L and S defined in Equations (9-34) and (9-35). Again the core
makes no contribution, so that the quantization properties of J are the same as those
480 Complex Atoms

Figure 9-20

Spin-orbit splitting of the 3/> level of sodium.

The 3p — > 3s transitions produce the two D
lines in the sodium optical spectrum.

--
2.11

i
0.0021 eV

J
C
2.10 , o

//
eV
//
',s

1 2
of the single valence electron. As usual, the eigenvalues of J are equal to h j{j + 1),
where the total angular momentum quantum number j takes on either of the two
possible values {— ~ for every nonzero <f. The spin-orbit interaction in
{+ l
, or
Equation (9-36) causes the energy of a given n^j-orbital level to shift by an amount
that depends on the values of the three quantum numbers. The formula for the shift is
the same as that found in our detailed remarks at the end of Section 9-4:

h' forj = /+ |

(Vsl) <uo> -{- for; = (-

1 \,

This result implies a fine structure splitting in the form of a doublet for every ( ¥=
level in Figures 9-18 and 9-19. The final outcome is a splitting of spectral lines that
bears a certain resemblance to the line splitting in the spectrum of hydrogen.

Example

We find conspicuous evidence of spin-orbit coupling in the alkali atoms when

2
we look at the radiative transitions of the lowest P level of sodium. Figure 9-20
shows the relevant ?>p and 3^ states on an enlarged portion of the Na Grotrian
diagram. The energies of the 2/> 3 / 2 and states at the 3/? level appear in the

figure above the energy of the unsplit 'S ground state at the 3^ level. The i

spectroscopic notation
2
i( L.

summarizes all the quantum numbers (ntsj) needed to identify any of these
states. The figure also quotes the wavelengths of the radiation emitted in the two
transitions

2 2
3p P3/2 3.r o 1/2 and 3p P ' -
3s S 1/2"
 9-8 Angular Momentum Coupling 481

These radiative processes obey the electric dipole selection rules appropriate to
the transitions of a single electron:

A^= ±1 and A/ = Oor ±1.

We note that the familiar single-electron conditions are transferred directly to

the quantum numbers of the whole atom. In general, the selection rules allow
three different transitions between the pairs of doublet levels. Note, however, that

Figure 9-20 describes an exceptional case since an unsplit t* = § state is involved.

We indicate the resulting ranges in wavelength for the various spectral lines of
sodium in Figure 9-19.

9-8 Angular Momentum Coupling

The central-field model describes the complex atom in leading approximation, and the
Pauli principle defines the electron configurations of the atom within that context.
Two additional dynamical effects also influence the structure of the atom. One of
these corrections arises from the fact that the central field includes only part of the
noncentral Coulomb repulsion between the electrons. The spin-orbit coupling of the
electrons provides the other correction. These secondary considerations have already
been encountered in our discussions of certain atoms.
We wish to organize the corrections to the central field on a systematic basis and
apply the resulting scheme to all electrons outside filled subshells. We continue to be
concerned with optical excitations, and we recognize that every outer electron
participates equally in the optical activity of the atom. The configurations of the atom
are known in terms of the orbital and spin angular momenta of each electron. Our
intention is to sort out the secondary corrections in stages with the aid of conservation
laws among these quantities.
Let us examine the construction of the central field more closely so that we can
specify the first correction to the model. The Coulomb potential energy for the
Z-electron system consists of central and noncentral contributions, as written in
Equation (9-4):

Ze
2 z 1 e
1 z 1

477£; n ,= ,
1
r,
',
4-7TE
,•</=!

We know that the noncentral repulsion between electrons is not small enough tobe
treated as a secondary effect. We proceed instead to extract a central approximation from
this part of the potential energy by rewriting V in the following manner:

V=LK('i)+ K„ (9-37;

where

LK(r,)= -T—E- +
477£ r 477£ o |r,
(9-38)
\ ,< ;

and

V.. = (9-39)
4-ne ,< j,Ti-*j\ 4 ^«>
\ ,<j |r,- - Tj\
482 Complex Atoms

Figure 9-21

Coordinate vectors in the definition of a central

field for the ;th electron in an atom.

Note that a new quantity is added and subtracted to make this construction. We
define the new expression by an averaging procedure in which an ith particle is

singled out, as in Figure 9-21, and an average is taken over all other particle
coordinates and over all directions of the vector r ;
. The result for the ith particle is the
desired spherically symmetric potential energy V c
with only one remaining variable,
the radial distance r
r Equation (9-39) then defines the residual electrostatic interaction Vrr
as the leftover part of the repulsion between electrons, after the removal of the central
approximation. Our treatment of the model in Equations
independent-electron
(9-6)-(9-10) is based on the leading central contribution in Equation (9-37). We have
given the main role to this part of V, and so we regard the residual term Vee as a small
perturbing effect.

The spin-orbit couplings of the electron account for another secondary interaction.
We employ the central-field function £/r) in Equations (9-36) and express the sum of
these couplings by the formula

VSL = Xi(OS, ' L... (9-40)

The two Vee and Vsl perturb the central field with different relative
corrections
strengths depending on the position of theatom in the periodic table. We have learned
that the spin-orbit effect is quite weak for small Z and grows much stronger with
increasing Z. We therefore identify two broad regimes of atomic number, and we
argue that Vei dominates over VSL for low-Z atoms, while VSL dominates over Vf( for
high-Z atoms. Different conserved angular momenta are associated with the two
effects, and so different procedures are needed to analyze the corrections in the two

regimes.
We devote most of our attention to atoms at low Z and apply the so-called
Russell -Saunders coupling scheme. (The method is named after the astronomers H.
N. Russell and F. A. Saunders for their pioneering interpretations of complex atomic
spectra.) We temporarily ignore the spin-orbit interaction VSL , and we use the
Coulomb potential energy in Equation (9-37) to find the states of the atom, in first and
second approximation. Figure 9-21 tells us that the noncentral Coulomb interactions
of the ith electron cause the orbital angular momentum L, to be a nonconserved
quantity. The forces produce torques, but the torques sum to zero over the whole
 9 8 Angular Momentum Coupling 483

atom, so that a conservation law holds for the total orbital angular momentum

L=EL,. (9-41)

The interactions in Equation (9-37) do not affect the spins of the particles, and so
another conservation law also holds for the total spin

IS,. (9-42)

The separate conservation of L and S implies that the states of the atom can be
specified by the associated total orbital and spin quantum numbers (fm^-) and (sm We s
).

define these parameters in terms of the quantities L2 , L,, S2 , and S: by the following
eigenvalue assignments:

L2 ^ /*¥(/+ 1) and L z ^tim e ,

S. — hm
2 2
S -» h s(s + 1) and >
s
.

The total j-component quantum numbers are given as sums of the individual
^-component quantum numbers,

m^= zl^f and m =

s 2L m s >
(9-43)

in keeping with Equations (9-41) and (9-42). The allowed values of the quantum
numbers <? and by the rules of vector addition and angular
s are determined
momentum quantization. This method of combining angular momenta produces a set
of good quantum numbers (c"m^sm ) for each atomic state. Since the procedure is s

based on the construction of L and S, the more suggestive name for the method is the
LS coupling scheme.
We interpret LS coupling according to the roles played by the two parts of
Equation (9-37). The central contribution Y.,V-(r ) gives the familiar electron con- :

figurations in which the good quantum numbers refer to the individual angular
momenta L, and S,. The noncentral interaction Vee violates the conservation of L, and
S, but maintains the conservation of L and S. This violation affects the configurations
in the following way. A typical configuration may contain many assignments of the
c
individual quantum numbers (n c m^m The corresponding states can be associated t l i
).

with definite values of m^ and m by virtue of Equations (9-43), and can be s

,

superposed in linear combinations to form states with definite values of c" and s.

Electrons in such a configuration experience the noncentral and assume Vet effect
different energies for different orientations of their angular momenta. Thus, the
correction Vtt produces a splitting of degenerate states in the given configuration so
that separate energy levels emerge for different pairs of total quantum numbers ( and
s. We have seen a simple example of this splitting in the case of the \s2s configuration
of the He atom. Equations (9-27) and (9-28) represent product combinations of
{n x
^ x
m^m 5 ) and {n 2 t"2 m f m s ), with ^=0, in which the m =
i
eigenfunctions
separate into an (c*= 0, 5 = 0) state and an (/= 0, s = 1) state. The energies of the
states are different because of the Vee effect. We have given these He energy levels the
3
names 2s
X
S and 2 s S in Figure 9-16.
 .

484 Complex Atoms

The L and S implies a rotational symmetry' and a corresponding

conservation of
degeneracy among the states of the LS coupling scheme. We find that the energies of
the states may depend on { and s but cannot depend on m f and m as the latter two s

quantum numbers range in integer steps from — £ to £ and — s to s. Therefore, a

given energy level for a particular £ and s comprises (2/+ 1) times (2s + 1)
degenerate states labeled by the quantum numbers (c*m f sm s ). We can also perform a
final addition of angular momenta and introduce the conserved total angular
momentum of the atom

J = L + S.

The total angular momentum quantum numbers j and m f

are then defined by the usual
eigenvalues

h j( j + l)fory~' and hm )
for J,

It is possible to rearrange the (2/+ l)(2s + 1) degenerate states with quantum

numbers (("m^smj and construct as many alternative states with quantum numbers
(c"sjm ). This rearrangement from one set of good quantum numbers to another
exactly parallels the transformation from (nfm^mj to (nfjm^ for the one-electron
atom, as described in Section 8-8 and Figure 8-22. The two sets of quantum numbers
(fm^sm^) and (Ssjm-) afford equally good representations of all the states with the
given energy, at this stage of the LS coupling procedure. Such a collection of states
with definite c* and s is denoted spectroscopically as

2s + X
L

and is called a term. The (2/+ \){2s + 1) degenerate states of a given term are
designated by the final spectroscopic notation

2s+ \r

when the states are sorted according to the quantum number j. We have already-
3
state and the S and S
X
employed this notation to describe the
X

S ground t
excited
states of helium. We emphasize that it is meaningful to assign and spin
total orbital

quantum numbers t° and s to the levels of an atom only in circumstances where it is

legitimate to follow the LS coupling scheme.
The next stage of the procedure is the incorporation of the spin-orbit interaction
VSI from Equation (9-40). We weak coupling between the orbital and
find that this
spin angular momenta of each electron introduces a weak breakdown of the separate
conservation laws for L and S but maintains the conservation of J since the atom
remains an isolated system. Hence, the total angular momentum quantum numbers j
and m are still good for labeling the states. The spin-orbit interaction produces a
small energy shift among the previously degenerate states of a given c"s term and splits
the term energy level into distinct fine structure components for all the possible values of
j. These final energies cannot vary with m and so each component has a remaining
,

(2j + 1 )-fold degeneracy with respect to this quantum number for each assignment

of j.

Figure 9-22 summarizes the LS coupling treatment of the two corrections to the
central field. We begin with the central potential energy £,F(r ;
) and specify con-
figurations by sets of independent-electron orbital quantum numbers («,^,). We then
 9-8 Angular Momentum Coupling 485

Figure 9-22
2s +
Development of atomic energy levels 'L
;
in the LS coupling scheme. The corrections to the

central field break the degeneracy of a given electron configuration in two stages.

CM)
Multiplet

(s
2s+1 L,.
2sTT^ 1
v (2; + 1)
^- Degeneracies —*

Fine structure
Configuration Terms components
?V c
(r£ )
+ V ei 'SL

add the residual electrostatic interaction Vtt and divide each highly degenerate
configuration into term levels with quantum numbers ( and s. We finally include the

spin-orbit interaction and split each term into its j-dependent fine structure compo-
~ J +
nents. The final collection of all levels
1
L ;
constitutes a multiplet originating from a
single configuration. Note that if and s continue to be used through the final stage of
the procedure, even though these quantum numbers are only approximately good in
the presence of weak spin-orbit coupling. It is clear that the utility of f and s, as well
as the validity of the entire LS scheme, must eventually break down as the spin-orbit
interaction grows in strength with increasing Z.
We turn to another method known as jj coupling when VSL becomes dominant over
Vee The two
. corrections have this property for atoms in the high-Z part of the
periodic table. The states of such an atom are determined in first and second
approximation by the central-field and spin-orbit interactions

LKW + VtSI •

while the weaker electrostatic correction Vee is set aside until the final stage. We see at
once that the conservation laws for the various angular momenta take a different
route under these conditions. The leading potential energy E,Fc(r;) conserves L and S ( ;

for each electron. The next-to-leading contribution VSI does not conserve these
angular momenta individually but does conserve the sum

J,
= L, + S,.

We can therefore employ the eigenvalue assignments

2
h2J, (Ji+ 1 ) for J, and hm h for Jiz

to introduce j and
i
m as good quantum numbers, and we can label the states of the
electrons as (j x
m )
j 2 m Ji • • •
) in the absence of the residual interaction Vtt The
. total
486 Complex Atoms

Figure 9-23

Comparison of LS and jj coupling schemes.

Orbital and spin angular momenta are
combined horizontally-then-vertically in LS
coupling and vertically-then-horizontally in jj
coupling.

L, L2 ... —^ L

\ I

angular momentum of the atom is given by the sum of the individual J vectors

J=IJ,

and is conserved whether Vet is included or not. Consequently, we are able to use the
already-defined total angular momentum quantum numbers j and m along with the
individual quantum numbers j i
for each electron, as an alternative set of good
quantum numbers (j j2 l
" " "
jm ,)- We are then in position to use this specification of
the states when we finally include the correction Vee .

These brief remarks summarize all that we intend to say about the method of jj
coupling. Figure 9-23 shows a schematic plan of the LS and jj coupling procedures. It

is understood that a specific pattern of conservation laws is selected according to the

relative strengths of the two corrections, so that a corresponding pathway is taken
across the figure in the two different schemes. We use the horizontal-then-vertical
route and concentrate on the LS coupling scheme in the applications that follow.
We have yet to deduce the quantum numbers, /, s, and j associated with the
quantities

L= !>,, S= £S„ and J = L + S.

These exercises in angular momentum addition are quite similar to the vector-addition
problems encountered in Section 8-8 and Figure 8-22. We begin with the observation
that electrons in filled subshells form a S core and make no contribution to L and S.
X

It follows that the vector sums E,L and £,S pertain only to the optically active
; (

electrons in the atom. Let us be content to examine the case of two electrons outside
filled subshells. We recall that S has already been constructed for two electrons in

Section 9-6 and that the results s = and s = 1 are obtained when we add the two
spin-
]
- vectors. The remaining constructions

L = L, + L2 and J = L + S

then reduce to a single problem involving the addition of two integer-valued angular
momenta.
 9-8 Angular Momentum Coupling 487

The quantized vectors L, and L 2 have magnitudes h jtf (if + ) and ti^2 { tf2 + 1 ] ] l
1 ) ,

and z components hm f and hm f The L z quantum number satisfies the relations

.

m( = rrif + mf and —£< m f < t '.

This parameter has its largest value when m f = /, and m, = £2 and , so the total
orbital quantum number { cannot exceed «f, + £2 . Every lesser integer down to

\£x — t?
2 \
is also allowed in the addition of the two quantized vectors. We therefore
obtain the following list of possibilities for the total orbital quantum number:

t=\t - x
t2 \> K, - <,i + i
,
• • •
,
t +
x 4- 1 > 4 + lv ( 9 - 44 )

As usual, m f ranges from — £ to ( in integer steps for each of these values of ( Thus, .

for the case /, = (2 = 1> we have

£= with m;= 0,

t= 1 with m t = -1,0,1,
{= 2 with m f = -2, -1,0,1,2.

These nine different states describe all nine possible orientations of the selected pair of
vectors L, and L 2 .

The vector addition of L and S proceeds along exactly the same lines to a similar
conclusion regarding the total angular momentum quantum number j. For given
values of t and s we find the following list of possible results:

j = \f-s\, \£- s\ + 1, ...,€+ s- 1, t+s. (9-45)

Each choice of j admits a range of values for the ^-component quantum number m-
from —j to j in 2j + 1 steps. It should be clear that Equation (9-45) holds equally
well for integral or half-integral values of the total spin quantum number s. We add
in closing that these same rules for combining angular momenta are readily adaptable
to the jj coupling scheme.

Example

Let us apply LS coupling to an atom with two optically active electrons, taking
the configuration to consist of one p electron and one d electron. The spin-orbital
assignments for the two particles are (/, = 1, s {
= ^) and {(2 = 2, s2 = -,). We
combine the spins in the usual way to form total spin states with s = and 1,

and we use Equation (9-44) to obtain the values /= 1, 2, and 3 for the total
orbital quantum number. The terms in this configuration are classified as
singlets (2s + 1 = 1 for s = 0) and triplets (2s + 1 = 3 for s = 1). The three
choices of / generate the singlet terms l
P,
X
D, and ]
F and the triplet terms 3P,
3 3
D, and F. Each term level has fine structure components with values of j as
given in Equation (9-45). The s = terms must have j = /, and so the singlet
components are

l
'P,, 'A, and F..
488 Complex Atoms

The s = 1 terms can have

J = 0, l,and2 for (- = 1,

J = 1,2, and 3 for/ = =

2,

1
= 2, 3, and 4 for^ = 3.

The corresponding triplet components are

3n 3
ro, 1 ,2'
Z)
^1,2,3) and r 2,3,4-

Thus >, the entire multiplet consists of 12 different energy levels in all.

9-9 Spectroscopic Aspects of LS Coupling

The dynamics of LS coupling produces a multiplet from a configuration via the two
steps shown in Figure 9-22. This procedure has clear implications for theory and
experiment, since the breakdown of configurations into multiplets is a predictable
phenomenon with observable spectroscopic consequences.
We are concerned with the evolution of multiplets in electron configurations of two
types. A configuration is said to describe equivalent electrons if the same orbital
quantum numbers are assigned to all the electrons outside filled subshells. Examples
2 2 2
are the Is configuration of helium and the ls 2s 2p configuration of carbon. The
electrons are called inequivalent if their («,-/,-) assignments are different, as in the He
configuration ls2s and the C configurations ls 2s 2p3s
2 2
and ls
2 2
2s 2p3p.
We find that particular attention must be given to the Pauli principle whenever we
analyze a system of electrons in the equivalent category. The analysis isassisted by
three observations, put forward originally by F. Hund during the early period of the
quantum theory. These empirical rules refer specifically to the application of LS
coupling in ground-state configurations containing equivalent electrons. The first two
of Hund's rules pertain to the Vee effect and the splitting of a configuration into
A-term levels:

The term of least energy corresponds to the largest possible s while

other term energies increase with decreasing values of s,

and
for maximum s the lowest-energy term occurs for the largest possible t '.

These guidelines can be used to address the problem of finding the lowest-energy level
in a given configuration. The statements do not imply that every term level of
maximum s must lie below all those of the next largest s and do not imply that the
maximum ( must
term of have the lowest energy when s is not maximum. We
illustrate the limited applicability of the rules later in this section.
The first Hund an extension of our arguments about the energies of the
rule is

singlet and triplet states in the two-electronatom. We know from Section 9-6 that
there is less repulsion between electrons in the spin-symmetric triplet states of helium
because the accompanying antisymmetric spatial eigenfunctions give smaller probabil-
ities for finding the two electrons close together. An atom with several electrons is in a

state of maximum s when the system has parallel spins. Such a state is spin
 9-9 Spectroscopic Aspects ol LS Coupling 489

symmetric, and so again the accompanying spatial eigenfunction is antisymmetric in

space and admits minimal repulsion between electrons.
The second Hund rule associates minimal electron-electron repulsion with the
observation that electrons stay farthest apart in states of maximum ( . To see the
plausibility of this argument we first note that the largest choice of / allows the largest
possibility for \m f \. We then refer back to Figure 7-3 and recall that these states have
highly equatorial polar probability distributions in which the electrons are able to
have maximal separation.
We deduce the terms in a particular configuration by applying the addition of
angular momenta and imposing the Pauli principle. Our concern is still limited to
electrons outside filled subshells. Our attention is further restricted to the case of two
electrons so that the two pairs of quantum numbers {n f n,/.,) suffice to identify any x x

configuration. The two spin- particles can form singlet and triplet term states with
77

total spin quantum numbers 5 = and s = 1. To specify the terms completely we

must also determine the allowed values of the total orbital quantum number f This .

straightforward exercise in angular momentum addition is already in harmony with

the Pauli principle as long as the electrons are inequivalent, since the individual
subshell quantum numbers {n/ ) are t
different and automatically satisfy the exclusion

principle. The exercise becomes more involved for equivalent electrons because the list

of proposed terms must be examined for possible violations of electron antisymmetry.

We illuminate these remarks and illustrate Hund's rules in the following paragraphs.
The inequivalent-electron configuration np n'p contains singlets and triplets with {
values 0, 1, and 2, as noted in our comments following Equation (9-44). The singlet
3 3
P, and and the triplet terms are S, P, and D. Hund's first two
l l
terms are S, '/),

rules tell us that the

3
D term should have the lowest energy.
The simplest equivalent-electron situation arises in the configuration ns . Our
discussion of the He atom in Section 9-6 has already covered the application of the
Pauli principle to this problem. We see that both
l

S and S terms are possible under

the rules for angular momentum addition, but we find that only the KS term is allowed
by the exchange antisymmetry of the two electrons.
The np 2 configuration provides our first opportunity to sample the real difficulties

posed by equivalent electrons. To analyze this case we could list all the possible values
for the electron quantum numbers {m ( m s m e m s ) and then strike those entries with
the same assignments for {m / m and (m ( m $ ). i
) Instead, we adopt a more efficient
way of treating two electrons antisymmetrically by following the approach introduced
in Equations (9-22). These constructions sort out the choices for m and m into
singlet (5 = 0) and triplet (s = 1) combinations and associate antisymmetric and
symmetric behavior under exchange of the two electron spins. The spin states are
accompanied by spatial eigenfunctions whose exchange properties are appropriate for
the overall antisymmetric description of the two electrons. We can take advantage of
2
this procedure and organize our list of
to reduce possible np states. The detailed
arguments are discussed at the end of the section.
The main result of our analysis of the np 2 configuration is the list of values of (
and s in Table 9-2. We find that (= and f= 2 occur only for s = and that f= 1

occurs only for 5 = 1. Hence, the only singlet terms are '5 l
and D, and the only triplet
3
term is P. The six s = entries in the table can be organized so that one state
belongs to 'S and five states belong to D. X
The 3P term contains nine states since there
are three mf values for £= 1 to m s values for s = 1. Thus, the
be coupled with three
3
P terms of the np 2 configuration represent 15 different states in all,
l
S,
l
D, and
appreciably less than the number found in the np n'p configuration.
490 Complex Atoms

Table 9-2 Orbital Quantum Numbers in the Configuration np

Total Spin s = Total Spin s = 1

m, m,c
'1 2
= mf + mf f m,<l
m'V,
'2
m /= m A + m f, *

1 1

'
1

&
1

1-1"
& 2,0

--1 1 .

2,0
"

- 1

&
-1

1 -1 -2

A third Hund rule is also available as another guideline to use in the final stage of
multiplet formation. We recall from Figure 9-22 that the spin-orbit correction VSL
acts as the last step to split the various A-term levels into their j-dependent fine
structure components. The empirical rule identifies an incomplete subshell of an atom
as either less than or more than half-filled and arranges the fine structure in either
normal or inverted order:

The lowest energy level in the lowest-energy term corresponds to the

smallest j value j = \( — s\ in the normal case, or the largest j value

j = /+ s in the inverted case.

We offer the following remarks to give some theoretical justification for this rule.
Equation (9-40) describes the spin-orbit interaction VSL in terms of the coupled
orbital and spin angular momenta of the individual atomic electrons. It is possible to
prove that electrons in filled subshells make no contribution to this expression. It is

also possible to reexpress the Vsl effect in terms of the total orbital and spin angular
momenta I, and S. In the end we find that the expectation value of Equation (9-40)
turns into a simple formula for the spin-orbit energy shift:

= 4<S-L>. (9-46)

The expectation value is taken in a term state with quantum numbers {^sjm
t
) and
produces a proportionality constant A whose value is independent of j. We use the
familiar inequality

<S'L> = -</ L2 -S )= j[j(j+ 1)-/(Y+ !)-*(*+

2
1)],
 9-9 Spectroscopic Aspects ot LS Coupling 491

and we immediately reduce the formula to a final expression involving the quantum
numbers t s, and j: ',

Ah 2 r

(Vsl) = —[Aj+ l)-'('+ D-s(s+ 1)]. (9-47)

This result predicts a splitting of fine structure components in a given A term and
orders the energies monotonically with j for the given choice of i and s. It is easy to
derive two conclusions from Equation (9-47):

and

It follows that the shift to the lowest energy occurs either in the state with j = j mm if

A is positive, or in the state with j = jmax if A is negative, as indicated in Hund's third

rule.

The difference in the energy of adjacent components is an interesting observable

quantity. We can predict this energy interval directly from Equation (9-47):

= —
Ah 2
[j(j+ !)-(>" lb'] =Ajh 2 . (9-48)

The result confirms Lande's interval rule, another relic from the early era of atomic
spectroscopy:

The energy separation of successive components in a given

term is proportional to the larger of the two j values.

Experimental support for this rule is well documented wherever LS coupling is

applicable.
Inverted fine structure is seen instead of normal fine structure when the incomplete
subshell is more than, instead of less than, half-filled. These situations are connected
by the fact that a fully occupied subshell has vanishing angular momenta and
vanishing spin-orbit interactions. We can relate occupancy and vacancy in a partially
filled subshell if we interpret summations of the type found in Equations (9-40) to
(9-42) as

n N N— n N-n
E
electrons
= I
electrons
E = - E ,

holes holes

where jV denotes the number of electrons needed for full occupation of the subshell.
Thus, n electrons and N—n
holes make equivalent contributions to quantities like L,
S, and (VSL ), except for the change in sign. Fine structure inversion follows from this
observation when the more-than-half-filled case n > N/2 replaces the less-than-half-
492 Complex Atoms

Figure 9-24

Schematic diagram of terms and fine structure components for an np n'p configuration and for
an np' configuration. Fine structure splittings are greatly exaggerated relative to the energy
differences between terms.

s = o e=o ,_ 7 = ,_ s =o e=o ,„ 7=0

s=0 f=l ;= i

°-=±Ji3i D >=2 lD2

s=o e=2 7=2
D l
D>

np n p np

^±Jl2is _ili_3o

7=2 j
= 2
3P 2 3
\s=l -p 2
f=l \s=i e=i
;'= l

3
p
<>
\ ;
=
1

7"
Pn

>=3 ,
D
W_f=2 3 ,
>= 2
;'= i

filled case n < A^/2. The argument also implies that no fine structure is expected
when the subshell is exactly half-filled.
We can use Hund's rules to deduce the state of lowest energy in a normal multiplet
by selecting the largest s, the largest /, and the smallest j, in that order. Let us also
imagine a conjectured extension of this procedure in which we order all the levels of a
multiplet with increasing values of the energy first by decreasing s, next by decreasing
l
£ and last by increasing j. This strategy is applied in Figure 9-24 to the terms S, P,
l
,

1), 'A', 7\ and I) in the np n'p configuration. Note that all s = 1 terms are predicted
1

to lie below all s =

S
terms and that fine structure is expected only in the terms P
and D. The entire multiplet is supposed to consist of the ascending array of energy
levels

I)
1,2,3 0,1,2
l

D, %
The figure goes on to show the altered prediction of levels for the equivaletit-electron
configuration np 2 . We have just learned that the Pauli principle excludes half of the
above terms so that the resulting multiplet contains only the levels

3d 17)
1Ji
"0,1,2
 9-9 Spectroscopic Aspects of LS Coupling 493

2
It is instructive to count the possible values of m- for each assignment of j in the np
case:

3
P , 2
has m- = 0, m = —
]
1 to 1 , and m — — )
2 to 2,

while
l
D
2
has m = —2 to 2, and 2S has m ] = 0.

The exercise demonstrates again the existence of 15 different states in this equivalent-
electron system.
The proposed ordering of energy levels in Figure 9-24 is actually realized by many
atoms, at least in equivalent-electron situations of the type np'. Figure 9-25 shows the
extent to which the carbon atom fulfills the predictions. We know that the ground
state of carbon has the configuration Is 2s 2p and we see in the figure that the ,

lowest configurations of the two optical electrons are 2p 2p3s, and 2p3p. It is clear ,

that the actual levels of carbon agree with the predictions for 2p~ but disagree
considerably with the ordering proposed for 2p3p.
The LS coupling scheme is based on certain good angular momentum quantum
numbers in the system of interacting electrons. Parity furnishes another good quantum
number to associate with the levels of the complex atom. This property is expected
because the dynamics of the atom is governed by the interactions

LK(r,)+ K + e
v,
SL

and because these quantities are not affected by the parity operation r -> — r. We use
the orbital quantum number c*
t
to obtain — 1)
( as the parity of the ith electron. We
then use all the independent-particle quantum numbers ((*](*, • • f7 ) to establish the

parity for an entire multiplet of states. Thus, Figure 9-22 tells us that the space-inversion
property of every term and component is decided at the configuration level and
remains good even after the conservation of each L ;
is broken by the secondary
corrections. A fully occupied subshell contains an even number of identical t"
l

assignments and contributes even parity, so that the optically active electrons de-
termine the overall parity of the multiplet system. As examples, both of the multiplets
for np n'pand np~ have two odd-parity electrons in their starting configurations, and
soan assignment of even overall parity follows for every level sketched in Figure 9-24.
Note that the evenness or oddness of the total orbital quantum number ( has no
bearing on this conclusion.
The energy levels in Figures 9-16, 9-18, 9-19, and 9-25 show many differences in
energy of order 1-10 eV. Radiative transitions among these levels generate spectral
lines in the visible range of wavelengths. We can attribute such optical transitions to
oscillations of the electric dipole moment of the atom, and we can assume the validity
of the electric dipole selection rules. We have argued that these rules act as conserva-
tion laws for the system of atom-plus-radiation, in which an electric dipole photon
away one
carries unit of vector angular momentum. Changes in
ft the total angular
momentum quantum numbers of the atom must therefore obey the conditions

A/ = 0or±l (but 0-^0) and Am- = 0or±l,

as in Equations (8-43) and (8-44). The parity of the atomic state must undergo a
change, either odd -* even or even -» odd, because the emitted photon also carries
away odd parity. We can go beyond the domain of strict conservation laws and
494 Complex Atoms

Figure 9-25

Energy levels of the carbon atom. Singlet and triplet terms are shown for the configurations
2/r, 2p3s, and 2p3p.

»S »P l
D '" 3
S 3
P 3
D
C * e

11
-

... ...

10 -

% l
D2
9 3
J\n.2
^X
2p3 Pj
3
«i 3
£,
/':
;

8 -

3
2p3s^ *0.l.:

L
s

2
2P

eV ^0.1.2

include the quantum numbers LS coupling scheme in these selection rules. The
of the
properties of the electric dipole moment are independent of spin, and so the total spin
quantum number is not affected in the transition. This observation implies that the
condition on j becomes an immediate condition on the total orbital quantum number
and results in the additional pair of selection rules

A* = and A<f= Oor ±1 (butO -f* 0).

These constraints on / and s hold as long as <f and s are sufficiently good quantum
 9-9 Spectroscopic Aspects of LS Coupling 495

numbers for the description of the atom. The independent-electron quantum numbers
(^,^2 • •
/z ) have a similar status in the radiation process. If the radiation can be
attributed to a single electron, then the electric dipole moment refers to that electron

and the orbital selection rule takes the form

A< = +1.
(Note that the possibility A/, = is ruled out because the parity of the atom must
change.) We observe that the A = 5 rule forbids singlet -triplet transitions in atoms
with two optical electrons, as in the case of the para and ortho systems in helium. Our
diagram for the carbon atom in Figure 9-25 is patterned after the helium levels in
Figure 9-16 so that attention can be drawn to this analogy.
We have been assuming that the atom is isolated from any applied external field.

We therefore have no preferred direction in space to select as an axis of quantization.

This existence of a symmetry with respect to the choice of z direction implies that the
energy of the atom cannot depend on the z-component quantum number m-, so that a
(2j + l)-fold degeneracy holds for every energy level with total angular momentum
quantum number j. We can introduce a natural choice of axis and break this

degeneracy by applying a constant magnetic field B. The additional magnetic

interaction between the atom and the field produces an m -dependent energy level
shift. This shift of levels is observed in the emission spectrum of the atom as the
familiar Zeeman effect.

We take the z axis in the direction of B and express the magnetic interaction by the
usual formula
VM = -n-B= -ix z B.

The magnetic moment of the atom is constructed from the orbital and spin contribu-
tions of each electron in the manner of Equation (8-45):

^= tv-i= -^L(U + 2S,)= -^(L + 2S).

Observe that g s
= 2 is again used for the electron spin g-factor, and note especially
that the result is ideally suited to the strategy of LS coupling. Let us consider an
energy level for a fine structure component 2s+ L with quantum numbers (Ssjm
X

)
). We
write the formula for the energy shift due to the magnetic interaction in terms of the
expectation value of VA{ in this state:

(VM )= - B ( ti z ) = ^-(L Z
+ 2SZ ).

We then recall the derivation of (/*,) in Equation (8-50) and realize that the same
techniques can be carried over by substituting the quantum numbers of the many-
electron atom. The final formula for the energy shift can therefore be quoted directly
from Equation (8-54):

( Vm) = gV-B Bm j'

where

j(j + i) + j(j + i) -(((+ 1)

s
' l +
uJTT)
Note that the Lande g-factor varies with if, s, and j as in Equation (8-51).
 : ,

496 Complex Atoms

These results admit the real possibility for an s = atom to exhibit a normal
Zeeman effect. An
atom is in a s = singlet state with j = ( and g = 1, just like the
hypothetical hydrogen atom without spin in Section 8-3. The selection rules allow
transitions only to other singlet states, and so the application of a magnetic field causes
the emission lines of the singlet-state atoms to trifurcate in the classical manner
predicted by Lorentz. This possibility is left for further exploration in Problem 24 at
the end of the chapter.

Detail

Table 9-2 lists the quantum numbers m f and m ft for two equivalent electrons
configuration. The compilation is separated into columns for s =
2
in an np

and s = 1 and is assembled in symmetric and antisymmetric combinations for

the three ( values 0, 1, and 2. Spatial states are symmetric for s = and
antisymmetric for s = 1, and are tabulated as pairs of (m^m f ) assignments by
A
the notation
s
and [
We convey the meaning of these symbols by letting
[ ]
.

entries in the table correspond to the following spatial eigenfunctions for two
electrons with quantum numbers «, = n 2 = n and ( = = 1 x
(.-,

for \m f — 1 mf = l]

mf = 1 mf =
for
mf = mf

A
mf = 1 mr =
for
777^- = mf = 1

Note that the angle-dependent factors control the exchange behavior of these
expressions in a manner consistent with the definition of the functions \p and
"V =
A
\p in Equations (9-22). It is clear that the symmetric function i/^ nas -

and /= 2, given the assigned values m f = m e = 1. Both functions »//f, and i^fj
have ^2^= 1, in view of their {m f m r assignments, and can belong to either
)

/= 2 or /= 1. We like the <?= 2 function j|/f2 and

note that \p 2l is symmetric, ,

must also have £— 2, so that the antisymmetric partner ^f, must have /= 1.
We have anticipated the demonstration of these total orbital quantum numbers
by labeling the functions as 4> S/J. Other entries and { values in the table can be
understood in similar fashion. (We note that our use of the eigenfunctions i|/^
is a device intended to impose the Pauli principle on the two outer electrons
alone. Thus, our procedure is not a rigorous application of the Pauli principle to
the entire Z-electron system and is meant to be applied only for the determina-
tion of the term quantum numbers £ and s.)
 9-9 Spectroscopic Aspects of LS Coupling 497

Example

The ground-state configurations at Z= 12, 13, and 14 are given in Table 9-1 as

2
[Ne]3/-' forMg, [Ne]3s 3p for AI, and [Ne]3j 2 3/> 2 for Si.

The Mg configuration is composed of filled subshells and is expected to have a

l
S ground The Al atom has one optical p electron, implying a doublet
state.

term with s = ^ and /= 1. The possible j values are \ and so that the P 77

term splits into 2P 1/2 and 2P 3/2 components. The P 1/2 state is predicted to have
the lower energy. The Si atom has two equivalent p electrons outside filled
subshells. The lowest levels should be just like those sketched on the right side of
3
Figure 9-24, where the P state is found to have the lowest energy.

Example

The ground state of the Fe atom at Z= 26 is a ls

2 2 6
2s 2p 3s 3p 4s' 3d
2 6 2 6

configuration. The occupation of the outer subshell by six d electrons is

equivalent to a subshell with four d holes. The largest possible value for the total
spin quantum number corresponds to the case of four parallel spins, where s = 2
and 2s + 1 =
happens that the \D term has the lowest energy. The
5. It

combination of quantum numbers s = 2 and t'= 2 admits the possible j values

0, 1,2, 3, and 4, and so the fine structure components 'Z) 2 3 4
are expected to ,

form an inverted system in which the 5 Z)4 component occurs at the level of least
energy.

Example

Let us conclude the section and the chapter with some remarks about the
He-Ne laser to add to our previous description of the device in Section 3-9. We
illustrate the relevant transitions of the two atoms in Figure 9-26. Operation of
the laser begins with a pumping process that raises helium atoms from the
ground state to the singlet and triplet ls2s excited states. Note that the electric
dipole selection rules do not affect these transitions since the excitation of atoms
in the gaseous medium of the laser is collisional rather than radiational. The
excited He states are metastable because the selection rules inhibit spontaneous
transitions back to the ground state. Helium and neon atoms transfer their
energies of excitation via the collision process

He* + Ne -» He + Ne*.

This mechanism populates the higher 2p 5 5s and 2p 5 4s levels of neon so that

population inversions exist with respect to the 2p 5 3p levels at lower energy.
Laser transitions can then be induced between these states, as indicated in the
figure. The particular stimulated emission of 1.96 eV photons in transitions from
5 5
2p 5s to 2p 3p results in the generation of a 633 nm laser beam. The
subsequent spontaneous decays 2p b 3p -> 2p 5 3s -> 2p 6 are allowed by the elec-
tric dipole selection rules.
 8

498 Complex Atoms

Figure 9-26

Energy levels and transitions of He-Ne laser. Two four-level laser systems operate in neon
5
through population inversions in the 2p^5s and 2/r 4s states with laser transitions to the 2p 5 3p
levels.

21

ls2s
20

L9

Pumping transitions

17

eV
Ls<

Problems

I. Show that the expression Ef<;=1 (l/|r, — r

;
|) consists of Z(Z — l)/2 terms. Show also

that the double summation can be rewritten

- i —
as

2. The ground state of the helium atom lies 24.6 eV below the ionization level for the singly
ionized system He + + e. Deduce the position of the helium ground state relative to the
t +
double-ionization level for He + 2e.

3. Suppose that, in first approximation, the helium eigenfunction i^(r,,r,) is assumed to

obey the equation

-—
2m
Vf + V./H-
477f r,
+
r.,
U = £*
e y J

with Z= 2. What would the ground-state eigenfunction and energy be in this case?
 Problems 499

The sixth row of the periodic table lists the elements from Z= 55 to 86. What electron

subshells are filled in assembling the ground states of these 32 atoms? Identify the
ground-state configurations for Z= 55 and 56 and for Z= 81 to 86.

Consider an alkali atom in its ground state, and assume that the single electron outside

closed shells experiences constant screening with Zcff

> 1 . Use the tabulated values of the

ionization energy to estimate Z cff

for lithium, sodium, and potassium.

The MN x-ray lines in the M series of any element correspond to M —> N hole

transitions in which an yW-shell hole is filled by an electron from an N subshell. Sketch an

x-ray level diagram showing all the M and N subshells labeled by their single-particle

quantum numbers, and identify all the allowed MN hole transitions.

The x-ray lines of tungsten include the following wavelengths:

KL U KL m KM 1U L X
M XU
0.02138 0.02090 0.01844 0.12627 nm

The K absorption edge occurs at 0.01784 nm and the A'-shell energy is given as 69.52
keV. Use these data to calculate the wavelength for each of the L absorption edges and
the energy for each of the L subshells. Compare the computed values with the results

given for tungsten in tables of x-ray information.

Let the eigenfunction for the three-electron atom be written as a Slater determinant:

*.0) M l
) * Y 0)

0.2.3)--^ * a (2) ^(2) * y (2)

*„(3) */,(3) * y (3)

Demonstrate the exchange antisymmetry of this construction, and show that \p(l,2,3)
satisfies the exclusion principle. Verify also that \p(l,2, 3) is properly normalized.

9. Show that a definite parity can be identified with any Slater determinant for the
Z-electron atom.

10. Express the singlet and triplet He eigenfunctions in the ls'2s configuration in terms of
Slater determinants.

11. Let there be a spin-spin interaction for two electrons given by the formula

vss = fs, • s,

in which f is a constant. Evaluate the interaction energy in the singlet and triplet states of
the two electrons.

12. Refer to the wavelengths given in Figure 9-18 for the spectral lines of lithium, and
calculate the energies above the ground state for the lithium levels shown in the same
figure.

13. The spectrum of sodium includes lines with wavelengths (in nanometers)

818.3256, 819.4790, 819.4824

corresponding to the 3d —> 3p transitions indicated in Figure 9-19. Use the spectroscopic
notation n£ L: to specify the states involved in each of these transitions. The deduction
should allow for the fact that the sodium 1
D states form inverted doublets in which j '
= \
lies above j '• = f Use the wavelength data
. to calculate the splittings of the initial and final

doublet levels.
500 Complex Atoms

14. The ~F levels of sodium consist of pairs of states whose closely spaced energies are difficult

to resolve. Assume a normal fine structure ordering of the j = -, and j = j states, and use
a hydrogenic model of the valence electron to predict the spin-orbit splitting in the lowest
F doublet.
15. Consider two optically active electrons in orbital states with quantum numbers (/, = 1,

m/ = 0) and (Y, = 1, m f
- = 0). Use graphical constructions like those in Figures 8-22
and 9-17 to represent the possible results for the total orbital quantum number t.

16. Let an atom have one p electron and one d electron outside filled subshells, and use jj
coupling to determine the possible values of the total angular momentum quantum
number j. Show that the occurrence of j values is the same as in the LS coupling scheme.
17. The lowest excited states of the Be atom correspond to a 2s2p configuration of optically
^ >+
active electrons. What 'Z,
;
components originate in this configuration? Assume that
Hund's rules hold for the multiplet and deduce the ordering of the energy levels. Refer to
a table of beryllium levels to see if the ordering occurs as predicted.

18. The spin- orbit energy shift takes the form

(VSL ) = A(S ' L) ( A independent of j)

LS
in the coupling scheme. Obtain expressions for the shift in states of maximum and
minimum j for given values of t and s.

19. Examine the terms and fine structure components in the configuration np n'd, and use
Hund's rules to identify the term and component of lowest energy. Extend the scope of
Hund's rules to predict an energy level diagram for the whole multiplet, showing the
ordering of all the various terms and components.
20. The atoms potassium, calcium, scandium, and titanium have atomic numbers Z= 19, 20,

21, and 22. Identify the ground-state configuration of each atom, and organize the energy
levels of each of these configurations according to the total quantum numbers s, /, and j.

Deduce the quantum numbers of the lowest-energy state of each atom, and identify the
";v f
state by the spectroscopic notation L .

21. Predict an energy level diagram showing the terms and fine structure components in the

2p3i configuration of the carbon atom. Compare the prediction with the known results

shown in Figure 9-25.

22. Refer to the energy level diagram for the carbon atom in Figure 9-25 and indicate all the

transitions allowed by the electric dipole selection rules.

23. The fine structure components for the lowest term of the iron atom have the following
tabulated energies (in cm _1 units):

5
A '7J j
5
a 5
A f,

A,
415.932 704.004 888.129 978.072

Use these numbers to check the validity of the Lande interval rule.

24. The excited singlet states of carbon 2p3s 'P, and 2/r 'Z)2 are shown on the energy level
diagram in Figure 9-25. The two excitation energies are quoted in tables as 61982 and
10194 cm" '. Let a 1 T magnetic field be applied to the atom and identify all the allowed

transitions between the two split levels. Show that the normal Zeeman effect should be
observed, and calculate the corresponding wavelength shifts.
 TEN
MOLECULES

In previous chapters we have studied the

properties of the atom, that is, a single nucleus surrounded by a cloud of electrons. In
our everyday dealings with matter, including that making up our own bodies, it would
seem that such isolated atoms are rather rare and are encountered considerably less
frequently than are molecules, which are the aggregates of two or more atoms. Indeed,
all of our bodily processes, including breathing air, digesting food, and the formation
of DNA in the cell, include chemical reactions that involve taking apart one molecule
and recombining its constituent atoms to form other molecules. Our very existence is

as inextricably linked to the nature of molecules as it is to that of atoms or nuclei.

Chemistry is the science of molecules. The various forces that hold molecules
together include the covalent, ionic, and van der Waals interactions as manifestations
of the chemical bond. All these forces are basically electromagnetic in nature but also
involve, as we see in this chapter, some rather subtle quantum mechanical effects.

The simplest molecular form is the diatomic hydrogen molecular ion HT , consist-
ing of two protons and a single electron. The next in order of increasing complexity is

H 2 , with one more electron than H.| These two molecules

. illustrate some of the basic
principles involved in molecular structure, including in the case of H , the covalent bond
inwhich the two nuclei "share" the two electrons equally. Other molecules, such as
NaCl in which one nucleus steals an electron from the other, are held together by a
somewhat different force known as the ionic bond. Atoms with closed shells such as
argon attract each other with only a much weaker force known as the van der Waals
interaction.

As with atoms, the most fruitful way to probe the structure of molecules is by
spectroscopy. Not surprisingly, molecular spectra are often more complicated than
those of atoms. This additional complexity arises because, in addition to electronic
transitions, there are energy changes involving the relative motions of the nuclei that
make up the molecule. Such motions are classified as rotational and vibrational. Because
the rotational transitions involve relatively small energy changes, the spectra occur in
characteristic groupings of very closely spaced lines called bands.

501
502 Molecules

While the most mundane features of our lives depend on molecular processes,
molecules are by no means restricted to our local environment. Astronomical observa-
tions at radio-wave frequencies have shown in recent years that molecular clouds are
spread throughout the universe. Molecules that do not occur naturally on Earth have
been discovered in space. Molecular clouds are found to be closely associated with
regions giving birth to stars in galaxies. It would seem that molecules may be equally
fundamental to our understanding of nature on every scale from the cosmological to
the biological.

+
10-1 Binding by Quantum Tunneling: H 2

A molecule is a collection of two or more nuclei and their associated electrons with the
whole complex bound together by electromagnetic forces. Solving the problem of a
complex atom is difficult enough; here we have an even more complicated multicenter
problem so that the electrons can be associated with one or more of several nuclei. To
simplify the difficulties inherent in studying molecules we look primarily at the
diatomic (two-atom) system. Furthermore, we begin our discussion with the simplest of
these, H.^, which consists of two protons and just a single electron.
Electrons are considerably less massive than protons so that electron rearrange-
ments occur much more rapidly than those of the more ponderous nuclei. This fact
results in a useful technique, introduced by Born and J. R. Oppenheimer and known
as the Born-Oppenheimer approximation. The nuclei are assumed to be at fixed points
and the electron energies and wave functions are then found as functions of the fixed
nuclear positions. The total electronic energy is then used, together with the direct
internuclear forces, to form an effective potential energy for the nuclear motion.
Figure 10-1 shows the arrangement of the two protons in H^; both are on the z
axis, one at — R/2 and one at R/2, so the distance between them is R. The electron is
at arbitrary position r. The nuclear positions are taken as fixed so we need write the

Figure 10-1

Molecular coordinates for HJ The

. protons
are at -R/2 and R/2; the electron is at r.

The z axis is taken along the internuclear

line.
 +
10-1 Binding by Quantum Tunneling: H? 503

Figure 10-2

Potential energy seen by the electron in Hj as it moves along the z axis. The dotted line gives
that part of the potential arising just from the proton at z = - R/2. The dashed line shows the
same for the proton at z = R/2.

Schrodinger equation for only the electronic eigenfunction ip (r):

e

2
ki- ke ke'
+ - - }xb (r) = e.iMr), (10-1
2ra,
r
|r+ R/2| |r- R/2| R '

where m t
is the electron mass, k = l/47re , and ee is an energy eigenvalue of the
electron. The first term in curly brackets is the electron kinetic energy operator. The
second and third terms are the attractive potential energies caused by the protons at
— R/2 and R/2. We have also included the last term, the proton-proton repulsion,
as a part of the electronic potential energy for convenience.
Figure 10-2 shows a cut through the potential energy function as one travels along
the z axis.The potential energy diverges at z = — R/2 and z = R/2 as it must for
the Coulomb force. Near z = the function is a bit lower than it would be if there
were only one atomic potential energy curve. The potential energy is symmetric about
this point. This double-welled potential energy function is analogous to that consid-
ered in Chapter 5 (Figure 5-25) and the wave functions have properties similar to
those found there.
Suppose that only one of the potential wells is present (e.g., the one around
z = R/2 as indicated by the dashed curve). Then the problem is quite familiar and
the ground-state wave function is just ^^(r — R/2), the hydrogenic Is state centered
at r = R/2. Similarly, a particle in the potential well centered at r = —R/2 has
wave function ^(r +
R/2). Because both potential wells are the same, just shifted in

space, the energy levels in each are identical and equal to e u .

Now consider the situation in the combined problem represented by the solid line in
Figure 10-2. While the electron is in the neighborhood of r = R/2 we expect the
ground-state wave function to be approximately equal to <p u (r
— R/2) because in
much of that region the dashed line and the solid line coincide. While the electron is in
the neighborhood of r = —R/2, the wave function is approximately u (r + R/2). A <j>

further necessary property of the wave function arises from the symmetry of the
potential energy about the point r = 0. We expect the probability P(r) of a particle
504 Molecules

being around r = — R/2 to be equal to that of it being around r = R/2. More

precisely, we require parity invariance P( — r) = P(r). In terms of the eigenfunction
this is equivalent to

*(-r) = ±*(r). (10-2)

Molecular wave functions that are even under a parity change (the upper sign) are
odd are ungerade. (These are the German words for
said to be gerade; those that are
"even" and "odd.")
Eigenfunctions that satisfy both of the above sets of requirements are given by

* + (r) = ^=(<Mr - R/2) + *,,(r + R/2)) (l0-3a)

and

*_(r) = ^(*i> - R /2) - 4>Jr + R/2)). (l0-3b)

When -
r is
u (r + R/2) * lt (R) is small and $ ± (r) * (1/ y/l )<$> u (r
near R/2, 4> <f>

R/2) as required. (The 1/ v2 is just an approximate normalization factor.) To see

the parity property of \p + (r) we note that

" r) = 'r ' r + R/2))

* ±( {4>ui ~ R/2) ± <Pui '

72

From Chapter 7 we know that the l.r state for hydrogen is also even under parity
inversion, that is,

<M-r) =*,,(*)>

so that Equation (10-2) is satisfied as well. A graph of the functions \p ± is shown in

Figure 10-3.
Note that the \p + °f Equations (10-3) are not exact solutions of Equation (10-1),
even though they behave reasonably. They are approximations to the two lowest states

Figure 10-3

Graph along the z axis of the approximate eigenfunctions \p _ (r) (Equations (10-3)) for H^
 101 Binding by Quantum Tunneling: H2+ 505

of H+ . An exact solution of Equation (10-1) is possible but the complications involved

in finding it do not offer as much physical insight into the problem.
The energies associated with these wave functions are found by computing the
expectation value

(e) = e
±
= jr ±
— h
2

v; + V(r) xp
± dr. (10-4)

This quantity is a simple generalization to three dimensions of the one-dimensional

energy expectation value given by Equation (5-65) in Section 5-7. The quantity
— (h 2 /2m)V 2 is the three-dimensional kinetic energy operator that replaces the
one-dimensional form — (h 2 /2m) d
2
/dx 2 and, V(r) is the sum of the three potential

energy terms in Equation (10-1).

To simplify the calculation of the energies we establish the following shorthand
notation:

2
h

lm e

2 2 2
ke ke ke
v — V ~ vR =
|r-R/2|'
b
|r + R/2f Y 2 '

4>fl = <#>,>- R/2); $ 4 = $„(r + R/2).

The total potential energy is then

V(r) = K+v b
+ vR .

Note that the \p ± are real because <pa and <p h are real. Putting the ip
+ of Equations
(10-3) into Equation (10-4) gives for the energy estimate

e
± =-f(<t>a ±<t> b )[T+ Va +V b
+ VR ](<j>a ±<t> b )dr

=
-f(<t>a ±<P b )[(T+ Va )4>a ±(T+ Vh )4> b }dr
'
1 , 1 ,
+
J Jti( y> + V^ dr + 2
}ti {V° + V ^ dr

±^f<t>a (K+ VR )4> b dr± (Vb + VR )4>a dr.

-f<> b

The fact that <pa and <j>

b
are hydrogenic functions allows us to write

(T+ Kh a
= ^A and (T+ V )$ = b h
e is<j> b .

We also note that

G = J€(V„ + VR )dr = j<t>i(Va + VR ) dx (10-5)

corresponds to the average value of the Coulomb interaction between the electron and
nucleus on site a (at R/2) and the nucleus on b (at — R/2) or vice versa.
 ,

506 Molecules

A quantum interference or overlap term also occurs in the energy. This is

S= f<t>a (K+ VR )<j> b dr = b

(Vb + VR )<t>a dr. (10-6)
f<p

This quantity arises as a cross-term in e + because the electron has probability

amplitude for being on either site. The overlap term is extremely important and is the
source of the binding of the atoms to form a molecule. Note that the term involves the
product <t>a<j> b - The function <pa is localized about R/2 and falls off exponentially as r
moves away from R/2, and similarly for <f> b
. The product is appreciable only in the
vicinity of r = where the two functions overlap. For this reason 5 is usually a good

deal smaller than the direct energy terms, such as e u or G, which depend on 4% or 2b <f>
.

Classically, a particle is trapped in a potential well (e.g., the electron near r = R/2
can not get into the well at r « — R/2 if its energy is less than the central barrier
height as indicated in Figure 10-2). But because of the quantum mechanical barrier
penetration effect, the wave function does enter this classically forbidden region,
resulting in a nonzero overlap integral. Thus, we obtain

e
±
=e u + G±S (10-7)

as the final result.

R becomes large, the overlap of <& and
In the limit that the nuclear separation </>.

and hence becomes exponentially small. It can be shown that G also becomes
S,
exponentially small. Then we have e + —* e, However, for smaller separations the two 5
.

energies e + and e_ are not equal but are split by 2S. The exchange integral 5 turns
out to be negative so that e + (corresponding to ip + the eigenfunction with no nodes) ,

is lower than e_ and is the ground-state energy. More importantly, even though G is

positive, e + is lower than e u which can be considered to be the energy of the

,

dissociated molecule. Thus, the molecule is bound.

The other state that we have formed, \p_, has an energy greater than eu . This state
turns out not to be bound.
Figure 10-4 shows the two energies e+ and e_ as functions of internuclear
separation R. These electronic energies can be interpreted as effective potential energy
functions of the two protons. They either cause the protons to be drawn toward each
other or repelled from one another. We write

V± = e
- eu
±

as the nuclear potential energy functions. Written in this way, the potential energy
goes to zero as R —> oo. V _ is always repulsive but V + is attractive until R gets so
small that the Coulomb repulsion between the protons dominates. There is a mini-
mum in V + defining the equilibrium separation of the two protons in the molecule.
,

The binding of the H^ molecule arises from the exchange integral S in Equation
(10-7). The physical origin of this term can be seen from the behavior of \p in .

Equations (10-3). From the plot of these two functions in Figure 10-3 we see that ^ +
is larger than either 4> = <|>,,(r — R/2) or = <p u (r + R/2) in the region between
a b <f>

the two protons. The probability density associated with the two functions is

2 2 2
l* ± l
= i[l*.l + l*»l ±2fc* 4 ]. (io-8)

The last term is the contribution from the overlap region. In \ip
+ \' this extra electron
 10-1 Binding by Quantum Tunneling: Hf 507

Figure 10-4

Effective internuclear potential energies for

H^~ as functions of proton- proton separation
R. These functions are related to the electronic
energies by F = (
e+— tu The minimum in
.

V+ gives R , the equilibrium internuclear

distance.

density implies a region of extra negative charge, which attracts each proton to it and
partially shields one proton from the repulsion of the other. This is the effect causing
molecular binding in H^; hence \j/
+ is said to be a bonding molecular orbital. On the
other hand, l^^l" has less electron density than it would have without the overlap
term (note \p _ vanishes at the midpoint between the protons), and \p_ is said to be
antibonding.
The G and
1

explicit calculation of i in Equation (10-7) leads to an equilibrium

distance of 0.132 nm and a depth of the potential V+ of 1.77 eV compared to the
results obtained from the exact wave function of 0.106 nm and 2.79 eV. The
approximate function \p + of Equation (10-3) tends to be inaccurate at small R; the
wave functions for the individual atomic wells become quite distorted from Is states at
such separations. Indeed, for R= 0, i/>
+ ought to transform into the ground state of
He + but does not in our approximation (see Problem 3 at the end of the chapter).
It is possible to construct other molecular orbitals analogous to those of Equations
(10-3) by substituting other atomic functions for the Is states. These orbitals represent
excited molecular states, some of which are bonding and some antibonding.
We next examine the angular momentum classification of the molecular orbitals of
HJ. To do this most easily we shift the molecular coordinate system so that the origin
coincides with one of the protons as shown in Figure 10-5. The atomic wave function
for the electron centered on the proton at the origin is now ^(r). This function is
clearly an eigenstate of electron angular momentum f=Q. To examine the angular
momentum properties of the molecular orbital Equation (10-3a), we must also
ip + of
look at the atomic function for the electron centered at r = R, that is, <p u (r — R).
Because this latter state is displaced from the origin, it is not an eigenfunction of the
electron's squared angular momentum L 2 Adding a second center of force at R has.
508 Molecules

Figure 10-5

Molecular coordinates for H.J with the origin

taken at one of the protons.

9<L

ruined the spherical symmetry of the electron's potential energy. The problem is no
longer one having a simple central force. Thus, molecular orbitals cannot be classified
according to if values.
Molecular wave functions for diatomic molecules like HT do have cylindrical

symmetry and therefore turn out to be eigenstates of the z component of angular

momentum L z . In molecular physics the eigenvalues of L. for a single electron are
denoted by \h, where A = 0, ± 1, +2 Just as hydrogenic atomic orbitals have
the letter code s, p, d, . . . representing /= 0, 1, 2, ... , molecular orbitals correspond-
ing to |A| = 0, 1, 2, . . . are designated by the Greek letters o, 77, 8, ... , respectively. As
is shown below, ^ (
of Equations (10-3) are both a states.

Detail

We can easily show that \p + is an eigenf unction of L.. Using the coordinate
system of Figure 10-5, write

l/2
|r - R| = = (r- + R2 - 2rR cos o\
a )

This arrangement of \p + , and hence + itself, depends on r and

i|/ cos > 8 but not
on the azimuthal angle <f>
shown in Figure 10-5. From Chapter 6,

h d
-
L. -»
1 1$
so that

M +
= 0,

and \p ^
therefore corresponds to X = 0.

10-2 Covalent Bonding: H ;

,

The H.J molecule discussed in Section 10-1 is useful in showing the elements of
molecular binding in a reasonably straightforward way. It is the "hydrogen atom" of

molecules. However, the simplest neutral molecule is H.,, which carries two electrons.

We now proceed to treat this fundamental problem.

 10-2 Covalent Bonding: H2 509

H 2 However, there
Figure 10-1 continues to describe the proton configuration for .

are now two electrons at positions an approximate electronic

r, and r2 . We construct
wave function first introduced by W. Heitler and F. London in 1927. Suppose for a
moment that the two protons are at the same point r = 0. We then have the charge
2
equivalent of a helium nucleus. The electronic ground state for this system is a Is
configuration with eigenfunction

;Hl,2)=4> l5 (r 1
)<|>
li
(r 2 )x"(l,2), (10-9)

where x A (h2) ls the antisymmetric or singlet spin function given by (see Equation
(9-25))

4
= ^(T,1 - l,T (10-10)
X' (1,2) 2 2 ).

The spin function must have one electron with spin up and the other with spin down
because both electrons are in the same atomic orbital. In this way eigenfunction
i^(l,2) satisfies the Pauli principle; that is, it is antisymmetric and i//(2, 1) = —^(1,2).
Next, let the two protons be drawn apart along the z axis, one to R/2 and the
other to — R/2. We might expect one electron to be dragged along with each proton.
Then Equation (10-9) would be transformed into

*(1,2) = 4>u(r, " R/2)*,,('a + R/2)x A (l,2). (10-11)

This might seem a good initial guess at a molecular eigenfunction except for two
important deficiencies. First, Equation (10-11) has not incorporated the physical
features found to be necessary for molecular binding in the HT analysis. Each
electron should have a probability of being at each proton, thereby spending extra
time in the intermediate region between the protons. This extra electron density yields
the net attraction that binds the molecule. A second deficiency arises from the fact
that the proposed function does not obey the Pauli principle; it is not properly
antisymmetric as it must be for fermions.

Fortunately, we can easily solve both problems at once by simply adding on to

Equation (10-11) the interchanged state with electron 1 at —R/2 and electron 2 at
+ R/2. The result is

^ L
(l,2) = -^KCr, - R/2)<Mr 2 + R/2) + *„(r2 - R/2)* If (r, + R/2)]

X X ^(1,2), (10-12)

where the superscript HL and the subscript S stands for

stands for Heitler-London
The HL approximately normalized.
singlet spin state. 1/ v2 is put in to make \p
factor
Because x (1) 2) is antisymmetric under electron interchange, the entire wave function
is now antisymmetric. Also, each electron now has a probability of being at each
nucleus. Note, however, that the electrons move in a rather coherent way, so that if
electron 1 moves from the nucleus at — R/2 to that at + R/2, electron 2 flips its
position in just the opposite way. In this way the wave function never allows both
electrons to appear simultaneously on the same nucleus. We might think that this a
positive feature because it would tend to minimize electron -electron repulsion;
however, we show later that mixing in a little of this double-occupancy state actually
improves binding.
510 Molecules

There is an alternative antisymmetric wave function that we can form from the Is
atomic orbitals. First, we construct triplet spin states from the spin eigenfunctions as
done in Chapter 9, Equation (9-26). These are

s '=
xi T 1 1 2 (10-13)

xl,= \Xo= -^(T,l 2

+ 1,T 2 ) (10-14)

,X-i = i i
i 2- (10-15)

Since these states are symmetric under electron exchange, the spatial part of the wave
function must be antisymmetric. By analogy with Equation (10-12) we have

*" L == ^k^i r
" R /2H l5
(r 2 + R/2) - *„(r2 - R/^Jr, + R/2)] X Sm/

(10-16)

The T subscript stands for triplet spin state.

As with H 2 , one of the two states formed from Is atomic functions is bonding and
the other antibonding. To see which is which, consider the squares of the two spatial
portions of the wave functions. The spatial probability densities are

Pff = lWu(^ ~ R/2)tf,(r2 + R/2) + tf,(r 2 - R/2)tf,(*i + R/2)

±2(*„(r, - R/2)*,,(r, + R/2))(*„(r2 - R/2)*„(r2 + R/2))]. (10-17)

The interference term (the last one, like that of Equation (10-8)) depends on the
overlap of electronic wave functions in the region halfway between the nuclei, and
implies that there is extra electronic charge there in the singlet case (plus sign) and
diminished charge for the triplet (minus sign). While the added charge density of the
singlet wave function does enhance electron -electron repulsion, this effect is more
than offset by the added attraction between the extra charge and the two protons. It is
this effect that provides the covalent bonding in the singlet case. The triplet wave

function, on the other hand, is antibonding.

In a molecule more complicated than H 2
there is often a closed-shell core of
electrons, quite tightly bound to their originating nucleus, which participate weakly or
not at all in this exchange phenomenon. The outer electrons that do exchange are
known as valence electrons. Since these electrons are paired in the sense that they
exchange cooperatively from one atom to the other, the bond is called covalent.
L
The energies associated with the two eigenfunctions \p^ and \fiP" may be
calculated. When this is done, forms analogous to those of Equations (10-7) are found:

e ST =2e u + G' ±S', (10-18)

where the upper sign refers to the singlet case and the lower to the triplet. The
exchange integral S' depends on teo-particle overlap integrals and contains terms like

//*,>, - R/2)* u (r2 + R/^Mr.^H./r, + R/2)*„(r2 - R/2) </r, </r2 ,

 W-2 Covalent Bonding. H2 511

where F(r,,r 2 ) can be any one of the various terms occurring in the energy operator.
G' is also a two-particle quantity somewhat analogous to the G of Equation (10-5). S'
turns out to be negative so that the singlet energy is lower than the triplet. The singlet

energy has a minimum as a function of R and exhibits binding while the triplet has no
bound state.
L
As mentioned briefly above, the approximate Heitler- London eigenf unction \p s

can be improved somewhat by including double-occupancy states:

L
^(1,2) = *? (1,2) + Y^[<Mr, - R/2)*u(r2 - R/2)

4
+ « lj (r + R/2)* u (r2 + R/2)] X
1
'

(1,2), (10-19)

where y is an adjustable coefficient. The first term of the new addition has both
electrons near the same nucleus at R/2; the second has both near that at —R/2.
While each of these terms increases the average value of the electron-electron
repulsion, it also gives the system an ionic structure in which there is some probability of
the formation of the ion combinations (H + ,H~) or (H~,H + ). The ions attract one
another and add to the molecular binding. At the equilibrium separation of the
molecule (the minimum of the electronic energy), it is found that y = 0.2, implying
that only a small percentage of the binding results from this process. Note that the
configurations (H~, H+ ), and (H + ,H ), with both
with both electrons on proton 1,

on proton 2, are equally likely so that H 2 does not have a permanent electric dipole
moment. In Section 10-3 we study systems that owe their bonding to the existence of a
permanent separation of charge and the resulting electric dipole configuration.
It is possible to construct bonding or antibonding molecular states from excited

atomic orbitals as well as from Is states. For example, simply replace the Is orbitals in

Equations (10-12) and (10-16) with 2s functions. Excited-state molecular energies

vary with internuclear distance R in a manner similar to the ground-state energy as
shown schematically in Figure 10-6. The R -* oo limit of such energies need not be
zero or all equal. As R — oo, G' and S' of Equation (10-18) go to zero and the energy
>

e s —> 2e u which is the electronic energy associated with the two isolated hydrogen
,

atoms. The bonding state constructed of two 2s states would have the limit 2e 0s as
R — * oo. A bonding excited molecular state such as £ 4 in Figure 10-6 has a minimum
at some R value and does not necessarily dissociate (i.e., separate into its atomic
constituents) even though its R -» oo limit is greater than that of the ground state. On
the other hand, excitation of the molecule from the ground state to an excited state
such as e2 or e 3 in Figure 10-6 would result in dissociation.
As a we consider why a closed shell (noble gas) atom does
last topic of this section

not interact covalently with any other atom. Consider the case of hydrogen and
helium. The bonding molecular wave function has been seen to have a singlet spin
configuration with one spin up and one spin down. Consider a covalent bond
involving the hydrogen Is electron with spin down, for example, and one of the
helium Is electrons with spin up. The wave function involves an exchange term that
brings the down electron over to the He, which then has two spins down and violates
the Pauli principle. This is a somewhat simplified view; a rigorous argument would
construct three-electron wave functions for the two nuclear centers. These wave
functions can be shown to vanish because of the Pauli principle for all but antibond-
ing molecular orbitals. Thus, the molecule H — He does not form.
While similar arguments can be made to show that two noble gas atoms, such as
He — He or He — Ar, cannot interact covalently, molecules such as Ar, do exist.
512 Molecules

Figure 10-6

Electronic states for a diatomic molecule as

functions of internuclear separation R.
Bonding states have minima as in f, or e 4 .

Antibonding states do not support bound

states.

These occur because there is another attractive force mechanism known as the
van der Waals interaction, which is discussed in Section 10-4.

10-3 Ionic Bonding: LiF

Hydrogen has a single electron, and the alkalis (Li, Na, Rb, Cs) have a single electron
outside a closed shell. When any one of these react with any one of the halogens
(F, CI, Br, which are one electron short of completing a shell, they form tonic bonds.
I),

Basically, what happens is that the single s electron of the alkali element (or of
hydrogen) is taken by the halogen to fill its shell; the resulting positive and negative
ions attract one another and the molecule becomes bound.
Consider the molecule lithium fluoride, LiF. The primary question to be answered
+
is why an electron would be pulled off the lithium atom to form Li and move over to
fluorine to form F . The case rests mainly in the fact that all the electrons in a single
shellhave roughly the same average atomic radius. The electronic structure of fluorine
is
22
\s 2s2p\ The n = 1 shell is complete and the n = 2 shell is missing one electron.
All the n = 2 electrons reside at approximately the same average radius, which, of
course, is larger than that corresponding to the n = 1 electrons. Each of the seven
n = 2 electrons is thus screened efficiently from the nucleus by only the two \s
electrons. The resulting Z value seen by each of the n = 2 electrons is not much less

than 7. An extra tenth electron borrowed from the lithium atom sees roughly the same
effective Z value and is bound. The binding energy of this electron to form a negative
ion is known as the electron affinity. This electron affinity, however, is usually smaller
than the ionization potential associated with forming the positive ion. In the case of
 10-3 Ionic Bonding: LiF 513

2
lithium (whose structure is \s 2s) it costs 5.4 eV to pull off the 2s electron (the
ionization potential), and in forming the negative fluorine ion 3.4 eV is released
(the electron affinity) — a net cost of energy of 2.0 eV. However, the energy released
by the binding of the resulting ions (about 8 eV) more than compensates for this
energy expense. This ionization process goes only in the direction indicated, as is easily
+
seen by considering the energy required to form (Li~F ). The electron affinity for
lithium is 0.6 eV; the ionization potential of fluorine is 17.4 eV. The energy
requirement is 16.8 eV, while the net gain through binding of the two ions is the same
+
as for (Li F~).
Note that homonuclear diatomic molecules (those made up of like nuclei, such as
H 2 )
have constituents with equal attractions for the electrons and so do not form
permanent ions within the molecule, although they may have ionic structure in their
wave functions as discussed in Section 10-2. Only heteronuclear molecules (those made
up of unlike nuclei, as HF) can have the permanent charge separation described
above.
There is a simple test by which we can judge the accuracy of the above idea of the
ionicbond in LiF or in any diatomic molecule. If the lithium's electron spends all its
time on the fluorine atom, then the electric dipole moment of the molecule, from
Figure 10-7, is

R\ R
— \
+ e— = eR.
2 / 2

The interatomic separation in LiF is found to be R = 0.156 nm so we expect

p = X 10" X 10' 10 m) = 2.5 X 10 29 C m. The experimental value
19
(1.6 C)(1.56 •

of the electric dipole moment is p =2.11 X 10 -29 C m, 85% of the above model •

value.The lithium's electron does maintain some probability of being on its home-base
atom in addition to spending time at the fluorine; this reduces charge separation from
the model value. There are also other small effects that tend to reduce the polariza-
tion.

The above result indicates the bonding of LiF is only partly ionic; it is also partly
covalent. The lithium's 25 electron pairs with one of the fluorine's 2p electrons to form
this covalent bond. To see how this takes place consider the possible angular parts of
the 2p wave function. There are three degenerate states with angular components

3~

10-20a;

and

(l0-20b)

(Refer back to Table 6-1.) Figure 6-8 shows how the angular lobes of the probability
density corresponding to these states are positioned. Combinations of the F, + ,

functions have lobes in the xy plane. The Y w function shown in Figure 10-8 has lobes
along the z axis. The upper lobe is positive and the lower one negative. Of the three
functions, the one expected to have the largest overlap with a 25 function centered at
a distance R away along the z axis is F 10 . We pair this so-called 2 p. function of
fluorine with the lithium's 25 function for a covalent type of wave function.
514 Molecules

Figure 10-7 Figure 10-8

Model of an ionically bound diatomic Angular function F10 -a factor in the 2p,
molecule. Atom B has the greater electron wave function of fluorine.
affinity and takes an electron from atom A.
The two atoms form an electric dipole with
charges +e and —e separated by distance R.

^- y

The eigenfunction describing the bonding orbitals in this molecule is then a

generalization of Equation (10-19). We place the fluorine at z = — R/2 and the
lithium at z = + R/2 so

*(1,2) = j^^/r, - R/2H 2/,(r 2

+ R/2) + <J>Jr 2 - R/2)^(r, + R/2)]

+ S* 2 ,(r - R/2)^(r2 - R/2)

1

+ C<^(r, + R/2)^(r 2 + R/2)U"(1,2), (10-21)

2 2 2
where normalized by taking \ A + B + C = 1 (see Problem 9 at the end of
\p iS

the chapter). The term with coefficient A is the covalent part of the wave function
and those in B and C involve the ionic structures. Unlike the case of H 2 we have no ,

reason to take B = C and indeed the ionic bonding mechanism we have described
requires B =£ C. Because we know the electrons may double up on fluorine but are
very unlikely to do so on lithium, it is reasonable to set B= as an approximation.
It can be shown that the electric dipole moment of the molecule may be related to
the parameters in Equation (10-21). The result, for the case of arbitrary A, B, and C,
is

p = eR(C 2 - B 2 ). (10-22)

For H 2 , whose eigenfunction is given by Equation (10-19), we have the equivalent of

B = C in Equation (10-21) and p = as expected. In the present case we have

p = eRC 2 . 10-23)

The expe rimental ratio of p/eR = 0.85 for LiF gives us C= v0.85 = A =
0.9,

V — C 2 = 0.4, the latter equality being

1 the normalization condition. Thus, we see
that the percentage of ionic bonding in the total bond of LiF is quite high.
Equation (10-21) we can determine the average energy
Given the wave function of
as a function of internuclear separation. This result tells us many of the properties of
 10 -3 Ionic Bonding: LiF 515

Figure 10-9

Electronic energy for an ionically bound

molecule as a function of internuclear distance.
The energy is adjusted to F(oo) = 0.

^R

the molecule. However, a more direct approach is one in which we guess the form of
the electronic energy on the basis of general physical principles. Such a "phenomeno-
logical" form contains coefficients that vary from molecule to molecule and are
determined by fitting the predictions derived from the potential energy function to
experiment.
The potential energy function usually chosen for a general ionically bound alkali
halide molecule has the form

aR
V( R =
) ae (10-24)
4ire Q R

The second term obviously represents the Coulomb attraction, at large separation R,
between the positive and negative ions. When the ions are so close to each other that
their closed-shell electronic clouds overlap, the electronic energy becomes repulsive
due to the Pauli principle as represented by the first term. The constants a and a,
which control the strength and slope of the repulsive part, are determined from
comparison with experimental data as shown in the example at the end of this section.
A qualitative plot of V(R) is shown in Figure 10-9. While V(R) looks much like V + of
Figure 10-4 or £ of Figure 10-6, it falls off at large R as \/R, which makes it much
longer ranged than either of those energies, since each drops off exponentially.
The equilibrium separation of the nuclei in the molecule is very near the position
R of the minimum in the potential energy. (Zero-point motion changes this slightly.)
This position satisfies

dV
~aae' aR + <>
- =0
~d~R R = R„ 4ite Rq
or
//.'..

(10-25)
477£ aR^
 -

576 Molecules

The curvature of the potential energy at R= R is

K= —
d2
dR
V
2
= a
2
ae- aR » -
477e
2e
2

/t
R=«

from which it is found that

KRl\
a= — 1 /
2 + 4^-^- . (10-26)

Spectral data give R and K directly, as we see in Section 10-8. Putting these values
in Equations (10-25) and (10-26) yields a and a.

The dissociation energy is the work needed to pull the two atoms completely apart
into isolated neutral atoms. If we were to separate the ions to infinity the work needed
would be — V(R ), the depth of the potential energy. The removal of the electron
from the negative ion and its return to the positive ion net a positive energy

d=I -A ,
(10-27)

where /,, is the ionization potential and A is the electron affinity. The dissociation
energy then is related to the potential energy by

D= -V(R )-Q (10-28)

if we neglect the zero-point energy.

Covalent and ionic forces are the primary molecular bonding mechanisms. There
are, however, other physical principles that contribute to interatomic interactions. We
consider one of these, the van der Waals attraction, in Section 10-4.

Example

For the molecule lithium fluoride spectral data yield the values of the inter-
atomic separation R =f)
0.156 nm and the potential energy function curvature
K= 248 J/m2 . From these values Equation (10-26) yields

3
2
1
(248 J/m )
(1.56 X lO^'m) \
6.13
2 +
0.156 nm (8.99 X 10
9
N -m 2 /C 2
)(l.6 X 10~ 19 C)
2
/
0.156 nm
\

39.2 nm -1 .

Then the parameter a is found from Equation (10-25) to be

(8.99 X 10
9
N m /C 2 )(l.6
•
2
X 10' 19 CV 6Ai _ in-16
l0
' .6.13
-e = i
1.1
1 ss 10" lb
J
6.13(1.56 X 10~ m)
= 688 eV.

Thus, the potential energy in Equation (10-24) for LiF becomes

/ 1.44 \
39 2 *
V(R)= |688<-
-

eV,

where R is given in nanometers.

 10-4 Van der Waals Interaction 517

To from V(R) we need the value of Q, in Equation

get the dissociation energy
(10-27). The ionization potential of lithium is 5.4 eV, and the electron affinity of
fluorine is 3.4 eV, so

£=5.4- 3.4 = 2.0 eV.

The potential depth at R ()

is

1.44
F(i? )
= 688^- ,392)(0156) -
0.156
= 1.5 - 9.2 = -7.7 eV.

From Equation (10-28)

D= 7.7 - 2.0 = 5.7 eV.

The experimental value is from the phenomenological

6.0 eV, so our prediction
potential energy function is only about 5%
is quite good consider-
in error. This
ing the fact that there are several small corrections to the potential energy to be
taken into account. These refinements include covalent, induced dipole (see
Problem 1 1 at the end of the chapter), and van der Waals (Section 10-4) forces.

10-4 Van der Waals Interaction

Atoms of the noble gases, having closed electronic shells, do not interact with one
another via covalent or ionic forces. However, there is a weaker attraction between
such atoms, called the van der Waals force. This force is also present in molecules that
do interact covalently or ionically but it is much weaker and of lesser importance.
Despite its relative weakness the heavier noble gas atoms — neon, argon, and so
on — are able to form molecules via the van der Waals interaction. Helium liquifies at

low temperatures only because of the presence of this force.

The Dutch physicist J. D. van der Waals proposed that all molecules have
attractive forces that, at sufficiently low temperatures, can cause liquification. The
force we discuss here has thus been named after him. However, it was London who in
1930 first explained the physical origin of this interaction, which is occasionally called
the London force.
The an induced dipole-dipole effect. We consider here a
attraction arises from
classical model is not totally adequate but does have many of the
of the force that
elements of the quantum mechanical picture. Suppose two neutral H atoms approach
one another, and assume no covalent force. At any instant in time an electron and the
nucleus that it is orbiting form an electric dipole. This dipole creates an electric field,
which is felt by the second atom whose positive charge is pulled one way and its
negative another. It becomes polarized; that is, it develops an induced dipole moment
as shown in Figure 10-10.
We can easily find the behavior of the electric field as a function of distance R
from the first atom. Consider for simplicity a point A on the perpendicular to the
dipole as shown in Figure 10-11. At this position only the vertical components £,sin#
of each field do not cancel. From the figure we see that sin satisfies sin 6

\a/ \JR
2
+ (a/2)" . When the field point is far away from the dipole so R » a, we
518 Molecules

Figure 10-10

Electric-dipole behavior of atoms. An atom

with an instantaneous dipole moment p t

creates an electric field that induces a dipole

moment p, in a second atom.
P2

have sin 8 ~ a/2R. The net electric field is then given by

2Q sin0 2Qa a
Ed = (10-29)
4ire 2
R + (a/2)
2
^e R 2R 2
4ire R3
'

where p x
= Qa is the dipole moment of the first atom. From this we see that E
d drops
3
ofT as l//? as we move away from the dipole, a result that holds even when the point
A is not on the perpendicular.
The second atom in the field Ed acquires an induced dipole moment p 2 having size

proportional to the electric field that it feels. So

«E //5 (10-30)

where a is called the polanzability of the molecule. This is a kind of Hooke's law
approximation in which the separation of the charges is proportional to the applied
force. (See Problem 11 at the end of the chapter.)

Figure 10-11

Electric field E rf
due to a dipole p, . The field is the sum of the electric fields E + and E of the
individual charges + Q. Position A in the xy plane at a distance R from the dipole is

considered. The charges + () are separated by distance a. The distance from either charge to A
2 2
is //? + \a .

»
 104 Van der Waals Interaction 519

The energy of a dipole p, aligned with an electric field E rf

is

U= -p,Ed . (10-31)

To derive this note that if a field is along the z axis, then while a dipole rotates from
the xy plane into alignment with the field, the field does work QEa/2 on the charge
+ Q and work - QE( — a/2) on the charge - Q. Thus, the total dipole energy is

-2Q<La/2)E= -pE.
If we combine Equations (10-30) and (10-31) and then use Equation (10-29), we
find

.? 1 aQ2a 2 1

U = - <xE; = - a
(4we )
2
-K
b
(4we )
2
Rb

We can do some dimensional analysis on a to estimate its size. Equation (10-30)

gives a = p/E, which dimensionally can be written as

a = — qt
— = 47re/ J ,

477C /2

where / is some length in the problem. For a dipole the appropriate length is the
charge separation a, which in this case is approximately the atomic radius. So we
substitute

a = Aire Q a
z
. (10-32)

This result agrees with that of Problem 1 1 . We get

U= - —^
477£ <2 \
-
R
• (10-33)
J

The leading factor is of the same order as I , the ionization potential of the atom.
Thus the van der Waals potential energy function has the form

^vdw(*)~ -I [j) (10-34)

An accurate calculation for two hydrogen atoms gives

^vdw(*)= -13.0/ (10-35)

(^j
instead of Equation (10-34).
This interaction is longer ranged than the exponentially diminishing covalent bond.
Atoms such as hydrogen, which do have the van der Waals
interact covalently, also
beyond the range of the covalent force.
attraction acting effectively at distances
Atoms of the noble gases are attracted to one another by only the van der Waals
force. When they approach so closely that their electron shells overlap, the Pauli
principle causes a repulsive force that increases rapidly with decreasing internuclear
 ~ ~

520 Molecules

Table 10-1 Parameters of the Lennard- Jones 12-6 Potential

a (nm) e (eV)
He 0.256 8.79 x 1(T 4
~
Ne 0.275 3.08 X 10 3
~
Ar 0.340 1.05 X 10 2
"
Kr 0.368 1.44 X 10 2
~
Xe 0.407 1.94 X 10 2

Source: Data from E. R. Dobbs and G. 0. Jones, Rep. Prog. Phys. 20: 516 (1957).

separation. In 1925 J. E. Lennard-Jones suggested a phenomenological potential

energy function that included both attractive and repulsive effects in a convenient
mathematical form. This energy function is

Vu (R) = 4e (10-36)
R \ R
The constants e, a, and n are parameters to be determined to fit gas, liquid, and solid
data. (Even though the energy function is sufficiently weak that the so-called noble
gases are indeed gases at room pressure and temperature, they do liquify and solidify
at sufficiently low temperature.) The most frequently used value of n is 12, in which
case we have the Lennard-Jones 12-6 potential. It is easy to verify that the potential
depth is f and that a is the value of R for which V\AR) = (see Problem 13 at the
end of the chapter).
Some values of e and a for the 12-6 potential for various noble gases are given in
Table 10-1. Note that as one progresses to heavier atoms the polarizability, which
depends on atomic volume, increases and the strength of the interaction also increases.
Molecules with one member an alkali atom (which has a high polarizability) and
the other a noble gas atom can be bound by the van der Waals interaction and can be
observed spectroscopically. Molecules made up completely of noble gas atoms are
difficult to observe but have been detected by use of mass spectrometers.

Example

The noble gases neon, argon, krypton, and xenon are able to form molecules
because of the van der Waals interaction. However, they are weakly bound by-

comparison with molecules held together by other forces. For the ionically
bound molecule LiF we know that the dissociation energy- is about 6 eV. For the
heavy noble gases the dissociation energy is approximately equal to the well
depth. The Lennard-Jones 12-6 potential has a depth equal to the parameter e

given in Table 10-1. For Xe, e = 0.0194 eV. A thermal energy equivalent to e

occurs for a temperature approximately equal to TXe = (fxe/^s)' where k B is

23 10 5
the Boltzmann constant 1.38 X 10 J/K or 8.62 X eV/K. For xenon
this is

0.0194 eV
TXe = r = 225 K.
8.62 X 10" 5 eV/K
At this temperature, which is a little below room temperature, most of the
 10-5 Polyatomic Molecules: H2 and CH4 521

molecules become dissociated by thermal agitation. A corresponding dissociation

temperature for LiF is

6eV
TUF
L,F
= 1
= 7 X 10
4
K.
8.62 X 10~ 5 eV/K
Obviously the van der Waals interaction weak by comparison. For a
is quite
4
pair of helium atoms the well depth 10
is eV. The equivalent
only 8.8 X
thermal energy is only 10.2 K. However, below this temperature we do not find
bound He 2 molecules. Quantum mechanical zero-point motion is large enough
to prevent these light atoms from forming any bound state at all. (See Problem
19 at the end of the chapter.)

10-5 Polyatomic Molecules: H 2 and CH 4

i i i
The electronic configuration of oxygen is ls 2s 2p . As discussed in connection with
Figures 10-8 and 6-8 the p functions have threefold degeneracy; one (call it 2p x
) has
lobes along the x axis, another (2p ) along y,
y
and the third {2pz ) along z. If the four
2p electrons occupy only two of these three states, with two electrons each, then each
of those two states is full. Then, according to the discussion at the end of Section 10-2,
none of the electrons is available to form a covalent bond. However, if the four
occupied states are, say, 2p:2px 2p y then two of the states each have only one electron,
,

which is said to be unpaired. Such a situation allows the possibility of the formation of

two covalent bonds, one with each of the unpaired electrons. In water this results in
the bonding with two hydrogen atoms. A first-approximation model of this molecule
involves simply the one hydrogen s function overlapping with an oxygen 2p and x
the
other with 2py as shown in Figure 10-12. This model has the bonds at a 90° angle.

Figure 10-12

Simple model of the water molecule H ,0.

The electron of one hydrogen has its \s

function involved in a covalent bond with an

oxygen 2/>, function. Another is bonded with
the oxygen 1p function. The angle between
the bonds is 90° in this model instead of the
experimental value of 104.5°. Figure 10-13

Methane molecule CH 4 .

> *
 .

522 Molecules

The repulsion between the two hydrogen ions causes the angle in the actual molecule
to increase to 104.5°. We have seen this example briefly at the end of Section 9-3.
The bonds in H 2 have a fixed angle. Further examples of such directed bonds occur
in the many compounds of carbon. One such molecule is methane, CH 4 Carbon's .

2 2 2 2
electronic state For a 2p configuration of 2px 2p it seems that carbon
is \s 2s 2p .

should form just two directed bonds like oxygen. However, carbon can bond to four
hydrogens by a kind of trick. One of the 2s electrons goes" into an excited p state so
2
that the configuration becomes \s 2s2px 2p 2pz There are then four unpaired elec-
.

trons that can form bonds.

These bonds are not formed by use of the bare states <p 9s , <$>
2p , <p
2p ,
$•>* Four
linear combinations of these four functions can be formed as follows:

*i = 2 (*2, + *2,. + *2 P, + *2,, ) ( 10-37a)

*2 = i(*2*- <hp, + <t>2

Pl
- *2,,)> (l0-37b)

^ 3 = H*2i + hp, - *2P,

- ^)> (lO-37c)

^4 = £(*2, - <hp. - $2 P) + *2p,)- (l0-37d)

It can be shown that these states are directed toward the vertices of a tetrahedron with
the carbon at the center as shown in Figure 10-13. These four states are completely
equivalent to one another in contrast to the original four functions. The ^ (
of
Equations (10-37) are known as hybrid orbitals . The energy cost of having a 2s electron
move to an excited 2p state is more than offset by the binding energy of the four
hydrogens whose \s functions each pair up with one of the states of Equations (10-37).
It costs 8.3 eV to excite the 2s electron but the binding of the four hydrogens yields an
energy of 25.3 eV.

106 Rotation

In the previous sections of this chapter we have assumed the nuclei are fixed while
solving for the electronic states. Starting with this section we consider how the nuclei
move if we allow the electronic energy found in the previous sections to act as an
interaction potential energy function between the nuclei. In a stable state the
electronic energy has a some internuclear separation R This distance is
minimum at .

usually an approximate equilibrium position for the molecule. As a first approxima-

tion we can consider the nuclei to be rigidly fixed at that equilibrium separation but
allow the molecule to rotate freely in space. In Section 10-7 the other possible nuclear
motion, vibration of the molecule about R along the internuclear line, is considered.
A rotational problem analogous to the one taken up here is treated in the example
at the end of Section 6-5 and the system in question is shown in Figure 6-6. The
rotational energy levels we seek are those given in that example. However, because it
is important to see precisely what approximations are involved we start here from

scratch.
The time-independent Schrodinger equation for the two nuclei of a homonuclear
diatomic molecule is

- tHv, 2
+ V-/ *(R„R 2 )
+ V(R l2 ) + (R lt R 2 ) = £*(R„R 2 ), (10-38)
2m
where R,, R 2
are the positions of the two nuclei and R x2 = |R, - R2 |. If we separate
 10-6 Rotation 523

variables into center-of-massand relative coordinates, we find, as with the hydrogen

atom, that the center-of-mass motion corresponds to that of a free particle, while the
Schrodinger equation for the relative motion is (compare with Equation (6-16))

F — +
2
2
A
— —
h

R 8R
2/x \
I

8R
1

2
8
2
8
—}
R
+ V(R) ^ rel
(^,0,$) = £ re ^, (i?,0,$), el

(10-39)

where R, 0,$ are the spherical coordinates of the vector R 12 is the reduced mass ,
ju

m m 2 /(m + m equal in this case to m/2, and A 2 is the angular operator (Equation
i l
)

(6-12))
2
i d d d
— —— sin0—— +
1

A2 = (10-40)
sin© 50 8@ sirr'0 (9<t)
L>

From Chapter 6 it is known that \p can be written in the separable form

+ Tel {R,®,<!>) = F(R)Y, m (Q,<!>), (10-41)

where Y^ m (S,^) is a spherical harmonic. The operator A" acting on Yim yields
— €({+ 1), where £ = 0,1,2,... with t* the nuclear orbital angular momentum
quantum number. That is, / is a measure of the angular momentum of the pair of
nuclei rotating about an axis perpendicular to the line between the nuclei.
In general, the total angular momentum of the molecule is the sum of the nuclear
plus electronic angular momenta. In the case where the electrons are in a state of zero
angular momentum, the nuclear quantum number f may be replaced by the total

quantum number j. In many situations in which there is nonzero electronic angular

momentum we can replace L 2 — —h 2A2 by the operator J 2 = (total angular >

momentum) 2 with the difference being absorbed into the electronic energy V(R). In
either case we end up with the relative motion equation

2
d d
h

27
— -R —
R dR
1

dR 2
2

R2
+ V(R)\F(R) = E^F(R). (10-42)

Given a functional form for V(R) we could now solve this equation for F(R) and
then find the average value of the rotational energy (h 2 /2n)j(j + \)(l/R 2 ). How-
ever, a simpler approach is possible. V(R) has a minimum at R so that the
equilibrium separation of the nuclei, that is, the mean value of R, is approximately
R . The kinetic and rotational energies are usually small enough that they do not
significantly alter this estimate of the mean value. So the molecular rotation energy is

very nearly

2
h j(j+ 1)
Etot i = 0,1,2, (10-43)
2M A*;

The quantity jiR^ in Equation (10-43) is the moment of inertia of the molecule.
E rot
is the energy associated with the rotation of a rigid dumbbell as obtained in
Section 6-5. The energy levels represented by Equation (10-43) lead to spectral lines
whose separation is so small that they are often unresolved and appear as bands, as
discussed in Section 10-8.
524 Molecules

Occasionally, it is necessary to go beyond the approximation made in replacing;

(R~~) by R^~ to arrive at Equation (10-43). Some spectra involving high rotational
quantum numbers show the effect of "stretching" of the dumbbell, and the resulting
increase of the moment of inertia becomes evident.

Example

A numerical estimate of the rotational energy is easily obtained. Consider the

hydrogen molecule H 2 for which 2jti is the proton mass and R ~ 0.07 nm. We
have from Equation (10-43)

E rol
(1.7
— (1 X 10" 34 J
X 10- 27 kg)(0.7 X 10- 10 m)-
- •
s)
1
2

r = 1.2 x 10" 21 J

or

1.2 X 10 "- 1

J
£ = 7 X 10" 3 eV.
rot
1.6 X 10-',„9 J/eV

This energyis to be compared to a typical size of a molecular electronic energy,

which can be shown (see Problem 16 at the end of the chapter) to be of order

h
2

=
M
— h h
2

E. = (1.8 X 3
10 )(7 X 10
3
eV) = 13 eV,
''
m R2
e
m M R t p
2
Q

where m and r
M are the electron and proton masses, respectively.

10-7 Vibration

The problem of the relative motion of two nuclei in a diatomic molecule (as described
by Equation (10-42)) is that of a particle in a potential well, V(R), having a
minimum. If the well is deep and narrow, it is reasonable to assume that the nuclear
rotation is the most easily excited type of motion. However, we know that a particle in
—
any well for example, in a parabolic well vibrates about the position of the —
minimum, even in the ground state. The harmonic oscillator treated in Section 5-5 is
our prime model in this regard. We now consider molecular vibrations and show this
problem can usually be reduced to the case of a one-dimensional harmonic oscillator.
Returning to Equation (10-42), we write

where E vib is the vibrational energy that we want to determine and E rot
is the
rotational energy of Equation (10-43). We then have

2
dF\
h
- — d
—\R
R dR
1

2
I
2
—\
dRj
+ V{R)F(R)
K V
= E v,b
vlh
F(R).
V
'
'
'
2n \

In analogy with the hydrogen-atom problem we let U{R) = RF(R). This results in
 10-7 Vibration 525

Figure 10-14

Morse potential energy V( R ) with depth -A

at /?„. The dashed line is a parabolic potential
V that fits the Morse potential at the
minimum.

the equation

ti
2
d 2 U(R)
+ V(R)U(R) = E vib U(R). (10-44)
2/i dR 2

so the problem has been reduced to that of a one-dimensional Schrodinger equation.

For many covalently bonded molecules a suitable form for V{R) is the Morse
potential energy. This expression, deduced by P. M. Morse, is given by

V(R) = A{e- 2a ^' R ^ - -a(«-/?, ,

)
2e )

(10-45)

where A, a, and R are parameters varying from molecule to molecule. The form of
this function is basically just an intelligent guess, as in the cases of Equations (10-24)
and (10-36), but it does do an adequate job of correlating many molecular properties.
For only a very few molecules, notably H 2 can accurate theoretical potential energy ,

functions be derived from Most molecules are much too complicated

first principles.
for one to do much better than to fit Equation (10-45) or an equivalent form to
several pieces of molecular data. Figure 10-14 indicates that the depth of the Morse
minimum is — A, which occurs at R = R The parameter a determines how fast the (}
.

potential energy falls off with distance and curvature of the well.
For small oscillations about equilibrium such that the nuclear separation does not
deviate very far from R ,
it is reasonable to approximate V( R) by a parabola centered
on R Such a parabolic potential energy
. is shown as the dashed curve in Figure 10-14
and is denoted as V(R). We can write

V(R)= V(R ) + $K{R-R o y ( 10-46)

where the constant K is to be determined so that V(R) and V(R) have the same
curvature at R . This means the second derivatives of V(R) and V(R) have to be the
526 Molecules

same:

V"(R ) = K= V"(R ) = 2
2a A. (10-47)

Equation (10-46), with K given as 2a A, is the result obtained with a Taylor

expansion of V(R) about R = R if only up to quadratic terms in R — R ()
are kept.
With the substitution of V for V, the Schrodinger equation becomes

2
h d 2 U(R) 1

"2^"^" +
2
K{R ~ Ro) U{R) = ^ vib ~ F(*o)M*)-

If we let y = R - R , e = £ vjb - V(R ), and u( y) = U( y + 7? ), this becomes

2 2
ti d u{y) 1
-" 2
y-r- + -Ky u{_y) = eu( y). (10-48)

This equation is almost the Schrodinger equation for simple harmonic motion, as
treated in Section 5-5. The one small difference is that the radial coordinate R is

restricted to R > so y > —R

However, this is really an unimportant
that .

restriction because if the particle motion had such an amplitude that it got to

y = —R it would certainly be in a region where the parabolic approximation is

()

invalid anyway. The gaussian wave functions for the low states of the harmonic
oscillator restrict y to avoid this forbidden region and we can simply forget the
restriction. On the other hand, the highly excited states in the oscillator well have
much wider amplitudes than the ground state and they should not be expected to be
reliable approximations to the true states of V( R ).

The radial Schrodinger equation with the exact Morse function in Equation
(10-45) can actually be solved analytically. However, the mathematics involved is

sufficiently complicated that we lose sight of the simple physics of the vibratory
motion if we attempt to review the exact solution here.

The energy eigenvalues derived from Equation (10-48) are just those of the
harmonic oscillator (see Equation (5-46)) with quantum number v:

e„= fiLo (v + l
2 ), v = 0,1,2,...

where

u (10-49)

We therefore obtain

£vib= -A + ho> (v+±), ^ = 0,1,2 (10-50)

These are the energy levels corresponding to oscillations in the length of the diatomic
molecule, in the approximation in which we think of the two nuclei as being
connected by a stiff spring. For highly excited states this approximation fails and the
Morse or other appropriate potential energy must be used to find Evib .

Polyatomic molecules can often be thought of as several atoms connected by a

number of springs. Such a system has a number of oscillatory patterns known as
normal modes. The techniques of classical mechanics may be used to find the frequen-
cies of these modes from which the vibration spectrum may then be found.
 W-8 Spectra 527

Example

The values of the Morse potential energy parameters for the 2

molecule are

A=5.2eV, R = 0.l2nm, a = 27nm~ l

.

From these values we find

K= 2a A
2
= 2(27 nm"' )"'(5.2 eV) = 7600 eV/nm 2 = 1.2 X 10
3
J/m 2

so that a characteristic vibrational energy is

K 1.05 X 10" J4 J s • 1.2Xl0 J J/m-

hu = h -27 0.2 eV.
ju 1.6 X 10-' 9 J/eV W 8(1.7 X 10 kg)

Note that the reduced mass used is one-half the oxygen atomic mass. This
vibrational energy should be compared with typical electronic and rotational
3
energies of about 10 eV and 10 eV, respectively, as computed in Section 10-6.

Example

The dissociation energy D, the energy to pull the molecule apart, is approxi-
mately A, the depth of the potential energy well. This is not exactly right
because the molecule has zero-point vibrational energy i,hu . Thus, we have

L
D ,hco .

For O, we obtain

D= 5.2 - 0.1 = 5.1 eV,

in agreement with the experimental value.

10-8 Spectra

Much of whatknown about molecules comes from examining spectra. Because a

is

molecule is more complex than an atom, molecular spectra are often more
inherently
complicated than atomic spectra. From the spectral lines the various effects caused by
electronic, vibrational, and rotational transitions must be disentangled. The energy
scales of these three types of transition are quite different, as we have seen above, with
typical values being of order 10, 10" ', and 10 3 eV, respectively. Because the
rotational energy is so small, the spectra often appear as bands of very closely spaced
lines, the most noticeable characteristic of molecular spectra.
We examine three main spectral types: pure rotational, rotation vibrational, and
electronic. To
keep the discussion simple only those transitions between molecular
states having the angular momentum quantum number A = are considered. Our
analysis is therefore not quite as general as possible but does illustrate most of the
essential elements.
528 Molecules

Figure 10-15

Molecular absorption transitions. Transition I is pure rotational with A7 = 1 and no change in

vibrational or electronic state. Transition II involves a vibrational change A; = 1; the rotational
change is Aj = +1. Transition III involves an electronic change of state with possible
vibrational and rotational changes as well.

V~i>=2

v= 1

A molecular energy level within the approximations discussed in previous sections

is, by Equations (10-43) and (10-50),

e = ed + ha (v+ \) + Bj(j+ 1), (10-51)

where

B = (10-52)
2fiRl

Figure 10-15 presents a schematic illustration of transitions involving all three terms in
Equation (10-51).
The first transition to be considered is a pure rotational change of state. Such a
change is shown in Figure 10-15 as I. Because of symmetry considerations, a pure
rotational transition, that is, onewhich j changes but the electronic and vibrational
in

quantum numbers remain cannot occur for a homonuclear diatomic

the same,
molecule, such as H.,. It can occur, however, in a heteronuclear molecule having a
permanent electric dipole moment, such as LiF.
There is a selection rule for a pure rotational transition that forbids transitions
other than
Aj= ±1.

For absorption spectra j — > j + 1 and from Equation (10-51) the frequencies are
given by

hv = B[{j+ l)(j+2)-j(j+ 1)] =25(>+ 1). (!0-53a)

 10-8 Spectra 529

Figure 1 0-1

Spectral form for a pure rotational transition as I in Figure 10-15. The lines are equally spaced
with energy interval 25.

-2B-

-^- hv
2B AB 6B SB \0B 1ZS
0-1 1-2 2-3 3-4 4-5 5-6 y'-y + 1

For emission spectra j —* j — 1 so

hv = B[j{j+ l)-(i- lb'] =2Bj. 10-53b)

In both cases the frequencies vary linearly with j, which means the lines are evenly
spaced with frequency separation

2B
Ar = (10-54)
h

as shown in Figure 10-16. These transitions are in the far-infrared or microwave

range.
From pure rotational spectra, and in particular from Equation (10-54), we can find
B. The equilibrium interatomic spacing R is then found from Equation (10-52).
Vibrational transitions cannot take place in a homonuclear molecule without an
accompanying electronic change but can in a molecule with a permanent dipole
moment. In such a case the selection rules are

Ai> = ±1 and Aj = ±' 1

A typical vibrational transition is shown as II in Figure 10-15. Absorption always

implies Av = +1 since the vibrational energy much larger than the rotational. In
is so
the usual situation the initial vibrational state is v = since the higher vibrational
states are not thermally excited at room temperature. Then the energy change is either
that with j — * j + 1 given by

hvR = hu (\ + 9 + B(j+ l)(>+2)- $hu -Bj(j+ 1)

= hu + 2B{j+ 1), 7 = 0,1,2,..., 10-55)

or that with j — > j — 1 given by

hv p = Au (l + L
2
)+B(j- 1)>- Lhu -Bj(j+ 1)

= htc -2Bj, j =1,2,.... (10-56)

As indicated by the subscripts on the v 's, these spectral lines are as the R and
known
P branches. Each of these branches gives a group of lines much due to the pure
like that
rotational transitions except that the frequencies are in the range about hco so that ()

they fall in the infrared.

 »

530 Molecules

Figure 10-17

Spectral form for a vibrational- rotational transition. There are two branches with a missing
line at hu f)
. The corresponding transition in Figure 10-15 is II.

P branch R branch

-> hv

7H

Figure 10-17 shows how the vibrational -rotational spectrum splits into the two
branches in accord with Equations (10-55) and (10-56). Note that there is a gap
between the two bands at the vibrational frequency go /27t. This exists because
A7 = is not allowed and because in Equation (10-56) j = does not occur. (That
would correspond to the transition j = to j = — 1.)
Transitions in which there is an electronic change of energy are represented by III
in Figure 10-15. The transition frequencies can again be deduced from Equation

(10-51). However, now note that co and B are not generally the same for the initial
and final electronic states. B depends on the molecular moment of inertia and hence
on the interatomic separation R which varies with the electronic state. In Figure
,

10-15, for example, the minima in e, and e., occur at different values of R. The
vibrational frequency w depends on the curvature of the electronic energy in the
neighborhood of its minimum. (See Equations (10-47) and (10-49).) The curvature is

also expected to be different for different states. For absorption the change in

electronic and vibrational energy is

hv. es ,
s
+ h^{v'+ 1) -ha (v+ i), (10-57)

where to () and to,', and final states, s and v are

are the vibrational frequencies for initial
the initial state electronicand vibrational quantum numbers, and s' and v' are those
of the final state. In absorption the initial electronic and vibrational states are usually-
ground states so s = and v = 0.
Equation (10-57) sets the scale of the transitions, which run from the near infrared
to the ultraviolet. The fine structure of the spectrum is determined by examining the
rotational transitions that occur simultaneously with the above change hvev What the .

rotational structure does is to spread the electronic-vibrational line into a band of

many very closely spaced lines. The selection rule is again Aj = + 1 so that there is

an R branch corresponding to j
'
— j + with energy changes
> 1

hv R = hve ir(,+ i)(j + 2 )-Bj(j+ 1), j = 0,l,2,, (l0-58a)

and a P branch for j — j — 1 given by

hp p =hpev + B'j(j+ l)-Bj(j- 1). j= 1,2,. (10-58b)

Because B =£ B' the quadratic terms in j no longer cancel out and the spectra are
not made up of evenly spaced lines as in the previous situations. We can write

hv. hvrv + (B' - B)j 2 + {W - B)j + (2B' - B) (l0-59a)

 10-8 Spectra 531

Figure 10-18

Spectral form for an electronic transition. The electronic- vibrational transition energy is kvev
The band due to rotational transitions has a band head at the left (red) and degrades to the

right (blue).

-> hv
IBand head
hr,

Figure 10-19

Pure rotational absorption spectrum of HC1 gas. Note the even line spacing as indicated
schematically in Figure 10-16. The frequency axis is v = v/c in units of cm~ .

20 40 60 80 100 120 140 160 180 200 220 240 260 280 300

Hem" 1

Figure 10-20

Vibrational-rotational absorption spectrum of a diatomic molecule like that shown schematically

in Figure 10-17. The absent line is denoted by vv .

r n 1

R branch P branch
532 Molecules

Figure 10-21

Electronic spectrum of the molecule AlO. See Figure 10-18 for a similar schematic version. Note
the bands caused by the small spacing of the rotational states.

4MK _>» X 4K4; 27 \

and

hv P = hp„+ (B' - B)j 2 - {B' + B)j. (10-5%)

If > B these v R and v p results increase quadratically toward higher frequency.

B'
The function v P(j) has a minimum at a frequency somewhat lower than vev In this .

region the lines are also more closely spaced than at high j values; at high j the
spacing becomes greater because of the increasing influence of the j 2 term. A
schematic drawing of this spectrum is shown in Figure 10-18. The band is said to be
degraded to the blue and to have a band head (the
(i.e., the high-frequency end)
minimum) at the red (low-frequency) end. If B' band head is at the blue end < B, the
and the degradation is toward the red. The details of just how the spectrum comes to
look like that of Figure 10-18 are given in the example below. Such a band appears
for each possible v -» v' transition. The spectra appear as a series of adjacent bands.
Examples of real spectra of the types discussed in this section are shown in Figures
10-19, 10-20, and 10-21.

Example

To see how the frequencies in Equations (10-59) produce a spectrum like that
shown in Figure 10-18, rewrite the equations in the form

yR {j) = 10
2
| 1) ={b' - b)j
2
+ (3b' - b)j + (2b' - b) (10-60a)

and

yp {j) = 10
2
—
''/
-!=(&'- b)j
2
- (b' + b)j, (l0-60b)

where

W 2
B 2
10 B'
b = and b' = .

Then let b and b' take on the typical values b = 3, b' = 4, so that

}'r(
2
j)=J + 97 + 5 and yP { j )
= j2 - Ij.
 Problems 533

Figure 10-22

Frequency functions yR {j) and yr (j) of Equations (10-60) for 6 = 3 and b' = 4. The y values
corresponding to integers are the allowed frequencies and are indicated by arrows on the y axis.
The band head is at the left end corresponding to the minimum in y,,.

If we consider yR or y p to be a function of j as a continuous variable, we can

plot each as shown in Figure 10-22. The plot is laid on its side so that the

frequency variable y runs horizontally. Integral values of j are shown as dots

along the curves; their projections on the y axis give the frequencies of the
allowed transitions. It is easy to see that yP has a minimum:

dyr
= 2j - 7 = at j = \ = 3.5.
dj

The value of at the minimum — L

7( >) = —12.25. The minimum
yp is (^)
frequency occurs at the band head. The y P parabola opens to the right so that
the allowed y values become more separated in moving to larger y values. This
is band degradation to the blue. The R branch does not have a minimum for
positive j but also degrades to the blue.

Problems

I. A particle of mass m moves in a "double-oscillator" potential energy given by

V(x) = 2^(|*|
— a) > 3s plotted in the figure. When the separation 2a between wells is

sufficiently large, good approximations to the eigenfunctions for the two lowest states are

*±"
jf(*«±*-«)'
where

.
2«\''/4

is the single oscillator ground-state eigenfunction centered on x ±a, with a = T-,mu, }

/h
and o> = Jk/m .
534 Molecules

(a) Given the above approximate eigenf unction, show that the energies ? + of the two
lowest states can be written in the form of Equation (10-7), where

G= ftf_ a
V(x)dx and S = jV( *) £_ a
dx

with F= -/:(* + |jc|)«, and where eu is replaced by e = t#w > the ground state
of a single oscillator,

(b) Evaluate S and show that the separation between the two lowest states is propor-
2 "" 2
tional to e" .

The ammonia molecule NH ., has a tetrahedral structure as shown in Figure 5-25. The
nitrogen atom has two equivalent positions either on the right of the plane of the 3
hydrogens or in the "inverted" position on the left. It can tunnel between these two
positions and so has a wave function analogous to that of the H.J electron or to the
particle in Problem 1. The splitting between the two lowest energy levels is e_— e+ =
r

9.8 X 10 '
eV.
(a) Find the time it takes the nitrogen atom to invert.

(b) Use the potential energy of Problem 1 as a model for that seen by the nitrogen
atom. Take a = 0.038 nm. What is the height V of the potential barrier separating

the two wells?

What is the electronic ground-state eigenf unction of He + ? Show that \p+ of Equation
(10-3a) does not reduce to it for R —» 0.

(a) By what constant should the eigenf unction of Equation (10-19) be multiplied in

order to be normalized properly? Neglect all overlap integrals.

(b) For H 2 , y is about 0.2. What is the probability of both electrons residing in a single
nucleus?

An alternative to the Heitler- London approach in approximating the H , electronic wave

function is the molecular orbital method. Two electrons, of opposite spins, are considered to

be in the same Hi -type state \p t

(Equation (10-3a)) just as two electrons are put into the
\s orbital to describe atomic helium. The eigenfunction then is \p^ (r, )\p + (r>)x 0> 2).

(a) Show this function is properly antisymmetric.

(b) Express this eigenfunction in terms of the Is atomic orbitals and compare with the
form of Equation (10-19). In particular, determine the value of y that governs the

amount of ionic structure implied by this function.

(c) What is the probability of both electrons residing on a single nucleus in this

approximation?

In the binding of HJ a portion of the electronic charge is shifted from the regions
immediately around the nuclei to a position in between. A simple model of this is shown in
 Problems 535

the figure. The total charge in the system is +e. What portion of electronic charge Se

must be placed in the intermediate position for binding to result? [Hint: Note that binding
implies a negative total energy of the system.]

7. Other molecular orbital combinations, besides that in Problem 5, may be formed out of
products like 4' + (r )ip_(r2 l
) and 4'-( r \ )4'-( r2) times singlet or triplet spin functions. Five
additional functions, all representing excited states, may be formed. What are these
functions? Be sure they are all antisymmetric in electron coordinates. By writing these out

in atomic functions and examining the form of the covalent part of each function,
determine which are bonding and which are antibonding.

8. (a) The ionization potential for hydrogen is 13.6 eV. The electron affinity for fluorine is

0.8 eV. Evaluate the Q_ value of Equation (10-27) for HF. Compare this with the
value for LiF as worked out in Section 10-3. From this result do you expect HF to

have a greater or lesser ratio of ionic to covalent bonding than LiF?

(b) The equilibrium separation of the two nuclei in HF is R = 0.092 nm. The
experimental value of the electric dipole moment of this molecule is p = 0.6X
10 C •
m. Calculate p/eR. Does the result here confirm your answer to the
question in part (a)?

9. (a) Verify that the eigenfunction of Equation (10-21) is normalized if A2 + B2 + C 2

= 1.

(b) Construct an eigenfunction analogous to that of Equation (10-21) for HF.

(c) Determine the coefficients A and C (assume 5 = 0) for this eigenfunction by use of
the value of p/eR found in Problem 8(b).

10. (a) The internuclear separation for NaCl is R = ()

0.236 nm. Spectral data show that
the curvature K of the potential energy is 109 J/rrr. The ionization potential of
sodium is 5.1 eV and the electron affinity of chlorine is 3.65 eV. From these values

determine the parameters a and a in Equation (10-24), and find the dissociation
energy D. How does your result compare with the experimental value of 4.22 eV?
(b) Find the zero-point energy correction to the calculation of D.
11. As a classical model of atomic polarizability consider a positive point charge +e (the

nucleus) surrounded by a uniform charged sphere of radius a and charge density

p = — e/{\ma ) (the electron "cloud").

(a) Show that if the nucleus is displaced by a distance z from the center of the sphere it

feels a restoring force F = —(ep/3e )z.

(b) Show that if this system is put into an electric field E it develops a dipole moment
given by p = aE with a = 4fre a
i
.

12. Show that a hydrogen atom placed a distance R from H* has a potential energy U of the
form U ~ — I^a/R)* where , /n and a are the ionization potential and the atomic radius
of the hydrogen atom, respectively. How should the phenomenological potential energy,
Equation (10-24), for ionically bound molecules be modified to take account of this effect?

13. Show that the Lennard-Jones 12-6 potential of Equation (10-36) has a minimum of —e at

an interparticle separation R = 2' 6

o.
536 Molecules

14. Above approximately what temperature is a diatomic argon molecule expected to be

dissociated?

15. The Lennard-Jones interaction between a carbon atom and a helium atom is given by
Equation (10-36) with n = \2, f = 1.5 X 10 eV, and a = 0.3 nm. Suppose a helium
atom is at position r = (0,0, h) above the flat surface of a piece of solid carbon. The
origin (0, 0, 0) is on the surface and the carbon solid extends from — oo to oo in x and y,
and — oo to in z. The carbon density is n .

(a) Give a brief argument that shows that the helium atom has potential energy
£/(r ) = n /^Lj(l ro
~~ r l
) dr, where the integral extends over all the carbon, which
is taken as continuous.

(b) Carry out the above integral and show that U has the form

a b

What are a and b?

(c) Find the value of the helium position h for which U is a minimum when the carbon
density is n = 113 particles/nm
!
. What is the potential energy function depth

there?

(d) To what value must the temperature be lowered for a layer of helium atoms to
begin forming on the surface?

16. In the example at the end of Section 10-6 the expression £d = h^/m R^ f
is used to
estimate typical electronic molecular energy. Justify this formula by use of (a) the energy-

levels of a particle in a box and (b) the uncertainty principle.

17. The Born-Oppenheimer approximation, the basis of studies of molecules, claims the
nuclear motions are so much slower than electronic that the electronic energies can be
computed for fixed nuclear positions. Compute the orders of magnitude of the periods of
rotational and vibrational nuclear motion for H , and compare them with the period of an
electron in a Bohr orbit. The Morse potential parameters for the H-H interaction are

A = 4.75 eV, R Q = 0.074 nm, and a = 19.5 nm '.

18. Give arguments that show that E TOX

— (m/M)E^ and £vib - (
m/M )' Ed
/2
, where Ee] ,

EmX , and £vib are electronic, rotation, and vibrational energies, respectively, m is the
electron mass, and M is a nuclear mass. Evaluate these relations numerically (with
E ~
rt
10 eV) and compare with the estimates given in the examples at the ends of Sections
10-6 and 10-7.

19. (a) By determining the curvature K at the minimum of the Lennard-Jones 12-6
potential, evaluate the harmonic oscillator approximation \fiuQ to the zero-point
energy of the argon molecule Ar>. Compare this value with the depth of the
potential and estimate the binding energy of Ar,. See Table 10-1.

(b) Repeat the above for the He_, molecule. What does your result suggest about the
possibility of ever forming a He_, molecule?

20. The Morse potential for two interacting hydrogen atoms has the parameters given in

Problem 17. From this compute the vibrational frequency wn and the dissociation energy

D for H.,. Compare the results with experimental values.

21. The internuclear separation for the CO molecule is R = 0.113 nm; the dissociation
energy is 9.60 eV; the vibrational frequency is vt) = w /2t7 = 6.51 X 10 13 Hz. Use these
data to find the parameters of the Morse potential for the interaction between carbon and
oxygen.
 Problems 537

22. The separation between spectral lines in the pure rotational spectra of HC1 is 6.35 X 10"
Hz. Use this information to find the internuclear spacing Ru .

23. Draw a diagram analogous to that of Figure 10-22 for the case b = 2.5, b' = 2. Is the

band head to the red or blue? In which direction does the degradation take place?

24. Suppose you are a molecular spectroscopist and you have collected the data shown in

Figure 10-18. The values of the first few y's (defined in Equation (10-60)) are —4.4,
-4.2, -3.4, -3.0, -2.0, - 1.4, 0.8, 1.6, and From these data
3.6. find the values of the

molecular rotation constants b and b' . [Hint: What value of the initial state quantum
number j corresponds to the band head at y = —4.4?] Give the values of the j's
corresponding to each of the quoted transitions and tell to which branch each belongs.
 ELEVEN
QUANTUM
STATISTICAL
PHYSICS

In Sections 2-3 and 2-4 we have seen how

statistical reasoning could be used in conjunction with the quantum hypothesis to
derive the Planck law of blackbody radiation. The procedures applied by Planck
involved the kinetic theory techniques that had been developed in the 19th century by
Maxwell and Boltzmann. This approach developed into the discipline of statistical
mechanics with the work of J. W. Gibbs, an American physicist who was a contem-
porary of Planck.
The powerful techniques of statistical mechanics exploit the fact that macroscopic
systems are made up of a large number of particles. It is clearly impossible to follow
everything going on in so large a system. Usually only certain average quantities, such
as pressure, volume, and temperature, are measured in experiments or calculated by
theory. These variables are the quantities that have their origins in the joint behavior
of all the particles. For example, the pressure of a gas is the result of an enormous
number of individual molecular collisions with the walls of the container. The position
or any other detailed dynamical property of an individual gas molecule is a variable
that cannot be observed.
The seeming disadvantage of working with a small number of averaged quantities
is offset by the fact that fluctuations in these averages are extremely small in a large
system. The readings on a and on a thermometer are usually quite
pressure gauge
steady. The mechanism of probability theory at work here is the same as in coin
tossing. If a coin is tossed ten times, a result, for example, of three heads and seven
tails, quite far from a 50-50 split, is not rare. However, if the coin has been tossed a

billion times any result not very close to an equal number of heads and tails (within
~ 10~ 3 %) is quite surprising.
The use of a billion coins to determine the probability of tossing a head or tail is an
example of the ensemble method of determining the averages. This technique is

introduced and used in the present chapter to study the thermal properties of
collections of particles having three different kinds of probabilistic behavior: those
obeying Maxwell-Boltzmann statistics, Bose-Einstein statistics, or Fermi-Dirac statis-
tics.

538
 //-/ Particle Indistinguishability 539

Before quantum mechanics, all particles had been thought of as completely

distinguishable. When two billiard balls collide it is easy to tell which one is which

after the collision. However, for microscopic particles, we now realize that the
uncertainty principle makes it impossible to figure out which particle was incident and
which particle was target. This feature of particle indistinguishability implies that all

elementary, and many composite, particles obey either Bose-Einstein or Fermi-Dirac

statistics. Microscopic particles of the same species that are distinguishable cannot
actually exist in nature. However, they may be treated theoretically and are said to

obey Maxwell -Boltzmann or classical statistics.

The macroscopic thermal properties of a system depend crucially on the statistics
obeyed by the constituent particles. Electrons in a metal (Fermi-Dirac particles)
behave very differently from the atoms in liquid helium (Bose-Einstein particles).
However, at high temperatures all three kinds of particles have the same general type
of thermal behavior.
Radiation may also be treated by the use of a particular form of quantum statistics.
Planck had originally treated the properties of blackbody radiation by considering the
effect of quantizing the charged oscillators in the solid walls of the cavity that emitted
the radiation. Einstein pointed out that Planck's argument was flawed: Planck had
calculated the energy density in a particular frequency mode of the radiation in terms
of the energy of the oscillators by assuming the oscillators could emit radiation
continuously. He then quantized the oscillator energy. The work of Bose on radiation
and Einstein's subsequent generalization of it to massive particles led to a slightly
different interpretation that we follow in this chapter. Light is made up of discrete
indistinguishable massless entities called photons and the oscillator state nhv is

interpreted as describing the energy of n photons each of energy hv. This interpreta-
tion is consistent with Einstein's treatment of the photoelectric effect. Photons are thus
found obey Bose-Einstein statistics.
to
Blackbody radiation certainly did not provide the only evidence for the need to
modify classical mechanics. The classical theory of solids predicted the heat capacity C
to be independent of temperature. While this result held for high temperatures, at low
temperatures C was found to drop toward zero. Einstein explained this phenomenon
by modeling the solid as an independent set of quantized oscillators. This model was
improved upon in 1912 by Debye who considered the solid as a set of particles
coupled harmonically to one another. This theory, which gave the correct low-temper-
ature behavior, has turned out to be remarkably similar to that of blackbody
radiation. Indeed, the concept of massless Bose-Einstein particles called phonons
traveling through the crystal lattice has proved to be very analogous to the photon
idea.
Fermi and Dirac are responsible for the development of the statistics obeyed by
electrons, protons, neutrons, and a host of other particles. The statistics forms the basis
of the Pauli principle according to which one Fermi-Dirac particle is allowed per
quantum state. The thermal properties of electrons in atoms and metals, protons and

neutrons in nuclei, the atoms in liquid ''He, and even the nature of white dwarf stars
can be understood with Fermi-Dirac statistics, as described in this chapter.

11-1 Particle Indistinguishability

If two identical particles A and B pass within a de Broglie wavelength of each other,
then after the encounter we are unable to tell which of the two particles is A and
 )

540 Quantum Statistical Physics

which is B. To do so requires knowledge of their positions to such an accuracy that, by

the uncertainty principle, the encounter is essentially changed.
In Sections 5-10 and 9-5 we have seen how this property of microscopic encounters
can be built into the wave functions of the particle pair in terms of their symmetry or
antisymmetry. In the case that the potential energy function V is a sum of individual
one-particle functions,

V{\,2) = V(\) + V(2),

the solutions to the Schrodinger equation have the form

>«(D^(2) (11-la)

M 1 '2) = \
<Ml)* a (2) (11-lb)

with the 4* J- 1 ) satisfying

2
V, + V(i) ^(0 = ^„(0,
2m

where Ea is an energy eigenvalue and ip

a ls a one-particle eigenf unction. The
discussion of Section 9-5 leads us to two possible forms for the two-particle eigenfunc-
tion. One of these, the antisymmetric state

^( 1,2) = -^(^(1)^(2) - ^0)^(2)), (H-2)

is discussed at length in that section. It satisfies a relation like Equation (9-16),

*i(2,l)= -*J,(1,2). (H-3)

The other form is constructed in an analogous way to be

fyi,2) = ^(ifl)V2) + ^(l)i(2)), (11-4)

and is symmetric under particle interchange:

^(2,o = +*yi,2) (11-5)

as in Equation (9-15).
We know from Chapter 9 that particles with half-integral spin values (\Ti, |A, . .
.

have antisymmetric eigenfunctions and are known as fermwns. These include electrons,
protons, and neutrons, as well as composites of odd numbers of particles having
3
half-integral spin such as He atoms, and others. All these particles are said to obey
Fermi-Dirac statistics.

whose eigenfunctions behave like Equation (11-5) are said to obey

Particles
statistics and are known as bosons. All such particles have integral spin
Bose- Einstein
(0h,lh,2h,...). These include photons, certain elementary particles called mesons,
and certain so-called collective modes in many-body systems (phonons), as well as
composites of even numbers of fermions such as He atoms, and others.
 //-/ Particle Indistinguishability 541

Figure 11-1

Intuitive description of the terms in the probability density Equation ( 1 1 -6). The coefficient g
has the value g = 1 for bosons, g = - 1 for fermions, and g = for Maxwell-Boltzmann
particles.

2 +
l* ai8 (l,2)l
=
}t*a(l)* a (l)*p(2)* /
8(2) ^(D^(D*o(2)* a (2)
©

+ ***(l)* (l)tfp(2)* a (2) + **£(1)* O (1)**(2)*0(2)]

i8

Let us now examine more closely the properties of these two-particle eigenfunc-
tions. The measurable quantity, the probability density, is, for both cases simulta-
neously,

2
1^(1,2) |
= ^(1)^(1)^(2)^(2) + ^(1)^(1)^(2)^(2)

+^S(0M 1 )^(2)^(2) +^1(1)^(1)^(2)^(2)], (11-6)

where g = + 1 for bosons or — 1 for fermions. A possible intuitive interpretation of the

meaning of the various terms in Equation (11-6) is illustrated in Figure 11-1 and goes
as follows: The first term on the right represents an encounter in which particle 1 has
state a and particle 2 has state /3 both before and after the meeting; the second term
puts 1 in ft and 2 in a before and after. If only these terms exist (i.e., if g = 0), the
final measurable results are equivalent to the situation in which the particles are

distinguishable with, for example, particle 1 painted blue and particle 2 painted red.
The new effects due to symmetry are contained in the third and fourth terms, the
quantum interference or "exchange" terms. The third term has particle 1 starting out
in /? and particle 2 in a. However, after the encounter the two switch places so that 1
is in a and 2 is in ($. The last term describes a similar process with 1 and 2
interchanged in roles. We have already seen how such interference terms can affect
the energy of a system in our treatment of the H 2 molecule in Chapter 10. In Problem
2 at the end of the chapter we consider some further aspects of this phenomenon.
Particles of the same species, yet somehow distinguishable, are described by either
of the Equations (1 1-la) or (1 1-lb). We can tell the difference between the two forms;
for example, the blue particle is in a and the red is in /?, or vice versa. Such particles
do not actually occur in nature but are useful conceptually. They are said to obey
542 Quantum Statistical Physics

Maxwell-Boltzmann statistics. Later in this chapter we show that the behavior of

fermions and bosons becomes identical to that of Maxwell-Boltzmann particles at

sufficiently high temperature. We can produce theEquation effects of the statistics in

(11-6) by keeping only the by taking g = 0. (We can tell the

first two terms, that is,

difference between the two forms in Equations (11-la) and (11 -lb), and still have the
Maxwell-Boltzmann case in Equation (11-6) while keeping both with equal ampli-
tudes, as long as we do not let the two forms interfere.)
We
can see when quantum effects become important by considering the pair wave
function in the case that 4> a{i) and \pp(i) are localized, or peaked up at some position
in space. We assume each of ^ a (l), ^(1), ^P a (2), and ^(2) has the same spatial
width d. It is fairly obvious that the appropriate de Broglie wavelength with which to
characterize such a localized state is A ~ d. (This can be proved but we are not going

to do it Suppose ^„(1) and ^(1) differ mainly in being centered at different

here.)
positions separated by a distance a. (An example of this situation occurs in Chapter 10
in which the H 2 molecular eigenfunction is written in terms of Is atomic orbitals, each

localized on one of the two protons.) If A «

a, the interference terms in Equation

(11-6) vanish; that is, where ^„(1) is large, ^(1) is zero, and vice versa.
Maxwell-Boltzmann statistics is then valid. On the other hand, if A > a the single-
particle eigenfunctions overlap, the interference term is nonzero, and quantum effects
are present. In Section 11-3 we introduce the thermal de Broglie wavelength A th ,

which is a measure of the average value of A as a function of temperature. The ratio

A th /a determines the importance of quantum effects in the thermal properties of a
system.
We have seen previously that the fermion function in Equation (11-2) vanishes, in
accord with the Pauli principle, when both particles are in the same state:

^(1,2) = 0.

Fermions are antisocial. Bosons, on the other hand, are gregarious. They actually
show a preference for being in the same state or place when compared to distinguish-
able particles. To see this take both particles at the same position, that is, r L
= r2 = r,

in Equation (1 1-6). Then it is easy to see that we get

-

2 2

k a/J
(r,r)| =|^(r)r|^(r)| (l+ 5 ).

For fermions g = — 1 and this expression vanishes as one expects. For the
Maxwell-Boltzmann case g = and (1 + g) = 1, while for bosons (1 + g) = 2. This
preference that bosons have for being in the same place (or state) is important in
4
understanding several physical phenomena including the superfluidity of liquid He.
As by the Slater-determinant eigenfunctions of Section 9-5, it is possible
illustrated
to generalize our symmetry principles to functions for more than two particles. To get
the boson version of the Slater determinant, expand it into a series of terms and
change all the minus signs to plus signs. The result is a function symmetric under the
interchange of any pair of the variables.

Example

Suppose we have three particles in three states a, ft, y. The fermion version of
the eigenfunction for this case is written in Problem 8 of Chapter 9. The boson
 / 1-2 Thermal Distribution Functions 543

version is found, from the prescription given above, to be

^(1,2,3) = -^{* a (l)^(2)* y (3) + ^(l)^(2)^ y (3)

+ ^(1)^(2)^(3) +^ a (l)^(2)^(3)
+ ^(l)^ y (2)^(3)+^ y (l)^ a (2)^(3)}.

(In the fermion version the second, third, and fourth terms are negative.) The
indices a, /?, y on the right appear in all possible permutations of three quanti-
ties so it is not surprising that, when two variables are exchanged, or when any
possible permutation of the three variables 1,2,3 occurs, the eigenf unction is

unchanged.

11-2 Thermal Distribution Functions

A distribution function n t
gives the average number of particles to be found in an energy
state e, at temperature T. If a system is heated(T raised) particles are redistributed to
higher energy states and « ;
is altered. We also expect n t
to depend on the nature of
the particles. For fermions n t
must be zero or one because of the Pauli principle; for
bosons n i
behaves in a manner consistent with the particles' tendency to be in the
same state.

Section 2-3 contains a presentation of the Maxwell-Boltzmann distribution func-

tion. The derivation given there yields correct results but is seen to suffer from a slight
flaw when examined closely. The average number of particles in a state where the
energy is less than unity and yet Stirling's approximation, which is
very large drops to
valid only for numbers much greater than unity, has been used for all states. We
might argue that such sparsely occupied states do not carry much weight and that the
error is therefore unimportant. However, what is an unimportant difficulty for
Maxwell-Boltzmann particles becomes an intolerable one for fermions for which
n < 1 for all energy states e Consequently, we must refine the techniques of Chapter
l
-.
f

2 somewhat before we can apply them to quantum particles. The need to do this
provides us with the opportunity to look more closely at the ensemble concept that is
at the heart of all statistical reasoning.
In the introduction to this chapter, we mention the flipping of a coin a very large
number of times to determine the probability of finding a particular head or tail

outcome. An alternative procedure is to solve the classical equations of motion of the

coin given the prevailing conditions of thumb speed, height above the table, distribu-
tion of metal in the coin, and
Such a direct approach is nearly impossible.
so on.
Another such situation involves an insurance company interested in the likelihood
that an individual might die before the company has accumulated sufficient premiums
to cover the awards to all the beneficiaries. Someday, perhaps, medical science might
be able to predict from the results of a medical exam precisely how long a person can
expect to live. Since this prediction is not possible today, an insurance organization
uses the medical exam to place the individual in a group or ensemble of people with
similar medical histories. The ensemble varies depending on whether the individual is,
544 Quantum Statistical Physics

forexample, a smoker or has had a heart attack. The ensemble consists of people of
known medical history all of whom have died so that an average age of death may be
computed. Whether our individual dies much earlier or much later than the average is
not terribly important to the finances of the company. On the average they are going
to collect sufficient premiums to cover both possibilities.

The last sentence tells us that a statistical analysis gives information not only about
average values but about fluctuations about those values. An instructor may construct
a bell-shaped curve by using the grades on an exam; the curve is described by a width
as well as a mean or most probable value. An interesting aspect of physical systems
containing very many particles is that fluctuations of most variables about their
averages are so small that we need concern ourselves only with computing the mean
values.
We are interested in the behavior of a system composed of N particles. To measure
any quantity, such as pressure, we put a gauge on the system and follow its readings
over a sufficiently long period. A
same quantity might in
theoretical calculation of the
principle be carried out by solving the time-dependent many-body Schrodinger
equation and following the evolution of the wave function. This is extraordinarily
difficult; what is done instead is to examine the average behavior of a great number of

similarly constructed systems at one single time. There are reasonable assumptions
built into the latter approach which make it much the simpler procedure.
Suppose our system is a box containing a gas of N particles. We assume there are
energy levels e,, e
2 , e3 , . . . for each particle in the box. This assumption is usually
possible only if the particles are nomnteracting. The energy levels are, at any one time,
occupied by n ,, ™ 2 « 3 , ,
particles just as in the notation of Section 2-3. To find the
average values of the n i
a large number M of apparently identical boxes, each with N
particles, is examined. In accord with the fact that it is impossible to follow individual
particle motions, no attempt is made to select M systems all with identical sets

of particle trajectories. On the contrary, to infer accurate average behavior of a

typical system, we choose random initial conditions and random subsequent behavior
for the particles in the various boxes. This assembly constitutes our ensemble. Figure
11-2 illustrates the idea. All the systems have the same set of single-particle energy
levels; any energy level e, of system y contains n\ y) particles. The numbers n\
y)
may

Figure 11-2

Ensemble of M identical systems. Each system contains an average of TV particles and has
single-particle energy states e,, e2 , e3 , .... Any state e, of system y contains ny' particles. The
total number of particles at level e, for all the members of the ensemble is T.
y
n\
y) = N,.

3
_ y M
System number >
 / 1-2 Thermal Distribution Functions 545

differfrom system to system because of the random variation of the states of particle
motion from system to system.
If each system has a total of exactly particles the sum over energy levels (a N
vertical sum in Figure 11-2) yields

oo

£ n^ = N.
i= i

However, in the following derivation we are going to relax this condition somewhat.
The particular procedure we use results in an average of N particles per system, with

fluctuations about the average that are quite negligible. With this in mind we replace
the last equation with
00

£ n\
y) = N {y)
,
(11-7)

where N <- y)
is the actual or instantaneous number of particles in system y. Since the
average value of jV (y) is N in each of the M systems, the following relation holds:
M
£N {y) = MN. (11-8)
y=l

If we consider a given energy level e, and sum horizontally in Figure 1 1-2, the result

is the total number of particles N t

in level i for all members of the ensemble. That is,

we have
M
X>! T) = ty- (11-9)
y=\

The quantity of interest is the mean of the n\ y) averaged over all the systems of the
ensemble. This average is denoted simply by n without the superscript y and :
is

n, = — (11-10)'
'
M V

Another important attribute of each system is its total energy. Just as in the case of
particle number we relax the restriction that each system have exactly energy E and
assume only that it has that value on average. System y has actual energy E iy) so that

E" (

,
Y)
e, = £ (Y \ (H-ll)

which is another vertical sum in the scheme of Figure 11-2. Since the average value of
E {y) is E in each of the M systems, we have
N
£,E™ = ME. (11-12)
y=l

To determine the average value of n !

we imagine repeatedly throwing particles at
random into the ensemble's systems and levels and counting how often any particular
N t
occurs. The most probable N :
value is the one to be used in Equation (11-10).
546 Quantum Statistical Physics

(i) Maxwell - Boltzmann Statistics Let us begin by reproducing the Maxwell-Boltzmann results
of Section 2-3 in order to illustrate the method. systems each with an average of A* M
particles imply a total of NM
particles. We distribute them all throughout the entire
ensemble without worrying about getting exactly of them into each system. The N
number of particles in all energy levels £, throughout the ensemble is there are X, N x
;

particles in all levels e 2 and so on. We want to count the number of ways to distribute
,

N t
particles horizontally in level e t
across the ensemble. The first of the N t
particles
can be put in any one of M
systems so that there are ways of placing it. There are M
also M
ways for the second particle. For each of the ways of placing the second
particle there remain the original M
ways for the first so that there are 2
ways of M
positioning the two particles in the M
sites. One of the ways involves, for example,

two particles in level e of system 1. The method counts this situation only once; an
;

interchange of those two particles does not produce a new configuration even when
they are distinguishable. For the third particle placed in the ensemble on a level e,

there are again M positions so that there are A/ 3

total ways to place three particles,
and so on. The total number of ways of distributing the N
t
particles horizontally on
level e ;
among all the systems of the ensemble is

with the subscript h referring to a horizontal distribution.

If the above procedure is repeated for a different energy level e-, it is obvious that
the number of ways of distributing N particles among all the ensemble's systems on
level e is

W£fi = MN >.

The total number of arrangements of particles on both levels £, and £ is the product
W^W^ J)
. If this process is repeated for all energy levels the number of all possible
horizontal arrangements is found to be

w h
= w^wpwp .

Since the particles are distinguishable in classical statistics, interchanges of two

particles vertically between two different energy levels in the same system or diago-
nally between two different energy levels of different systems produce a new con-
figuration or microstate, in the terminology introduced in Section 2-3. The total

number of ways of interchanging MN particles is (MN)\ However, this includes all

horizontal interchanges on each of the levels e,; these have already been considered in
the calculation of h
W
To remove them from the total number we must divide by the
.

number ways of interchanging N particles on level e,, given by A7,!, and the
of x

number of ways on level e 2 given by N2 \, and so on. It follows that the total number
,

of vertical or diagonal interchanges that can be made to obtain new microstates from
one of our original configurations is

(MN)l
Ko N \N2 \N3 \
X

where the subscripts v and d refer to vertical and diagonal interchanges.

 / 7 -2 Thermal Distribution functions 547

Figure 11-3

Ensemble with three Maxwell- Boltzmann particles in two systems. Each system has two energy
levels with TV, = 2 and N, = 1 (In this example each system does not contain the same number
.

of particles.) The particles are distinguishable and so can be labeled 1, 2, and 3; microstates 2
and 3 are then distinct. There are 24 possible configurations of which four are shown. We can
generate other configurations in two ways by interchanging particle 1 with 2 or with 3 for
3X4=12 microstates. The other 12 microstates are found by putting any single particle in
energy level e , of system 2.

© 0) © ©
® ® (D © ©©
System 1 System 2 System 1 System 2 System 1 System 2 System 1 System 2

Microstate 1 Microstate 2 Microstate 3 Microstate 4

Since there are W vd new configurations for each original one previously considered,
the total number of microstates that can occur for a fixed set of the numbers
Nu N N 2 ,
3, . . . is the product of W h and W vd :

AT' M N;

W= W W vd
= W vd Wi Wt
l) 2)
= {NM)\
h
N x
\ N 2
\

This can be written symbolically as

M'
W= (NM)\]~[ (Maxwell-Boltzmann), (11-13)
•V

where the product is over all energy levels e,.

As a special case consider two systems (Al = 2) with a total of three particles
(MN = 3). Take N x 2
= N =
Note that we do not have an equal number A^
2 and I.

of particles in each system; that condition has been relaxed as mentioned above.
Equation (11-13) tells us that the total number of configurations is

2 1

2 2
3! 24.
2! 1!

Figure 11-3 demonstrates how these 24 microstates are generated.

The method of Section 2-3 may be adapted here to search for the most probable set
of A^ 's. Since W{ N N2 x
, , . . .
) gives the number of microstates for a given set of A^-'s,
the most likely set is the one occurring most often, that is, the one causing W to be
largest. We therefore maximize W{ x
, N 2 , . . ) with respect to the values of N N x
,
2 , . . . .

As in Section 2-3 we find it easier to maximize In W rather than W itself. This process
gives the same result because the logarithm of any function has its maxima and
minima same locations as those of the function itself.
in the
Unfortunately, we cannot maximize In directly because not W all the Nt
's are
independent variables; there are two relations involving the N t
's. One such constraint
 A 1 .

548 Quantum Statistical Physics

is that the sum of all particles on all energy levels is the total number of particles in
the ensemble:

oo oo M M oc M
E^ = E=
1=1 i 1
E"! T) =
y= 1
E
y= 1 i
E»! Y) = I,N {y) = MN,
= 1 y= 1
(ll-14a)

which follows from Equations (11-7), (1 1-8), and (11-9). Similarly, the total energy of
the ensemble is given as

oo oo A/ M oo M
£.*M= E^,E"! Y, = E= Ev4 Y) = L£ {y)
= ME, (n-i4b)
/=1 i =1 y= y
= l' l
Y
= '

which makes use of Equations (11-9), (11-11), and (11-12). By using Equation (11-10)
we can put these constraints into a slightly different form for later use:

N= T:E^=E", (H-15a)
M
and

E= wE^-e,-= £»,*,-. (ll-15b)

In order to incorporate the constraints into the maximization procedure, we follow

the method of Lagrange introduced in Section 2-3. Recall that, instead of using just

In W we form the auxiliary function

F(N ,N2{
a, fi) = \nW - d^N, - NAf) - fil Ec.-ty - EM ] ,

where a and /?, often called Lagrange multipliers, are as yet undetermined. We then
apply the conditions
3F
--0 (11-16,

for all i, treating all N t

as independent. The multipliers a and /? are found, and can
be eliminated, by use of the constraint equations. The net result is that In W is

maximized and the two constraints are also satisfied simultaneously.

Before applying Equation (11-16) it is helpful to simplify In W
by use of Stirling's
approximation, Equation (2-26). For the W of Maxwell-Boltzmann statistics, Equa-
tion (11-13), we find

In W= ln( NM\ + ) In MN '

+ In MN * + - In JV, - ! In A^2 !
- • •
•

= ln( NM\) + £ { A^ln M - N,ln N + {

A] }

The function F becomes

F= ln( NM\) + £ {
r
,ln M - A> A[ + N, - aN, - (3N,e, } + aNM + (SEM.
 11-2 Thermal Distribution Functions 549

It is now easy to carry out the maximization:

dF
0= = \nM -InN,- a - fie r
dN

Solving this for N t

yields

N = Me~ ae-^. (H-17)

The Lagrange multiplier a may be eliminated by using the constraint Equation

(ll-15a):

M .

If, as in Chapter 2, the partition function Z is defined by

Z-E*-**, (11-18)

then

AT
e~° = — (11-19)

Putting this back into Equation (11-17) gives the result for the most probable N t

value,

MN
N, = e-K.
Z

By Equation (11-10), the Maxwell Boltzmann distribution function n x

becomes

AT
»,.= —*-* (Maxwell -Boltzmann), (11-20)

in agreement, of course, with the result of Section 2-3, Equation (2-35).

The second Lagrange multiplier ft can be eliminated by the other constraint
relation, Equation (11-1 5b). However, as shown in Chapter 2, (5 is \/k R T, so we
choose to keep it as an independent variable.

(ii) Fermi - Dirac Statistics We again suppose our MN particles have been spread over the
levels so that N i
are in all the e ,
levels, N.> in all the e levels,
2
and so on. We ask how
many ways a horizontal dispersal of Nt
particles can be made. Since these particles
are fermions, no more than one can be put in a single energy level of one system.
Obviously, we must have > Nr M In any configuration we have N filled levels t

(particles) and M
— N empty onest
("holes") as shown in Figure 11-4. To develop
new and holes.
microstates interchange particles The number of ways all objects M
can be interchanged M\; however, this involves interchanges of particles with
is

particles and holes with holes which do not generate distinct microstates for indis-
tinguishable particles. Consequently, we must divide by the number of interchanges of
each of these quantities, given by, respectively, A^! and (M — A',)!. We find then that
 >

550 Quantum Statistical Physics

Figure 11-4

Possible configuration of N:
Fermi-Dirac particles in M systems on energy level e t
. A new-
configuration can be generated by interchanging a particle and a hole (empty

12
_o o_ _o
3

;;;
N,

o_
level).

E .

'
1 2 3 4 -
M-\ M
System number —

the number of horizontal configurations is

Ml
ryfo =

an expression that the reader may recognize as the coefficient of the general term in
the formula for the binomial expansion.
In the Maxwell -Boltzmann case the next step is to consider vertical or diagonal
rearrangements. However, here the particles are indistinguishable so that an inter-
change of a particle with energy e, with one of energy e does not produce a new state. •

Accordingly, we have finished counting and the total number of configurations is

given by the product of the W^ for all the various levels e t
:

Ml Ml
W=
N X
\(M - N x
)\ N l(M- N2 2
)l

In terms of the product symbol this is written as

^=11
„ Ml
;
r (Fermi-Dirac). (11-21)

Figure 11-5 illustrates this counting scheme for the example of M= 2, TV, = 2,

N 2
= 1. Equation (11-21) gives

2! 2!
= 2.
0!2! 1! 1!

In this case there are only two ways of interchanging particles to generate distinct
microstates.
Next we maximize In subject W to the constraints. From Equation (11-21) and the
Stirling approximation we find

F = £{lnM!-(Af- A0ln( M - N, ) + (
M - N, )
- N,\n N,

+ N, - aN,- PeM + aNM + } fiEM.

The differentiation proceeds as before:

dF
=
dN
= ln(v M-N ,))
- In N - a - fie,
 / 1-2 Thermal Distribution Functions 55!

Figure 11-5

Ensemble with three Fermi- Dirac particles in

two systems. Each system has two energy levels
with N = 2 and A^ = 1 Because the particles
{
.

are indistinguishable they are not numbered

as in the Maxwell- Boltzmann case. Since the
particles are fermions an energy level can be
occupied by no more than one particle. Thus,
there are only two possible configurations,
both of which are shown.

o o
o o o o
System 1 System 2 System 1 System 2

Microstate 1 Microstate 2

so that

M- N,
a
= e e^
N
The solution for the most probable value of TV, then gives N /M as
t

' pt
(Fermi-Dirac). (11-22)
„<»„P£
e"e -
+ 1

a p *'
The quantity e e is nonnegative for all values of the parameters. This property
leads to a result expected for fermions, namely, that for all energy levels £,,

«,< 1.

Instantaneously, no state can hold more than one particle; on the average, there is

usually less than one.

In the above discussions we have not considered the spin of the particles. Since the
fermions do have spin, this effect can be included simply by supposing that each spin
orientation corresponds to a distinct state £,-, even though each of these states may
have the same value of the energy. In this way, for fermions, we still always have
«,< 1.

Now that we have gone through the procedure of deriving the fermion distribution
function it is possible to see why the simpler method used in deriving the
Maxwell-Boltzmann distribution in Chapter 2 could not have been used here. That
derivation assumes that n t
\ can be represented by the Stirling approximation, which
requires n !
^> 1 for its validity. This condition does not hold for fermions. The
derivation presented here requires only that jV, » 1, which can be satisfied for
particles of by making
any large enough.
statistics M
a
The constant e in Equation (11-22) is not as easy to eliminate as in the
Maxwell-Boltzmann case. For this system a has important physical significance, as
we see in Section 1 1-6. Nevertheless, it is still related to the particle-number condition
 — !

552 Quantum Statistical Physics

Figure 11-6

Possible configuration of N, Bose- Einstein particles in M systems on energy level e,. New
configurations of indistinguishable particles can be generated by interchanges of the N :
particles
and M— 1 partitions.
• •

6
'66ol 61 ooool lo-l —
System number
I

12
,
1 t^l

^Partition
I

3
,
1
1^1
4
l^J
5
...

in Equation (11 -15a) so that we can write

K= E", = E ,^p ,^ t ,
(Fermi-Dirac). (11-23)

In certain limiting cases this equation can be solved analytically and a can be
expressed in terms of N, as we show in Sections 11-3 and 11-6.

(iii) Bose - Einstein Statistics In this case we are concerned with indistinguishable particles
but are not limited to assigning just zero or one particle per energy level. Horizontal
counting is a bit tougher here, but there is a trick that can facilitate the task. A
possible configuration of N l
particles among the M systems is shown in Figure 11-6.
The systems are separated from one another by partitions. We generate all configura-
tions by considering all possible interchanges of the partitions and particles shown in
the figure. For example, if we interchange the second particle and the first partition
we get a new microstate having one particle in system 1 and three in system 2. The
number of ways of making interchanges of all N particles and all — 1 partitions is t
M
(N + t
— M
1)!; however, this includes the N interchanges of particles among them- t
\

selves and the (M — 1)! interchanges of partitions among themselves. To get the
correct count we must divide out these interchanges. It follows that the number of
horizontal configurations on the th energy level is /

{N, + M- 1)!
W U) =
N,\(M - 1)!

Again we need not consider interchanges of particles on different energy levels for a
given N,, N 2 , . . . because of particle identity. So the total number of states is found by
1
taking the product of all the Wf '
to get

{N,+ M- 1)! (N2 + M- 1)!

W=
N \{M-
t
1)! N \(M-
2 1)!

oi

„(N;'+M-
— 1 )

jy=n r~ (Bose-Einstein). (11-24

V N,\{M- 1)!
t
 / / -2 Thermal Distribution Functions 553

Figure 11-7

Ensemble with three Bose- Einstein particles in two systems. Each system has two energy levels
with jV, = 2 and Af, = 1. The particles are indistinguishable but more than one can be in a

state. Three of the possible configurations are shown. The other three are obtained by changing

the single particle in e, from system 1 to system 2. Note that an interchange of the
two e, particles in the middle configuration does not generate a new state, unlike the

Maxwell- Boltzmann case.

o o o
E, -
oo o o oo
System 1 System 2 System 1 System 2 System 1 System 2

Microstate 1 Microstate 2 Microstate 3

As an example of the formula we again consider the possible microstates of an

ensemble with M N
= 2, A/, = 2, 2 = 1, but with bosons now populating the states.
Equation (11-24) tells us that should be W
3! 2!
= 6.
2! 1! 1! 1!

A total of 6 states agrees with the counting shown in Figure 1 1-7.

If we now repeat the maximization procedure with use of Equation (1 1-24), we find

n. = (Bose-Einstein). (11-25)
e"e^ 1

(The proof is left to Problem 8 at the end of the chapter.) The Lagrange multiplier a
is again determined by the condition in Equation (1 l-15a) so that the average number
of particles in each system is given as

*—> „«„/3f,
(Bose-Einstein). (11-26)
1

To see the effect of statistics on the distribution function in this case let us consider
the lowest energy level, which we can take to be e, = by adjusting the arbitrary zero
of energy. Equation (11-25) gives

(11-27)
e
a - 1

Since n x
is number it must be positive; Equation (11-27) then tells us that
a particle
the parametera must be positive for a Bose system. It turns out that at a sufficiently
low temperature a becomes quite small and n then increases dramatically. This {

sudden congregating of particles into the lowest state is called the Bose -Einstein
by Einstein alone). This phenomenon is a vivid example of our
condensation (discovered
claim that bosons prefer to be in the same state, and is used in Chapter 1 3 to illustrate
some aspects of the superfluid behavior of liquid He at low temperatures.
 .

554 Quantum Statistical Physics

We end this section by stressing the limitations of our results. The derived
distribution functions are useful in treating independent, or noninteracting, entities
(e.g., elementary particles, atoms, molecules, phonons) that have well-defined single-
particle energy states. Many (perhaps most) systems are made up of particles that
interact with one another so that single-particle energy eigenvalues are not identifi-
able. There are procedures for dealing with the thermal properties of these systems;
however, we do not treat them here.

11-3 High-Temperature. Low-Density Limit

There are circumstances in which quantum indistinguishability effects are not particu-
larly important. Our discussion of eigenfunctions in Section 11-1 shows that this

occurs when exchange terms (as in Equation (11-6)) become small. The special case
given there, of localized single-particle functions each with de Broglie wavelength
small compared to the interparticle separation, illustrates one way
this could happen.

Such a situation actually arises in a tightly bound solid where strong interatomic
forces hold the particles close to their lattice positions and the eigenfunction for any
given particle is highly peaked.
For a system of independent particles like those described by our thermal distribu-
tion functions, we can define an average or thermal de Broglie wavelength A th This .

quantity depends inversely on the average particle momentum. If the temperature is

sufficiently high or the density low enough that X th is much smaller than the
interparticle spacing then a Fermi or Bose gas behaves classically and Maxwell-Boltz-
mann statistics does a good job in describing the gas.

To see how thishappens refer back to Equation (11-19) where the Lagrange
multiplier a in the Maxwell Boltzmann case is given by

Z
e
a = —
By evaluating the partition function Z, defined in Equation (1 1-18), we can show that
a
the conditions of low density and high temperature make e very large. This gives us
a clue about the appropriate limit to take to find classical behavior in the Fermi and
Bose distributions. In the example at the end of this section we show that Z is given
by
V
(11-28)

where X th is given by
l 2

th
\2itmk B T] '

In Problem 6 at the end of the chapter this quantity is shown to be proportional to

h/(p 2 ) l/2 which

, qualifies it as an average de Broglie wavelength. We find from these
results that

V 1

(11-30)
*K
which we see obeys e
a
;» 1 if we have small density N/V or high temperature.
 11-3 High-Temperature. Low-Density Limit 555

a t
If, in the Fermi or Bose distributions (Equations (11-22) or (11-25)), we take e e^ '

very large compared to unity we immediately get

this indeed reproduces the Maxwell-Boltzmann distribution of Equation (11-20).

Next, let us calculate the pressure in an ideal gas at high temperatures and low
densities. To perform this computation we need to show how a formula for pressure
may be derived.
Consider a many-particle quantum system in a single energy state E n
. If some
external variable, on which E n
depends, is very slowly changed, the system remains in
that state whileE n slowly changes. For example, if a simple pendulum is in its ground
stateand the string length is slowly shortened, the pendulum rides up in energy with
the ground state. However, if a change is made rapidly an oscillator might change its
energy state as well as have the levels themselves change.
Suppose we compress a gas by a slow volume decrease dV. An energy level e,
increases to e, + dz and particles in this energy level gain an energy de r The total
t

gain in energy by the entire system is

dE=Y n de J i i
. (11-31

This increase in energy comes from the work done on the system by the external agent
compressing the system. If the gas is in a box having edge of length L, the length is

diminished by dL and the work done by force F is

dW = -FdL.

(The minus sign occurs because positive work is done on the system when L
decreases.) The force F is opposed by the pressure of the gas on the walls of the
container, each of which has area A. Since pressure is force per unit area we have

F= PA
or

dW= -PAdL= -PdV. (11-32)

This work dW must be equal to the change in energy in Equation (11-31) so that
the pressure becomes

P=-E«,^. (H-33)
i

For an ideal three-dimensional gas in a cubical box of length L the energy levels
are given by Equation (5-99),

2 2
«W,= ('l + '2 + 'l)T-7
LmL~
(11 " 34 )

with ff
l5
nf
2,
«f
3
positive integers. Since L is V x/i we can write e, = C V~ 2/3 where C
t
,
t
556 Quantum Statistical Physics

is a quantity independent of volume. It follows that

—=
de

rfF
t
2
--C,F" 5/3 =
3 '
--C
2

3 '
F-2/3

V
=
2

3
e,

V
L
.

Thus, for any ideal gas, whether classical, Fermi, or Bose, we have

21 2 E
P = --Y,n,e, = , (11-35)
3 V; ' '
3 V

where E is the average total energy of the gas.

For the Maxwell-Boltzmann gas (or for Fermi and Bose systems in their high-tem-
perature, low-density limits), we can use the result, derived in Section 2-3 and in a
Detail at the end of this section, that the average single-particle energy is

(e) = \k B T. (11-36)

But we know that (e) satisfies

E= N(e)
so

PV=Nk B T, (H-37)

the familiar ideal gas law.

We have shown that the quantum distributions reduce to the Maxwell-Boltzmann
function if we take e" very large. The quantum distribution functions can be written
as

a pt '
(11-38)
IU
'
e"e '
±1 1 + e~ e- '

where the upper sign refers to fermions and the lower to bosons. The Maxwell
distribution results from taking the denominator of the last form in Equation (11-38)
equal to unity. This is equivalent to e'^'^ 1 ' <s: 1. Suppose we go one step further
and make a binomial expansion in small x using

= 1 + x + x- + ••• , (11-39)
1 + x

the Taylor expansion in powers of x. The result gives the Maxwell-Boltzmann

distribution and the first quantum correction:

„.= e-^-^il + e- e-
a pf -
+ ). (11-40)

From Equations (11-33) and (11-40) we can show, by a somewhat involved

argument that we do not present, how the pressure is changed by the extra term in
Equation (1 1-40). We find that

PV=Nk B T i±-^+... . (11-41)

 1 1-3 High-Temperature. Low-Density Limit 557

The terms given are the first two in an infinite series, called the virial expansion, which
is powers of (X\ h N/V). This factor is small at low densities and high temperatures.
in
Note the sign of the correction term. The upper sign in Equation (11-41) refers to
fermions, the lower to bosons. The pressure for fermions is higher than for Maxwell
particles, confirming what we expect from the Pauli principle. Because two fermions
cannot be in the same spatial location, each fermion moves in a smaller volume than
if the particles were distinguishable so that the pressure of the gas on the walls of the
container is increased. Thewhat occurs if there is a force of repulsion
result is just
between Maxwell -Boltzmann Bosons, on the other hand, prefer to be
particles.

located in the same state. Their statistics gives a result analogous to a Maxwell-Boltz-
mann gas with an attraction; the particles do not hit the walls as often, so the pressure
is reduced slightly over the high-temperature limit.

In Section 11-6 we show the effect of statistics on the Fermi gas pressure in the

opposite (low-temperature) limit. In Chapter 13 we examine the low-temperature

situation for bosons.

Detail

To compute a sum over single-particle energies of the form L /(e), where /(e) is f

an arbitrary function, we need to carry out a procedure that has been discussed
in the example at the end of Section 2-3. We briefly repeat portions of that

derivation here to establish notation for later use and thereby introduce the
density of states function. We consider free particles in a large box with sides of

length L and volume V = L The particles can be fermions, bosons, or classical

.

particles. The energy levels of a particle in a three-dimensional box are given by

Equation (11-34) with /, = 1,2,3 The sum over e is just a sum over the
three £ For a very large box the spacing between energy levels, given by
{
.

h 77 /2mL~, is very small so that sums over the ( can be converted with t

negligible error to integrals. By this treatment a typical sum becomes

/• + oo f + oo /• + oo

E/(e) = E f(e) = i/ deA dlA dt3 f(e), (11-42)

f 4<f2 /3 -00 '-00 •'-00

where the factor g enters because we have extended the /, integrations over
negative as well as positive values. Just as in the case of blackbody radiation, we
can consider the £ as components of a three-dimensional vector t whose length
{

f depends on e according to Equation (11-34). Since /(e) varies only with the
magnitude of vector /, we change from the Cartesian integration of Equation
(11-42) to spherical coordinates and then change to an integration over e:

_
E/(e) = —
477

8
/
/.oo

Jn
dM f(e)2
= -
77

I
r oo

J(\
de^-f(e)
di
(it
(11-43)

2
with t= ^{[ + c°
2
+ t°l .The 477 in Equation (11-43) comes from integrating
over all directions of / The density of states function is defined as the number of
levels per unit energy in the range e to e 4- de. This quantity is denoted by Z)(e)
in the relation

E/(*)= pe/)(e)/(e).
 \

558 Quantum Statistical Physics

By Equations (11-34) and (11-43) we have

1/2
77 de 77 / 2mL 2 e 2mL ' !

\ f
2\ aV J { nv ) 2^
or

m 3/2
/2
DU) Vc' (11-44)
/2W .

1/2
Note that D(e) is proportional to e , a result that holds for nonrelativistic
particles of any statistics in three c imensions.

Detail

The single-particle partition function for Maxwell-Boltzmann statistics is

Z= J> _/Je with /3 = (k B T)~\ (11-45)

f

This quantity is easily computed by use of the density of states function derived
in the previous Detail. We have

,oo m i/2 V ,oo

2 3
^0 /2 77 ^ ^0

taking x = fie. The dimensionless integral has the value V77 /2 so that

V
Z=tt-, (H-46)
A th

where the thermal de Broglie wavelength is defined as

"- 47)
x
* = [^f) •
(

The probability of finding a particle in state c, for Maxwell-Boltzmann

statistics is

n, *-*
/'(£,) = — = (11-48)

The probability density for finding a particle in the energy range e to e + de is

«"* 2
p(e) = D{e)— = -frrfiW2*-* (11-49)
z yw
 11-4 Photon Statistics 559

The average single-particle energy is then obtained as follows:

< e>
= (°°deep(e) = -^ 2
f A^"'' = -^(k B T) 5/2 ^ 2
C dxx^e-
2 Zfr 3
=
7=(* B :r)—---k B T. (n-50)

In this calculation we again use the substitution x = fie to make the integral
dimensionless. The final result is the same as that found in Section 2-3.

11-4 Photon Statistics

Planck was able to make use of a counting procedure equivalent to that of

Maxwell -Boltzmann statistics when he derived his blackbody radiation formula. The
oscillators that constituted the distinguishable particles in the various states nhv were
the radiators in the walls of the cavity. These particles were distinguishable because
they were highly localized on the lattice sites in the walls. He calculated the radiation
energy density by considering the radiation to be in equilibrium with the oscillators.

Einstein pointed out that this argument was inconsistent because the part of the
derivation involved in finding the relation between the radiation energy density u v
and the average energy (e) of an oscillator, given by

2
877- v
", = ~^-( £ )'

was completely classical; that is, it did not take into account the quantization of the
oscillators emitting the radiation. It was only in writing down the correct expression
for (f) that the oscillator quantization was invoked.
We have avoided this pitfall by considering the radiation field itself to be
quantized. The radiation field energy can be thought of as that of distinguishable
oscillators of frequency v, which can be in states nhv.
This view is quite valid but can be improved by making greater use of the photon
picture involved in the photoelectric effect and in Compton scattering. Instead of
thinking of the radiation field as having, for example, one oscillator of frequency v in x

an excited state nhv and another of frequency v2 in state mhv>, we envision there
x

being n photons each of energy hv and m of energy hv 2 and so on. This is the view
]
,

introduced in Chapter 2, but now we make it explicit in the thermal calculations.

Photons are spin-1 particles and are therefore bosons. The calculation of their
average energy must take into account their indistinguishability according to the
discussion of Section 11-2. Since photons are massless particles they can easily be
created and destroyed while being emitted and absorbed. Thus, the number of
photons in a cavity is not constant. Indeed, their number depends on the temperature
and frequency. What this means is that the condition imposed by using the Lagrange
multiplier a in the derivation of Equation (11-25) is unnecessary here. We can get the
result appropriate to photons by taking a = in that equation. The average number
of photons of frequency v at temperature T becomes

fih.
e
560 Quantum Statistical Physics

The average energy in frequency mode v is then given as

hv
<«>=«>= -^ (11-51)

in agreement with Equation (2-38). The rest of the discussion of blackbody radiation
follows precisely as in Chapter 2.

11-5 Phonons

It was Einstein (again!) who recognized that the quantization of the oscillators in the
blackbody cavity walls had implications concerning the thermal properties of solids
themselves as well as the radiation with which they were in equilibrium. Deviations
from the classical laws for the heat capacities of solids had already been discovered.
The explanation of these deviations was another step toward the verification of the
new quantum ideas.
That the thermal properties of radiation and of solids are explicable by the same
quantum ideas comes from the very close analogy between photons and the quantized
sound waves in a solid.
We first consider a solid by a simplified treatment known as Einstein 's model. In
most crystals each molecule is bound tightly in place by the forces resulting from the
surrounding molecules; a molecule oscillates about its lattice site. Einstein's model lets
every molecule oscillate harmonically with the same frequency v as if each particle is
attached to its lattice site by a single spring with the spring constant the same for
every particle. A more accurate picture is one in which all the particles are intercon-
nected by springs. We see below how this changes the results, but first let us consider
the Einstein picture.
If the particles are highly localized about lattice sites, their wave functions do not
overlap much. Hence, particle indistinguishability need not concern us and we can use
Maxwell-Boltzmann statistics. Each oscillator has energy levels nhv and the average
energy per oscillator (e) is calculated in precisely the same way as in Equation (2-42),
so that we find

< e>
X /
= —-— with0=
3hi>
-Si
e^"" 1 kBT
1

.
(11-52)

The factor 3 arises because each oscillator is three-dimensional and we consider it to

have equal frequencies for vibrations in the three spatial directions.
The total energy for N particles in the solid is

E= N(e).

The heat capacity C is defined as the total heat required per degree of temperature rise
in the entire system. (The specific heat is the heat capacity per particle, C/N ). Here the
heat added is equal to the increase in internal energy E so the heat capacity is

C= —
dE
dT
=
3N(hv
T kB
a)
,
2
e
e^""

P»'»-\f
-. (11-53)
{

For large T (small ft) we can expand the exponential according to

,/»*»o= i + $hv + ••• . (11-54)

 11-5 Phonons 561

Figure 11-8

Heat capacity of a solid as predicted by the

Einstein model. At high temperatures C
approaches Nk B , the classical result, but drops
toward zero at low temperatures in general

agreement with experiment.

3» T

Such an expansion has been used previously in Problem 8 of Chapter 2. Then E

reduces to
1

E = 3Nh v -^— = 3Nk B T ,

(11-55)
'°Phv

in agreement with the classical law of equipartition, Equation (2-20). The heat
capacity becomes

C=3Nk B {k B T^>hv ). (11-56)

This is the law of Dulong and Petit (P. L. Dulong and A. T. Petit, 1819); the heat
capacity is independent of temperature at high T. Deviation from this law at low
temperatures was another element along with blackbody radiation in the case against

the classical theory. It was found experimentally that C dropped below Nk B at low
enough T.
We can see how quantization gives a cure for the inadequacy of Equation (1 1-56).

Figure 11-8 shows a plot of Equation (11-53). As the temperature drops C begins to
fall for k B T < hi> ; here the thermal energy is of the order of the energy level
separation and the discreteness of the energy levels becomes important. When
kB T <§: hv , the exponential in Equation (1 1-53) is large so

C-> "J < (

k sT«hv {) ), (11-57)
k B T*

which goes to zero as T —* 0. At T= all oscillators are in their ground states and if

the system is to absorb energy some oscillators must make the transition to a state hv
higher in energy. Until k B T approximates hv , this is unlikely so C is exponentially
small in this model.
Measured values of C in real solids do show C — Nk B > as T becomes large, and C
does indeed drop toward zero at low temperatures in agreement with the Einstein
model. However, at low temperature it is found that C does not obey the exponen-
tially decreasing form given by Equation (11-57).
562 Quantum Statistical Physics

Figure 11-9

System of springs and masses to be used as a one-dimensional model of a crystal. The

equilibrium interparticle spacing is a. Only longitudinal waves are considered.

^ — ~ ~ ~ X

The explanation for this deviation from the Einstein model was given by Debye
who assumed that the molecules in a solid were connected together by harmonic
forces. The solid was visualized as a set of masses in a kind of three-dimensional
bedspring.
One of the characteristics of such a system is that longitudinal and transverse waves
can travel through it. These modes are the solid-state version of sound waves. Such
waves can have very long wavelengths ~ length of sample) and very short wave- (

lengths ( ~ separation of molecules). For long wavelengths where the lattice discrete-
ness is not important, the modes obey a standard wave equation that shows the
frequency and wavelength of the standing waves to be related exactly as they are for
blackbody radiation in Equation (2-18). However, here c becomes the velocity of
sound in the crystal.
While the theory of sound waves becomes quite analogous to that of the radiation
discussed in Chapter 2, there are three differences between sound and electromagnetic
modes: (1) The number of modes is not infinite. Very short wavelengths (very high
frequencies) are not allowed; the minimum wavelength is equal to twice the distance
between particles in the lattice. (2) A relation like Equation (2-18) holds for low
frequencies but deviations from it occur for higher frequencies. This phenomenon
corresponds to dispersion of the sound waves (higher frequencies have smaller veloci-
ties) and occurs because the system is not continuous but is made up of discrete masses
connected by springs. (3) just two polarizations but three. For some
There are not
directions of sound waves through a crystal these correspond to two transverse modes
and one longitudinal.
A one-dimensional model of a crystal is shown in Figure 11-9 in which a large
number of particles are attached together with springs. In this model we consider only
longitudinal motion. We can show that in the limit of very large N the frequencies of
this system are

vn = v\\ -cos
/

—
mn \

j
'/ 2
(11-58)

with integer values of n = 1,2,3,..., N and v = (\ /2m)yj2K/m where , K is the

spring constant. (See the discussion in Section 12-8.) If we assume n/N to be a
continuous variable from to 1, this function can be plotted as in Figure 11-10. If we
had just one particle connected by two springs to the wall there would be one
frequency in the longitudinal direction having value v . For very many particles the
possible waves on the system are spread into a band from v = to v = v2 v .

For small n/N, the cosine in Equation (11-58) can be expanded and only
lowest-order terms need be kept. We use

2
x
cos x = 1 — — +
2
 7 1-5 Phonons 563

Figure 11-10

Allowed frequencies of the system shown in

Figure 11-9. The discrete variable n has the

values l,2,...,N; for large N, n/N may be

The system has a
taken as continuous.
maximum frequency vm = y2v where 2irv ,

= y/2K/m The slope of the curve is constant

.

for small n but decreases at large n, indicating

the presence of dispersion.

the Taylor series expansion about x = 0. Then Equation ( 1 1 -58) becomes

I 2
l / irn
-
+
1
ib'
vf m
n «: N. (11-59)
ft N
'

This equation describes the initial linear part of the curve in Figure 1 1-9. If we reduce
the discussion of electromagnetic waves summarized in Equation (2-18) to one
dimension by taking n, = n, n2 = n3 =
Equation (2-13)), we see that (or refer to
Equation (11-59) has the same form with the velocity of light now replaced by the
velocity of sound given by

c
s
= \f2TTP a. (11-60)

We have taken the length of the crystal to be Na with a the equilibrium interparticle
spacing. The group velocity of waves along this chain of particles is proportional to
the slope of the j'-versus-H curve, as illustrated by Equations (11-59) and (11-60). The
decrease in the slope of the curve in Figure 11-9 as n/N —* 1 corresponds to
dispersion; higher-frequency waves move more slowly.
Let us next consider a three-dimensional model of a solid, with each particle
connected by springs to nearest neighbors in all directions (bedspring model). Then
the frequencies v may be characterized by three integers «,, « 2 , n 3 , and for small n t

the relation turns out to be

/ I
<L
i, + i

n2 + i

n 3
(H-61
21

The total number of frequency modes is still jV if we allow only longitudinal waves to
564 Quantum Statistical Physics

move through the crystal. If we assume a crystal with a cubic shape having length L
on a side, the number of particles along one edge is

L
N x
= - = N l/ \
a

and each n t
then ranges over

I < n,< Nr
Small n t
in Equation (11-61) means n t
<sc N x
. For large «, Equation (11-61) is no
longer valid and the frequencies begin to show dispersion.
For each set (n {
, n 2 , n3 ) three polarizations of waves can occur, which in the
simplest situation are two transverse and one longitudinal as mentioned above. In
most situations the sound velocities of the three polarizations differ. We ignore this,
consider c to represent some average sound velocity, and simply multiply our results
i

by 3.

The analogy of sound waves to electromagnetic radiation is so strong that the idea
of a phonon may be introduced. A mode v (characterized by the three integers

«,, n.,, n.^) may be in an infinity of quantum states having energy

f„ = n v hv.

We say that such a situation corresponds to the presence of n v bosons called phonons,
each of energy hv, that move through the crystal. These massless "particles" are
actually collective modes, that is, cooperative motions of large groups of particles. These
particle-like objects move through a real "aether," the crystal lattice. The
phonon-photon analogy carries us quite far. Particle scattering is often used to study
the structure of crystals; for example, neutrons shot through a crystal interact with the
nuclei at the crystalsites. In the scattering processes we can see analogues of Compton

scattering of phonons by neutrons; the neutron can absorb or emit phonons while it
passes through the crystal.
At temperature T the average number of phonons is given by the Bose-Einstein
distribution function (with the Lagrange multiplier a set equal to zero as for photons)

"
e^ - 1
'

and the average energy in frequency mode v is

= (11 " 62)

<^> 7^TT
just as for photons. To find the total energy of the solid we sum (e„) over all integers

n l ,n 2 ,n 3 on which v depends:

£=3 L ;^— (11-63)

The factor of 3 is to account for the three polarizations.

We note that there is a maximum frequency vm among the values of v. In the
one-dimensional case this is v2 vQ as shown in Figure 1 1-9. Thus, it is meaningful to
 11-5 Phonons 565

consider a high-temperature limit of Equation T hvm the exponential (1 1-63). If k B » ,

denominator may be expanded in powers of the small quantity (Shv so that

e
phv _ ! = l + p hp + . . . _ x „ p hv

for all v values. The result for E is

£= 3 £ —
15
hv

hv
- =3Nk B T, (11-64)

where the last equality follows because the total number of integers n x
,
n2 n3 , is N.
This is the same classical result that occurs in Einstein's model, Equation (1 1-55), and
leads to the Dulong-Petit law, Equation (11-56), which is experimentally correct at
high temperatures.
At lower temperatures, such that k B T < hvm we cannot get away with such an ,

easy derivation. However, as we change one of the integers n, by a single unit while
summing over «,, n,,, « 3 the summand in Equation (11-63) varies very little. This is
,

true because, according to Equation (11-61), v behaves as n,/N where is a very

x
, N x

large number. Thus, it is always valid to convert the sum to an integral, so that we
have

rN. rN, rN. hv

= 3/ >,/ dnJ dn 3 -pTv
l

-. (11-65

Let us now change variables from the n :

to an integral over v. That is, we want to
write

rN, rN. rN. r"m

3 / dnj dn 2 \ dn 3 • • = / dv N„ •
, ( 1 1-66)
Jr. Jr\ Jr. Jr.

where A/ ,,
is another density of states function defined as the number of modes at
frequency v per unit frequency interval. To find this function we need detailed
knowledge of how v depends on n ,n 2 ,n 3 which for an arbitrary crystal
l
is often
known only numerically and is not just a simple generalization of Equation (11-58).
If we are interested only in the very- low-temperature behavior of E and C, we can

proceed further. For very low 7", many of the higher frequencies satisfy hv ;§> k B T or
fihv 3> 1. For only these frequencies, it is true that

1 1

nv = -^ « -jr- = e-
pi"
« 1 (^ » k R T)

so that these frequencies contribute negligibly to the sum in Equation (11-63). The
conclusion is that only frequencies such that hv E and, if the < kB T contribute to
temperature is low enough, only the low-energy nondisperswe frequencies given by
Equation (1 1-61) are important. The value of A^„ associated with this relation between
v and the n t
is now essentially the same as in the blackbody case. We find, by
examination of Equation (2-19),

2
\2-nv
566 Quantum Statistical Physics

This from the N„ of Equation (2-19) by a factor f, because of three possible

differs
polarizations instead of two, and in the replacement of c by cs the sound velocity. ,

Thus, we find the total energy of the solid to be

E= — 1277

cs
V
^oo

Jq
dvv2
n^—
e—H
hv
T
1
(
k sT«h Vm ). (11-67)

We are able to replace the upper limit vm on the integral by infinity because, at low
temperatures, the higher frequencies do not contribute anyway. Let us make the
substitution

z = fihv

in Equation (11-67) and obtain

\2ttV ,oo
~
.

E = -iir(* fl
7 ')7 dz

4
The integral has the value 77 /15 so the heat capacity dE/dT is given at low
temperatures by

C= -T^ k B(k B Tf (k B T«h,m ). (11-68)

5 cs h

Solids, at low temperatures, should have heat capacity contributions due to their
phonon excitations that are proportional to T h
(rather than exp( — fihv ) as in
Einstein's model) and this is the result that is found experimentally.
Debye was the first to derive the T !
result. He also defined a convenient
characteristic constant for a solid, called the Debye temperature, given by

3
he Af\'/
0n= —
kB
I

677
2 -
v
\

When expressed in terms of this quantity, Equation (11-68) becomes

C= — W *M^-T\
12 /
. (11-69)

The high-temperature limit, Equation (11-56), holds for T »

Q D and the low-tem-
perature result, Equation (1 1-69), holds for T <§; Q D . Debye temperatures range from
about 30 K for solid helium to 1860 K for diamond.

Example

Solid helium can be made only by pressurizing liquid helium at very low
temperature. It has a Debye temperature of about 30 K as determined by heat
capacity measurements. Its sound velocity is, by the definition of @D ,

_
kB @D 1

'

2 ,/3
* (6t7 A7F)
 //•<? Low-Temperature Fermi- Dine Systems 567

The interparticle separation, ~ (F/7V) 1/3 , is about 0.3 nm so that

(1.38 X 1(T 23 J/K)(30K) 3 X l(T 10 m

c.
= a 300 m/s.
173
1.1 X 10" J4 J-s (677
2
)

For comparison, the velocity of sound in air is 330 m/s. Most solids have sound
velocitiesat least an order of magnitude larger than this. Solid helium is
anomalous in many other ways as well.

Example

The maximum frequency wave in a solid is given approximately, from Equation

(11-61), by

vm = —
2L
4n 2 * ±
C

The vel ocity of a longitudinal sound wave in copper is about 5000 m/ s and the
average interparticle spacing isa ~ 0.2 nm. Thus, we find

3
5 X 10 m/s
vm ~ = 2 X 10 13 Hz.
2 X 10" 10
m
This va lue is considerably above audible frequencies It corresponds to wave-
lengths on the order of an interatomic spacing.

1 1 -6 Low-Temperature Fermi - Dirac Systems

Many common assemblies of particles in nature are degenerate Fermi systems. This
term means that the particles have crowded into their low-lying energy states; this in
turn implies that temperature is small on a scale that is explained below. Examples
3
are nuclei, metals, white dwarf and neutron stars, and liquid He. Before considering
these specific examples we examine the general low-temperature Fermi system.
The distribution function for fermions is, from Equation (11-22),

(3
= H-70)
+a
,j8t,
+ 1 kB T

The Lagrange multiplier a, determined by Equation (11-23), is temperature and

density dependent. At very low temperatures a is found to be negative. To incorpo-
rate this feature we write

a= -0e p (T),
where e F (T) is called the Fermi energy. Equation (11-70) then becomes

,/8(e,-f A
(11-71)
)
+ 1
568 Quantum Statistical Physics

Figure 11-11

Plot of the distribution n, = {exp[/?(f, - eF ) +1} 'at three temperatures. For T= n, is a

step function with Fermi energy e F (0) being the largest occupied energy level. For T> 0, but
T« Tf. = e F (0)/k H , the distribution spreads out to energies of order £ fl T above the Fermi
energy. The energy e F (T) for which n t
= \ is a slight bit smaller than e F (0). For large T
(T » TF ) the distribution becomes very spread out and reduces to the Maxwell-Boltzmann
value «, — exp( — /?£, ) while e F (T) becomes negative.

>£,-

when £/,. is used as a parameter.

A plot of Equation (11-71) as a function of e (
for several temperatures is shown in
Figure 11-11. For T= 0, n :
is a step function; all particles are in the lowest states
consistent with the Pauli principle. The largest occupied energy level at T= is

f,.(0). To see this let us consider a very small positive value of T; note that for
e, < eF, exp[/?(f ;
— e F )] has a negative argument and goes to zero as T— > or
/?
—> oo. For those e, values n :
is unity. However, for e :
> eF, exp[/3^ ;
— e F )] has a
positive argument and goes to infinity as ft
— » oo. In this region n(e) is zero. Raising
the temperature from zero removes particles from the levels e ;
< e^(0) and excites
them to higher states.
Let us investigate further the situation at T= 0. The average number jV of
particles in the system is given by Equation (11-23):

A^=I>,= £ ,£(£,

which determines e F in terms of jV and T. To evaluate the sum we use the density of
states function given by Equation (11-44) and obtain

Y £«,= 2 /"%/)(£,>,,
Jn

The factor of 2 in this equation arises from the fact that fermions are spin- \ particles.
In zero magnetic field each energy state is doubly degenerate and can contain two

particles, one with spin up and one with spin down just as in atomic orbitals.
Because n t
is a step function that cuts off at e, = e F (0) for T= 0, the result is just

the integration of Equation (11-44):

2i/2 m 3/2 V
N= 2T/)(e) de = ' 2
(o). (11-72)
•'n
'o 3tt-' /r

This formula serves to define £ f at T= 0. Solving Equation (11-72) for e F ,

we find

2
h
a> \2/3
MO) (3^ p) (11-73)
1m
 11-6 Low-Temperature Fermi- Dirac Systems 569

where the particle density is p = N/V. The Fermi energy is seen to depend on the
two-thirds power of the density so that, as more particles are placed into the system,

the highest occupied state eF increases. As the temperature is raised slightly from
T= 0, £ Fno longer the highest occupied state but is the energy for which n = l2
is t \

e F decreases as T increases and for sufficiently large T actually becomes negative

(which implies that all states contain on the average less than one-half of a particle).
The total energy of the A^-particle system at T= is

i/2

£=!>,", = 2/
f eF
deD(e)e=—T
2/2
—
m
r Ve /
5 2
(0).
J 5?T h

By using Equation ( 1 1-72) we can write this as

E = iNE F (0) (11-74)

so that the average energy per particle E/N is three-fifths of the maximum energy eF .

We have seen in Section 11-3 that the Pauli principle causes an increase in the

pressure over that of an ideal Maxwell-Boltzmann gas. This effect of particle

becomes more predominant as the temperature is lowered. Even at
indistinguishability
T = there is a residual pressure in the system. This Pauli pressure can be derived
from Equations (11-35) and (11-74) as

P=lpe F (0). (H-75)

Because of the dependence of eF on density p, P depends on the | power of the

density. This result is crucial to the existence of white dwarf stars, as we show below,
and has been observed in other Fermi systems.
The calculation of the properties of fermions at low but nonzero temperature is

considerably more difficult than at T= Rather than carrying out these computa-
0.

tions we give a heuristic argument for the temperature dependence of one of the most
important of the experimental quantities, the heat capacity. As the temperature is

raised particles in states having energies within an interval k B T below eF are raised to
states of order k B T or less above eF , as can be inferred from Figure 11-11. If

kB T <?c e F (defining the low-temperature or degenerate regime) then this region of

excitation is a very k B T about e F For an increase of
narrow band of width .

temperature from zero to T

a fraction (k B T/e F ) of the particles each receives an N
energy increase of order k B T. Thus, the total energy increase is

I k T\
kE~ N\—\k B T (A a r«f,.).

The heat capacity is AE divided by the temperature increase T or

where TF is the Fermi temperature defined as e F (0)/k B . A rigorous calculation gives

C=yMJ— (k B T«e F ). (11-76)

570 Quantum Statistical Physics

It is easily seen that the Fermi temperature provides a scale to measure the degree
of degeneracy. If r« 7F the system has strong particle-indistinguishability effects
and the low-temperature formula in Equation (11-76) holds; for T » TF the classi-
cal-limit formulas become valid.
In the following examples we present some applications of the Fermi formulas to
specific systems.

Example

Electrons in a metal: It is often a good approximation to consider the conduc-

tion electrons in a metal (these are the outer-shell electrons, which are free to
move and which conduct electricity) as if they were noninteracting particles.
Because of the Coulomb interactions between electrons and the positive ions and
between electrons and other electrons, the justification of this model is nontriv-
ial; however, let us accept it as valid. If we assume that the metal has one
conduction electron per atom, the mean separation between electrons is of order
a ~ 0.1 nm or so. The electron number density is of order p ~ I /a 3 The Fermi
.

temperature is found from Equation (11-73) to be

2 V3 2 2
eF (3 W )
h h
2
kH 2 kBm k B ma

(i x io- ;i4
j- s r 5
J
= 8 X 10 K.
23 31 10
(1.38 X 1(T J/K)(9.1 X 1(T kg)(lO" m)
(11-77)

Thus, we find that electrons in metals are in the low-temperature degenerate

regime in almost all experimental situations. The electronic heat capacity is
accurately given by Equation (1 1-76). Of course, the phonons created by atomic
thermal vibrations also contribute to the heat capacity. If the experiment is

carried out at temperatures that are below both the Debye temperature QD and
the Fermi temperature TF , the total heat capacity of a metal has the form

C = Nk B (11-78)

where A and B are numerical constants of order unity.

Example

Protons or neutrons in a nucleus: If we substitute the nucleon mass and

a ~ 10
15
m into Equation (1 1-77) in place of the electronic data we find

10
7> - 10 K.

The nucleons in a nucleus are obviously degenerate under any normal condi-
tions. Only in the early stages of the universe, soon after the Big Bang, could
temperatures of this order exist.
 Problems 571

Example

Electrons in a white dwarf star: Despite the high temperatures found in stellar-

interiors, the electrons in a late-stage star known as a white dwarf are quite
degenerate because the value of TF is so large. When a star burns all its

hydrogen fuel it is made up mainly of a plasma of helium nuclei and electrons.

The gravitational forces between the helium nuclei cause the star to collapse
until the Pauli pressure of the electrons given by Equation (1 1-75) brings a halt
to the collapse. The negative (inward) gravitational pressure can be guessed by
using a formula analogous to Equation (11-35):

Ec GM 2
1

Pg ~
T 1"?' ~

where EG is the gravitational potential energy, G is the gravitational constant, R

is the radius of the star, and M ~ Nm He is the mass of the star made up of N
helium atoms each of mass m He The outward
. Pauli pressure, from Equations
(11-73) and (11-75), is given by

N k
2
I N\ 2/ 3

Pf'~
F^\F
where m e
is the electron mass and the number of electrons is actually 2N y
twice
the number of helium nuclei. Equating Pp and PG gives the radius of the star:

R ~ ^ (11-79)
Gm e
m^M x

We have dropped all numerical constants from this expression to get just an
order of magnitude estimate. we put in numbers we get R = 7 X 10 2 km for
If

M = Mq, the solar mass. This means a white dwarf is a very compact object.
However, it is not quite that compact. Equation (1 1-79) is derived on the basis of
nonrelativistic theory. We show in Problem 21 at the end of the c hapter that an
R given by Equation (11-79) results in a Fermi velocity (v F = J2e F/m) large
enough that relativistic effects must be taken into account. Quite a different
radius-mass relation then results. While the basic idea of our calculation
remains valid, the relativistic treatment yields the interesting result that, for
stellar masses greater than about 1.4 MQ , the Pauli pressure can no longer stop
the gravitational collapse. The star continues its infall, a supernova occurs, and
ultimately a neutron star or a black hole is formed. This critical mass is known
as the Chandrasekhar limit, discovered by S. Chandrasekhar in 1934.

Problems

1. Verify by explicit calculation that the three- particle boson eigenfunction given in the
example at the end of Section 11-1 is symmetric under the interchange 2 <-> 3 and the
permutation 1,2,3 ** 3, 1,2. Write down the equivalent Fermi-Dirac function (see
Problem 8 in Chapter 9) and test its symmetry in the same two cases. Explain your
fermion results.
572 Quantum Statistical Physics

2. A single spinless particle has potential energy V(l), and has two real eigenstates ^ a (l) and
v/^(l) with energies ea and e^, respectively. Two such particles have potential energy
V= V(l) + V(2) + Vmt (l,2), where VmX represents an interaction between the two par-
ticles. Suppose that

/^ B (r)^(r)rfr-0

and that the only nonzero integral involving Fmt is

/^„(1) V 2) Kn,( 1,2)^(1)^,(2)^, dr2 =J,

where / is a positive constant.

(a) Evaluate the energy expectation value in the four two-particle states

*.0)*„(2), ^(1)^(2), and -j= [^(1)^(2) + ^(l)^„(2)]

in terms of e lt , eg, and /.

(b) Which of these states is allowed if the two particles are identical bosons? fermions?

distinguishable particles?

(c) Explain why, for the fermion case, the introduction of an intrinsically positive
interaction (J > 0) leads to a reduction of the two-particle energy.

3. How many distinct throws of a pair of dice can occur? How many ways can a four be
thrown? What is the probability of throwing a four? What number has the highest
probability of occurring in a throw of a pair of dice?

4. Consider an ensemble made of two systems ( M= 2) each having two energy levels f , and
f ,. Energy level f, is occupied by a total of two particles (jV, = 2), as is level e_, (A
:
,
= 2).

Find the total number of ways W of placing the particles in the states if the particles are

(a) distinguishable, (b) fermions, or (c) bosons. Use Equations (11-13), (11-21), and
(11-24) and also find W by explicit counting.

5. Show, for a Maxwell-Boltzmann system, that (c) = — d In Z/dfl, where Z is the

partition function. Use this formula to derive the result of Equation (11-50).

6. Evaluate A/(/?')' / " and show that the result, up to constant factors, is equal to A tl
.

7. (a) Use Equation (5-60) (with position x replaced by energy as a variable) to show that

the mean square deviation of the total energy E= L, =

N
,e
(,)
from its average value is

given by

2
(A£) =^((£2 >-< e >2 ),

where (e) and (f') are single-particle energy averages.

(b) Show, from the definition of the partition function Z, that the mean square
single-particle energy deviation for Maxwell- Boltzmann particles is

(Ae )2 = <E2 ) _ (e)2 = __

d
2
\nZ

Evaluate this quantity.

 Problems 573

(c) Use theresults of parts (a) and (b) to show that the fluctuations in energy of a large

Maxwell- Boltzmann system diminish with size according to

JF) ~ V 3W
'

Evaluate this for N= 100, 10

9
, and 10 23 .

8. Carry out the details of the maximization procedure for the function W in Equation
(1 1-24) to prove that the Bose-Einstein distribution function is given by Equation (1 1-25).

9. Consider a system of jV distinguishable particles in which each particle has two possible
energy levels e, = and e2 = A. An example of such a system is a crystal that can form

vacancies by exciting particles into interstitial positions.

(a) Find the distribution functions n, and n 2 and plot the ratio n 2 /n ]
as a function of

the parameter t = e~^, which has range < t < 1, while the temperature varies

from zero to infinity. Explain the behavior of the graph.

(b) Find the average energy (e) and the specific heat c = d(e)/dT. Plot (e)/A and
c/k H as functions either of t or of k s T/A. Explain the behavior of these functions.

10. (a) Consider a two-level system as in Problem 9 but containing spinless "Fermi-Dirac"
a
particles. Find n t
and n.,. To do this the Lagrange parameter e must be
eliminated by use of Equation (11-23). Carry the solution out for the only two
possible cases N= 1 and N= 2. Why is N > 3 not allowed? Plot the ratio n 2 /n ]

as a function of the temperature parameter t = e~ ' .

(b) Repeat with Bose-Einstein particles for the cases N= 1,2, and 50. The elimination
of the Lagrange parameter e" is not as easy here and may best be achieved by
numerical or graphical methods. Plot n .,/«, as a function of t for each of the above
values of N. Can you generalize the trend to N —» oc?

(c) Compare the plots of n _,/«, from Problem 9 and from parts (a) and (b) of this

problem. Explain the physical basis of the behavior. Why do even the N= 1 Fermi
or Bose distribution functions show quantum behavior?
11. A container filled with H, gas has a pressure of 1 atmosphere (1.013 X 10 5 Pa) at room
temperature. To what temperature must the gas be cooled for quantum effects to become
important? Estimate this temperature by equating the thermal de Broglie wavelength to
the interparticle spacing. Use the ideal gas law to estimate the density. Repeat for the
conduction electrons in a metal for which the average interelectronic spacing is fixed at 0.

nm.
12. Equation (11-49) gives the Maxwell-Boltzmann probability density for finding the
+ de as p(e) ~ e ""exp( — /?e). Find the most
single-particle energy in the range e to f '

likely energy by maximizing p(e). Compare with (e) of Equation (11-50). Find the

half-width of p(s) and compare with Ae evaluated in Problem 7(b).

13. Find the total energy E and heat capacity C of blackbody radiation in a cavity of volume
V. Show that C has the same temperature dependence as the low-temperature phonon
system. Find the average total number of photons present in the cavity as a function of
temperature. Estimate this number for room temperature (300 K) and a volume of 1 cm'.
14. Atoms adsorbed in a monolayer (a layer one atom thick) on a surface at sufficiently high

density sometimes behave like a two-dimensional solid. The low-frequency sound waves
obey a relation of the form of Equation (11-61) with n 3 = 0. Find the heat capacity of
such a solid at high and low temperatures. [Hint: A new density of states A^, appropriate
to standing waves in two dimensions must be derived. Paraphrasing the derivation for
574 Quantum Statistical Physics

radiation in Section 2-2 or even that for particles in the Detail at the end of Section 11-3
may be helpful.]

15. A scale of temperatures for solids, by which we judge whether T is high or low, is set by
the velocity of sound and density, through the Debye constant © D What
. is the corre-
sponding characteristic temperature in Einstein's model of a solid?

16. Find the density of states function A7

,,, as a function of, v, for all frequencies in the
one-dimensional phonon system for which v is given by Equation (11-58). Explain
physically why N v
diverges at c= vm . Find the heat capacity for low temperatures
kH T •« hvm and for high temperatures k H T » hvm .

17. Aluminum has a Debye temperature of 420 K. Use this to find the velocity of sound in

aluminum. What is the specific heat of the phonon system at 300 K? Assume the
low-temperature formula in Equation (11-69) is sufficiently accurate.

18. Calculate the Fermi temperature TF for metallic aluminum. What is the specific heat of
the conduction electron system of aluminum at 300 K? Compare this result with the result
of Problem 1 7.

19. Show that the condition T « TF for the degeneracy of a Fermi gas is equivalent to the
statement A th » a, where a is the mean interparticle spacing.

20. Liquid 'He is a system of fermions that interact quite strongly. Nevertheless, a useful
first-stage model is that of a noninteracting gas of helium atoms. Find the Fermi
temperature, for a mean interparticle spacing of a = 0.4 nm in the liquid. Find the
thermal de Broglie wavelength for
f
He at T= 1 K and compare with the given value of

a. Are the results consistent with the conclusions of Problem 19?

21. Show that the electron system of the white dwarf star in the example at the end of Section

1 1-6 must be treated relativistically. Do this by computing the Fermi velocity for a radius

of 700 km and comparing with the speed of light.

22. The rotational motion of diatomic molecules contributes to the specific heat c = d(e)/dT
in a gas of molecules. In this problem you are to calculate this contribution by considering
a set of distinguishable rigid rotators each with moment of inertia / and energy levels

Bj=j(j+l)B, J = 0,1,2,...,

where B = 2
h /2I.
(a) Show that the partition function is

[Hint: What is the degeneracy of the level e ?]

(b) Evaluate Z for high temperature (BB «: 1) by taking L ;

-*
f dj and then proving

1 /•«> d
J
BB J dj

Discuss the approximation. Find (f) and C by using the theorem proved in
Problem 5.

(c) Evaluate Z, (f), and C for low temperature (BB » 1) by keeping only the first

two terms in the j sum.

 T W E L y E

SOLIDS

wolids are materials that are resistant to de-

forming forces. A crystal is a special kind of solid usually showing facets, that is,

surfaces occurring at certain characteristic angles; these give evidence of a regular

array or latticework of the atoms making up the material. The term "solid" is more
general than "crystal" and can also describe amorphous substances, which may be
every bit as hard as crystals but which have no regular lattice structure. Diamond and
quartz are crystals, but glass is a solid that is not crystalline. Since the long-range
particle periodicity characteristic of a crystal is insufficient to specify what constitutes
a solid, we must look further into the distinguishing properties.
The study of solids has been a part of physics for as long as physics has been a
science. Before that, alchemists were interested in the nature of so-called "base"
metals and whether they could be turned into gold. Navigators found that a lodestone,
a natural permanent magnet, could be used as a compass. To satisfy their needs for
weapons, and jewelry, ancient metallurgists learned how to mix copper and
utensils,

tin to form bronze and to mix the right combination of iron and carbon to make steel.
As in these examples, fundamental knowledge has often followed from the need to
improve technology. In more recent times the order has often been reversed and
technology has entered quickly into areas where new knowledge has been found. In no
area of science has this interrelation been more apparent than in solid-state physics.
The outstanding examples of this are the developments of the transistor and the
integrated circuit, which have brought us into the computer age. These inventions
followed directly from the understanding of the nature of semiconductors and could
not have occurred without that basic understanding.
As important as solid-state physics is to the development of technology, even more
so is its fundamental contribution to our basic understanding of nature. Einstein's
explanation of the breakdown of the Dulong-Petit law of heat capacity in solids is
only one of several first examples of this. Furthermore, progress in solid-state physics
has often stimulated new lines of basic research in other areas. For example, after
years of study of the magnetic transition in iron, recent breakthroughs have led us to
an understanding of many kinds of phase transitions in a wide range of substances.

575
576 Solids

Several recent advances in other parts of physics are based on ideas used to describe
phase transitions in condensed-matter systems.
The passing of ideas from one area of physics to another is a common theme. We
know from our study of diatomic molecules in Chapter 10 that two atoms of hydrogen
bind together because the electrons are able to hop from one atom to the other; this is

the basis of the covalent bond. The periodic potential energies of electrons in regular
crystals also can have sufficiently low barrier heights so that electrons can tunnel from
one atom to another. This effect contributes to binding and so the solid behaves
somewhat as a gigantic many-atom molecule.
This rapid hopping results in a highly characteristic structure for the energy levels
of electrons in solids. The states fall into bands of very closely spaced energy levels
separated by forbidden energy regions called band gaps. The basic behavior of
crystals depends greatly on how the electrons fit into these states, which are filled

according to the Pauli principle. On this basis we are able to understand how
substances fall into the categories of metals, insulators, and semiconductors.
To understand the detailed distinctions among the various kinds of solids, experi-
mentalists can probe the materials by measuring such static properties as their
pressure-volume curves, heat capacities, and magnetizations. They also can examine
their transport properties by setting up nonequilibrium flow conditions. For example,
if we establish a voltage across a sample of metal, electricity is conducted through it
and we can easily measure its electrical conductivity. When we maintain a tempera-
ture difference between the ends of a sample of material, heat flows and we can
determine the thermal conductivity coefficient. The dependence on temperature, and
on other variables, of these coefficients tells us about the characteristics of the carriers
of electricity and heat, and also tells us with what objects these carriers may be
colliding as they traverse the solid.
Insulators are able to conduct heat, though not electricity, by means of lattice
vibrations. The associated phonons have been introduced previously in Chapter 11.
Several properties of phonons have only been quoted there in order to discuss heat
capacity as an example of the methods of statistical physics. In this chapter we justify
those results by deriving them.
Since the first awards in 1901 the Nobel Prize has gone to many physicists for their
work on solids. The achievements have been as significant as any in physics. More
research is published each year in solid-state physics than in any other field. Many of
the papers are reports of technological applications and many are quite basic. These
forms of activity demonstrate to every student of physics the importance of under-
standing the physics of solids.

12-1 The Structure of Solids

We cannot define a solid simply as a substance that is hard. Suppose that we put
water into a closed container with a plunger on one end and then attempt to squeeze
it. We would find it to be "hard" as well since under the application of ordinary

forces water is essentially incompressible. What differentiates solids from liquids or

gases is the ability of the solid to resist shear forces.

If we push vertically on a stack of several decks of playing cards, it does not

compress much. If we push horizontally near the top of the stack, it may collapse
because the cards can slide easily relative to one another. The stack has no shear
strength.
 121 The Structure of Solids 577

The molecules of a gas are basically free particles that only occasionally feel the
effects of intermolecular forces as they collide with one another. The molecules of a
liquid, such as water, constantly feel forces due to the other molecules. They are in a
many-body bound state. A bit of water floating freely in the space-shuttle stays
together as a roughly spherical blob. On the other hand, the total kinetic energy
shared by the molecules in water is still sufficiently great that each molecule does not
find itself bound permanently to a given set of neighbors. Such a particle almost
always has an escape route in one direction or another as it rattles about trying to
move to a new neighborhood. Even if the molecule momentarily finds it has
insufficient energy to escape from a certain small region, collisions are so frequent that
it soon has enough, so a new lower energy pathway opens up because of the other
particles' random motions. However, if one of the particles tries to leave the surface of
the liquid, it usually is unable to do so, because the forces from the other molecules
near the surface pull it back. Occasionally, however, some particles do have sufficient
kinetic energy to evaporate.
If we try to compress a difficulty because there is so much empty
gas, we have no
space. But liquids are far denserand compression causes the hard cores of the particles
to touch and create resistance. The same is true of solids. A shear force applied to
water does not try to push the water into a smaller volume like a compression does. It
simply slides the particles relative to one another somewhat like the playing cards
mentioned above. This costs very little energy; it is essentially what the individual
molecules are already constantly doing on their own.
We are led then to the idea of a solid, with its shear strength, as resulting from the
fact that each particle is bound in a potential energy well formed by its neighbors
from which it rarely has enough energy to escape. Shear forces are resisted because it
takes energy even to slide particles relative to one another. A solid can usually be
picked up without a container because of its shear strength.
One way that every particle can be made to sit in a potential energy well formed
by its neighbors is to construct a perfect array, that is, a crystal lattice. In the simplest
such situation every particle sees precisely the same arrangement of neighboring
particles. If one particle is bound then all of them must be.
Consider a situation in two dimensions
temperature. Suppose the
at absolute zero
particles are xenon atoms, each pair
which has a potential energy of interaction
of
described by the Lennard-Jones form, Equation (10-36). If we neglect the small
amount of zero-point motion, a pair of these atoms sits at the distance a of the
minimum of the potential energy curve and has energy — e, equal to the depth at the
minimum.
The best thing for a third particle to do is to position itself so that the three atoms
form an equilateral triangle having sides a. The energy of this trio is — 3e, correspond-
ing to the three bonds formed as shown in Figure 12-1.
A fourth particle can now be added, in our two-dimensional example, at any one of
three possible positions so that it similarly has two neighbors each at a distance a. If
we neglect the interaction energy between the two particles that are not near
neighbors, the total energy of the two triangles is now — 5e. We can continue in this
manner until whatever amount of two-dimensional space available is filled with
triangles as in Figure 12-2.
Note that every particle in this figure is the center of a hexagon so that it has six
neighbors. If we were arranging Ping-Pong balls on a table so that they were touching
one another, the most that we could pack about any center ball would be six. Those
six would form a hexagon made up of equilateral triangles. We would have packed
578 Solids

Figure 12-1 Figure 12-2

Three particles with interatomic separation a Part of a hexagonal or triangular two-

such that every pair interaction is at minimum dimensional lattice of particles. Particles 1

energy — e. The X 's mark possible positions and 2 are nearest neighbors; particles 1 and 3
for a fourth particle. are second neighbors.

O-O ® o o
o o Q-® o
o cAiA) o
O O O-O o
o o o o o

the balls as closely as possible to one another. More balls could be added to fill

two-dimensional space as illustrated in Figure 12-3. No denser arrangement of balls in

two dimensions is possible. The lattice formed is equivalent to that of Figure 12-2, and
is therefore called a hexagonal close-packed lattice, or simply a triangular lattice.
The energy of such a very large xenon lattice is easy to compute. Suppose there are
N particles. The energy of interaction of a particle and its six neighbors is — 6c. Each
particle is the center of a hexagon so we might think the total energy is —6eN.
However, from looking at any pair of particles in Figure 12-2, it is seen that we have
then counted that pair of particles twice, once when one of them. was at the center of a
hexagon and once when the other was at the center. We must divide our result by 2 to
get — 3c/V. Because every bond corresponds to a potential energy minimum, this is the

Figure 12-3

Close packing of Ping-Pong balls. Each ball is at the center of a hexagon and touches all six of
its nearest neighbors.
 12- 7 The Structure of Solids 579

Figure 12-4 Figure 12-5

Square lattice. Three-dimensional arrangement of four

particles. Each particle can be a near neighbor

o o o o of the other three by forming a tetrahedron.
4

o o o o
o o o o
o o o o

lowest energy possible for any structure in two dimensions for an isotropic interaction
like the Lennard-Jones function.
An alternative two-dimensional structure is the square lattice shown in Figure 12-4.
It is easy to see that the energy of this structure is — 2cjV, which is a third less negative
than the energy of the triangular lattice. Also its density is considerably lower.
The above discussion of crystals in two dimensions is far from purely pedagogic.
Gaseous xenon and many other elements, when bound to certain carefully chosen
planar solid surfaces, behave like two-dimensional gases, liquids, or solids.
We now try to treat three-dimensional systems in the same manner as we have
handled two-dimensional solids. One way to start out is by forming an equilateral

triangle of particles, as in two-dimensions, and then placing a fourth particle above or

below to form a tetrahedron as shown in Figure 12-5. Each of the four particles can
have the optimal distance a from the other three particles. Just as two-dimensional
space is covered by equilateral triangles, we might hope to cover three-dimensional
space by tetrahedrons. Unfortunately, this turns out to be impossible. Suppose we
consider the top particle in Figure 12-5 as a central one to be involved in as many
tetrahedra as possible, much as any particle in Figure 12-2 is the center of a hexagon
made up of equilateral triangles. The next three particles to be added are placed next
to the three upper faces of the tetrahedron. If we go on in this way, continuing to
make as many tetrahedra as possible centered on one particle, the central particle
ends up with 12 neighbors in the structure shown with balls in Figure 12-6. It does not
look very symmetric; in fact it has a sort of crack near the top. In 1694, the Scottish
astronomer D. Gregory claimed, without proof, that a 13th sphere could be squeezed
into such a crack so it would touch the central ball. Newton disputed this, claiming
correctly that the maximum number of touching neighbors is 12.

The relevance of this for solids is on a local basis, might

that a few particles, acting
form a number of tetrahedra. These do not quite fit together with tetrahedra from
other nearby systems of particles so that the overall arrangement of particles is filled
with cracks. Most particles are bound in potential wells, although those near cracks
are not bound so tightly. There is no long-range regularity as in the perfect lattices
that we describe below, but the system can form an irregular solid. There exist a
variety of types of amorphous, or irregular, solids classified generally as glasses, some
of which this simple model may actually describe. Even though the glasses have no
long-range regular structure, they do have shear strength because each particle is
580 Solids

Figure 12-6

Ping- Pong balls stacked to make as many tetrahedra as possible in an object consisting of a ball
and its near neighbors. The geometrical shape is a distorted icosahedron.

bound in a potential well. Generally, there is, for these materials, some lattice

structure having lower energy, but the atoms cannot get to that state because they are
each trapped in a local potential energy minimum.
Since nature cannot make regular solids by filling three-dimensional space with
tetrahedra, as it can fill two-dimensional space with triangles, it usually proceeds to
make regular lattice structures in other ways. Rather than maximizing the number of
tetrahedra, we look for a way
maximize the density of the entire system such that
to
all nearest neighbors of any atom are at some distance a. It is speculated, but has

never been proved, that the densest such arrangement is provided by the face-centered
cubic (FCC) lattice. This crystal structure is easily constructed by starting with the
two-dimensional triangular lattice of Figure 12-2. The particles in this layer are
designated by B's, as indicated in Figure 12-7. Particles are next added in layers
above and below this layer. Particles in the next layer above the first go in at sites

designated by A. A particle at A forms a tetrahedron with three first-layer particles.

All the particles in this layer again form a two-dimensional triangular lattice shifted
horizontally a bit from that of the first layer.

A third layer is placed below the first at the positions indicated by the C 's.

Additional layers are added so that the sequence • • • ABCABC -is formed.
If we look at the arrangement of a particle and its 12 nearest neighbors in the FCC
lattice, as shown in Figure 12-8, we see how
from the distortedthis grouping differs

structure of Figure 12-6. The seven second-layer particles are all on the same level,
whereas the levels of these same particles in Figure 12-6 are seen to alternate. Not so
many perfect tetrahedra are formed in this argument, but that is more than com-
pensated by the regularity of the packing throughout all space.
We
can easily compute the energy of the FCC lattice if we include only nearest-
neighbor interactions. Since each particle has 12 neighbors, this energy is — (v,) X
12eN = —6eN, where the factor l avoids the double counting of the bonds. This
,

energy is the lowest possible for a system with an isotropic interaction.

 12- 1 The Structure of Solids 581

Figure 12-7

Model of a face-centered cubic lattice. Two-

dimensional triangular lattices are stacked one
on top of the other in the arrangement
ABCABC . The four particles
A\,B\,B2, B3 form a tetrahedron with all

particles separated by the nearest-neighbor

distance a.

The FCC lattice gets its name from viewing the structure from a different angle.
Figure 12-9 shows this alternative view. The demonstration of the equivalence of the
two views is left to be shown in Problem 3 at the end of the chapter.
There are many other possible lattices. A simple variation of the FCC case is the
three-dimensional hexagonal close-packed lattice. Instead of placing a particle in a C
layer as shown in Figure 12-7, it is placed directly over a particle in the A layer
resulting in an • • •
ABAB pattern. With this arrangement each particle again
has 12 neighbors. It differs in energy from the FCC only in interactions involving third
nearest neighbors. Other possibilities are the simple cubic (SC) lattice shown in Figure
12-10 and the body-centered cubic (BCC) of Figure 12-11.

Figure 12-8

Central particle and its 12 nearest neighbors in an FCC lattice.

582 Solids

Figure 12-9

View of the FCC lattice showing the origin of

its name. Each of the faces of a cube contains
a particle at its center. Although all sites are
equivalent, the particles on the faces are shown
in a lighter shade for clarity.

Lattices can be classified according to their symmetry properties of translation,

rotation, and reflection. There turn out to be only 14 basic lattice types in three
dimensions when thought of in these general terms.
Wemight wonder why any substance settles into a lattice structure different from
the FCC if that is the densest one with the lowest potential energy for an isotropic
interaction. There are a variety of answers to this question. As shown in Chapter 10,
bonds are often directional, as for example, those of carbon; the structure of the lattice
can follow the directionality. Such a changed by applying
directional bias can be
pressure or otherwise changing the physical state of the substance. Thus, carbon can
be found in the form of graphite or diamond, two distinct lattice structures, depending
on the preparation of the carbon.
Another possibility is that the substance is made up of more than one element with
the relative size of the atoms playing a role in determining the crystal structure. The
CsCl atoms at the corners of cubes with chlorine atoms at the body
crystal has cesium
centers. This might seem to be a BCC arrangement, but it is actually simple cubic. It
is necessary to focus on just the cesium atoms or just the chlorine atoms to determine

the true structure.

Figure 12-10 Figure 12-11

Simple cubic lattice. Body-centered cubic lattice.

 121 The Structure ol Solids 583

Figure 12-12

Model of the sodium chloride crystal. Sodium

atoms are shown in black, chlorine atoms in

white. The crystal structure is FCC.

Another answer to the question of a substance's crystal structure is provided by

solid helium. While close-packed lattices do occur for this substance, under the
appropriate conditions of temperature and pressure a BCC phase also occurs. This
happens despite the fact that helium is elemental with a highly isotropic interaction.
The cause of this peculiarity is zero-point motion that is so large it destabilizes the
closed-packed lattice.

The types of binding that occur in molecules also hold solids together. A solid can
often be considered simply to be a large molecule. Covalent bonding occurs in the
diamond The NaCl crystal shown in Figure 12-12 is ionically bound, with Na
crystal.
the positive ion and CI the negative.
The hydrogen atoms in a water molecule are bound to the oxygen atom covalently.
Each hydrogen can also be attracted to an oxygen of another water molecule, thus
forming a second bond called the hydrogen bond. Ice then consists essentially of water
molecules connected together by such hydrogen bonds.
Hydrogen itself is another example of a substance that retains its molecular identity
in the crystalline state. The H 2 molecules attract each other by the van der Waals
force and form what is called a molecular solid. Other molecular crystals include, for
example, 2
and the solid states of the noble gases helium, neon, argon, and so on.
Under very high pressure, it is expected that the diatomic molecular bonding in solid
hydrogen gives up in favor of a homogeneous bonding among all atoms so that the
solid undergoes a transition to a metallic phase. This important effect is being looked
for inmany laboratories around the world.
The binding that occurs in a metal is somewhat analogous to that occurring in the
hydrogen molecule, with electrons hopping among all atoms instead of just between
two. We investigate this binding and the other properties of metals in the next two
sections.

Example

The NaCl crystal is ionically bound. We can try (unsuccessfully) to estimate the
contribution of its Coulombic energy to the binding of the crystal by summing
over the pair interactions in the lattice. Any given Na + atom is surrounded by 6
near-neighbor CI" atoms at a distance R , 12 second-neighbor Na + atoms at
+
v2/? , 8 CI" atoms at ]/3 , 6 Na at )/4R , and so on. The contribution to
584 Solids

the binding from this sequence of interactions is

12 8 6
E=
R \
+
w -)•
The bindin g energy per particle is N times this result, v\ 'here N is the number of
sodium ions. The sum in parentheses converges very slowly. Its value upon
truncating it after a given numbers of terms, is shown n the following table:

Number of Terms Sum

1 -6.0
2

3 -2.1
1 0.9

5 '1.9

6 -0.7

If the com plete sum is done, the resu It is - 1.75 ; spec rial mathematical proce-
dures must be used to evaluate it.

12-2 Bragg Scattering

An experimental means of probing and examining the structure of crystals was

provided by Laue early in this century, as we have discussed in Section 2-6. We know
that when one irradiates a crystal with x rays they are scattered by the electrons of the
individual atoms so that the regular structure of these atoms acts as a three-dimen-
sional diffraction grating. Waves from different atoms interfere with each other
constructively in some directions and waves detected
destructively in others. Scattered
on photographic film show a pattern characteristic of the particular crystal structure
being x rayed. Laue invented the idea and the Braggs used it to analyze the structure
of many crystals.
Other modes of radiation can be used as probes as well. We have seen in Section
4-2 that electrons can be diffracted from crystals; in 1927 Davisson and Germer, and
Thomson proved by this method that electrons behave as waves. Neutrons may also
be used. Note, however, that the neutrons interact with the nuclei and not with the
atomic electrons. The wavelength of neutrons is normally so short that they can be
used to probe smaller distances than can x rays. Because neutrons have spin, they can
also reveal the magnetic structure of crystals.
As in Section 2-6 we again consider x rays striking a set of parallel planes of
particles occurring in the lattice. Any crystal has an infinite set of such planes found
by slicing through the crystal at certain angles. Figure 12-13 uses a two-dimensional
representation of a crystal to illustrate some of the many possible planes that could
scatter x rays. Obviously, some planes are more dominant than others because the
density of particles on them is greater than that on others. The facet that appears on

the surface of a crystal represents one of a parallel family of such dominant planes.
From Figure 2-15 we recall that constructive interference occurs when the path
difference between the two rays in the figure is equal to an integral number of whole
 12-2 Bragg Scattering 585

Figure 12-13

Two-dimensional representation of the many

possible scattering planes in a crystal.

O O O O O O

wavelengths. According to Equation (2-49), this happens when the angle 6, between
the crystal planes and the incoming or scattered beam, satisfies

2d sin 6 = m\ . m = 0,1,2,, (12-1;

where d is the separation between planes.

A narrow beam of x rays hits the crystal. A scattered beam emerges from the
crystal for each family of parallel planes satisfying Equation (12-1). Each emerging
beam has an intensity depending on the density of atoms in the corresponding set of
planes. Photographic film, exposed to the scattered radiation, displays spots, caused by
the beams, which can be analyzed to give information about the crystal structure. An
example of a Bragg diffraction pattern is shown in Figure 12-14.
Each family of parallel planes can be characterized by a unit vector h normal to
them. Each possible scattered ray can be characterized by a vector along this
direction. To see this, suppose that k is the wave vector of the incident beam and k' is
the scattered wave vector. The momentum transferred to the lattice is /z Ak = h(k -
k'). Because the lattice is so massive, its recoil is negligible and we have

2 77
|k| = Ik'l = k = (12-2)

From Figure 12-15, we see that

Ak = 2*sin0 h.

Substituting from Equation (12-1) for sin#, and from Equation (12-2) for A., gives

Ak = — mh = G,
2 7T

d
w = 0,1,2,... (12-3)

Equation (12-3) defines a set of vectors G whose direction is perpendicular to the

family of lattice planes and whose length is inversely proportional to the separation
between the planes. There is a set of such vectors for each family of planes in the
crystal.
586 Solids

Figure 12-14

Photographic record of the x-ray diffraction pattern due to Bragg scattering from an NaCl
crystal.

The infinite, but discrete, set of these G vectors can be shown to define a lattice,
called the reciprocal lattice. Each point in this ficticious lattice corresponds to a possible
momentum that can be absorbed by the real lattice of particles. There is a one-to-one
correspondence between the sites in the reciprocal lattice and the spots in a scattering
pattern.
We see below that these vectors show up repeatedly in our analyses of solids. For
example, a conduction electron in a metal can be diffracted constructively by the

lattice of the atoms, just as an x ray is, if the scattering produces a Ak equal to one of
the G's. This phenomenon has important consequences relative to the possible energy
states of electrons in crystals.

Figure 12-15

Vectors describing the scattering of x rays

from a crystal plane. The momentum
transferred to the lattice is h Ak. The normal

to the reflecting plane is h.

 12-3 The Free-Electron Theory of Metals 587

Example

Suppose that the scattering angle in a first- order diffraction (m = 1) is 8 = 42°

and the x -ray wavelength is 0.2 nm. The separation between the lattice planes
can be found from Equation (12-1):

mX 1 X 0.2 nm 0.2 nm
- (1 IS nm
2sin0 2 sin 42° 2 X 0.67

A photon of this wavelength carries energy

he 1 .240 keV •
nm — ° L-rV
fi

0.2 nm

Example

If neutrons are used for the Bragg scattering in the above example, each has
wavelength 0.2 nm and energy E related to X by

h h
X = — = , =0.2 nm,
p )/2ME

where p and M are the neutron momentum and mass, respectively. Thus, we
find

34 2
2
h (6.6 x 10 J •
s)

2MX2 2(1.7 X 10
-'-' 7
kg)(0.2 X 10 9
m)
2

3.2 x 10" 21 J
3.2 X 10"-'
J iy
= 0.02 eV.
1.6 X 10" J/eV

Note how much smaller the neutron energy is than that of the photon of the
same wavelength. Neutrons having such low energies are said to be thermal, since
a k B T of this value implies a T near room temperature. Nuclear reactors are
often the source of neutrons for Bragg scattering. Because most such neutrons
originate with energies in the MeV range, it is necessary to slow them down by
many inelastic scatterings before using them in a diffraction experiment.

12-3 The Free-Electron Theory of Metals

The most notable properties of metals are their abilities to conduct heat and
electricity. The idea that metals contain electrons that can move freely and can carry
energy and charge was developed soon after Thomson discovered the electron in 1897.
P. Drude first suggested a model that assumed an electron behavior like a classical
gas. In Chapter 1 1 we have examined this assumption and have found that the
electrons must be a highly degenerate set of fermions. In 1928 Sommerfeld modified
the Drude theory to take degeneracy into account. The resulting model did a
surprisingly adequate job of describing many of the properties of metals.
588 Solids

Figure 12-16

Arrangement for measuring the coefficient of

thermal conductivity. The temperature
gradient is dT/dz ~ (T — ]
T 2
)/L. The heat
current is the flow rate per unit area, JT =
(\/A)dQ/dT.

Some of the static properties of a degenerate electron system have been described in
Chapter 1 The most important one for metals is that the electron heat capacity has
1 .

been shown in Equation (11-76) to be linearly proportional to temperature. This

characteristic dependence is found experimentally in metals.
Specific heat involves a static or equilibrium measurement. Another class of
experiments involves setting up nonequilibrium conditions in order to study how the
system returns to equilibrium. The quantities measured are the transport coefficients
of the material. For example, if one end of a metal bar is placed at a higher
temperature than the other, heat is conducted down the bar in an attempt to
reestablish constant temperature. The situation is shown in Figure 12-16. If the
gradient of the temperature in the z direction is dT/dz and if the heat current density,
that is, the heat flow per unit cross sectional area per second, is J T then we have ,

dT
Jt kt (12-4)

where K T is called the coefficient of thermal conductivity. The minus sign in Equation
(12-4) indicates that heat travels from high temperature to low temperature or in the
direction of negative dT/dz.
In a similar manner we define the electrical conductivity ke as the constant of
proportionality between an electric field E established in a metal and the charge
current density

JE =« E E, (12-5)

giving the charge per second per unit area moving in the material. From elementary
electrostatics, the field vanishes in a metal at equilibrium. The situation established
here is a nonequilibrium one. The charge is flowing in an attempt to set up a
distribution that cancels out the field in the metal. If the charge is removed from one
end and reinserted in the other continuously, a steady-state nonequilibrium situation
can be established as it is in any simple DC resistive circuit.
The transport properties of electrons are usually discussed by considering the states
of the particles in momentum space. We need to digress briefly to see what this space
 12-3 The Free-Electron Theory of Metals 589

is and how it is filled by a set of degenerate free particles. We know from Chapter 1

that the energy states for a Fermi system at T= K are filled up to the Fermi energy
eF and states above that are empty. If we calculate the energies of traveling-wave states
3
in a cubical box of volume L , we find

i 2

e = + +
^AA -
2mL71 \
o I 2 ^3 )•

Since £ = p 2 /2m, we can write the allowed momenta as

The allowed values of the three Cartesian components of momentum are

Pi=
K
— , < = 0, ±1, ±2, ±3,... (12-6)

where / is 1,2,3 or a-, y, z. These results for the energy and momentum are not quite
the same as the previous forms of Equations (5-99) because we are now considering
traveling rather than standing waves. We consider these differences in more detail in
Section 12-4; for now just note that both positive and negative momentum values are
allowed corresponding to particles traveling in opposite directions.

Each of these discrete momentum states may be occupied by one electron of each
spin type. The three momentum coordinates allow us to construct a space of states
similar to the one illustrated in Figure 2-7 for standing waves of electromagnetic
radiation. At T= K, the states in p space occupied by particles form a sphere,
known as the Fermi sphere, as shown in Figure 12-17. The radius of the sphere is pF ,

the Fermi momentum, which is related to eF by

pF =fime F . (12-7)

Figure 12-17

Fermi sphere in p space. The radius of the

sphere p F is related to the Fermi energy £ F
according to e F = p F/2 m At T = K, states .

below p F are all occupied while those above

are empty.

Pz
 .

590 Solids

The Fermi velocity is simply

vF =—m . (12-8)

We now consider the electrical conductivity. An electron of charge —e placed in an

electric field feels a force — eE and accelerates freely if it does not lose energy by
interactions with impurities, ion cores, and other electrons in the metal. These are the
resistive interactions of the metal. In a very simplified model we might assume that
they provide a frictional type of force whose size may be supposed to depend on the
electron's velocity. Newton's law becomes

dv
m —
at
= -eE - av, (12-9)

where a is a constant determined by the nature of the frictional forces. Obviously, the
frictional force operates only when the electron is moving and increases in size with
the velocity, much as the retarding force of air resistance on a moving automobile.
Suppose we consider the which the electron has been given an initial
situation in
velocity v in the absence of an electric field (and in the absence of any other
electrons). Then the electron's equation of motion is

dv a

dt m
which has solution

v *-
(fl/m) '.
v = (12-10)

We see that the velocity returns to zero in a time

m
t= — (12-11)
a

This constant is called the relaxation time for obvious reasons. By means of microscopic
calculations one can show that r is not much longer than the collision time, the time the
electron travels between interactions with impurities, ions, or whatever it is that is

interfering with the electron's motion.

In an electric field E, the system relaxes until d\/dt vanishes, in which case we
have a steady-state nonequilibrium condition. From Equation (12-9) the velocity then
satisfies

^E ei
v = = E. (12-12)
a m

We have used Equation (12-11) to eliminate a.

If other electrons are present, a given electron is not able to relax to an arbitrary
velocity or momentum because of the Pauli principle. In particular, in zero field most
electrons certainly cannot relax to zero velocity as implied by Equation (12-10)
because that state is probably already occupied. However, the energy loss processes
can relax a system of electrons to the many-particle ground state, which involves a
filled Fermi sphere centered on zero momentum.
 12-3 The Free-Electron Theory of Metals 591

Figure 12-18

Shift of the Fermi sphere by an electric field.

The indicated shift is 8k = -erE/fi for a
field in the —y direction. The shaded region
shows the states that are newly occupied; the
states in the cross-hatched region are now
empty.

When there is an external field E every particle cannot have the same small
nonzero velocity implied by Equation (12-12), since that violates the Pauli principle.
What happens is that every particle in the Fermi sphere is shifted in velocity by an
identical amount Sv equal to the v of Equation (12-12). So we have

Sv = E. (12-13)
m
Thus, the entire Fermi sphere is shifted over by 5p = m 5v, as shown in Figure 12-18.
Note that because this shift of origin of the sphere is usually quite small, most of the
momentum states that were occupied before the shift are still occupied. However, a
thin crescent of states at the left-hand edge of the figure has been emptied and another
at the opposite side has been filled.

This kind of effect is characteristic of degenerate Fermi systems; only the particles
near the Fermi surface take part in the process. We know from Chapter 1 1 that the
specific heat capacity involves absorption of energy by particles within k B T of the
Fermi surface.
In general, a current density or intensity of a beam is particle density times particle
velocity, as we illustrate in Problem 9 at the end of the chapter. Thus, the electrical
current density is charge density times particle velocity:

JE = -e8pvF ,
(12-14)

where 8p is the density of particles involved in carrying the current; these are the
particles in the crescent at the Fermi surface. All these particles move with velocity
very nearly equal to the Fermi velocity v F defined by Equation (12-8).

We can find the density 8p of current carriers by using the relation for the density
of states developed in the first Detail at the end of Section 1 1-3. We have seen that the
number of energy levels per unit energy in the range e to e + 8e is

D(e)= -
=^-Vt^\
1 2 3
]f27r h
592 Solids

By introducing the Fermi energy e f given by Equation (1 1-73),

, we can simplify D(e)
considerably so that it reads

3 P Ve ^
2 1

D(e)
4 4/2 '

Since, for fermions, there are two particles per energy level, the density of particles per
unit energy R(e) is obtained by multiplying D(e) by 2/V to give

2
3 pe'/
*(*)=«^7T- (12-15)

The density of current carriers is then the density of particles per unit energy'
evaluated at the Fermi energy times the energy width of the crescent:

3p
8p = R(e f )8e = 8e. (12-16)
2e F

The energy width 8e is related to the velocity shift of Equation (12-13) by

de 1 d(mv 2 )
8v = -
8v = mvF 8v. (12-17)
2 do

Combining the results of the last few equations, we have for the current

p er e~rp
JE - ev F —mv F —E E, (12-18)
eF m m

where we have dropped constant factors of order unity because our estimate of 8p
contains inaccuracies of that order. From Equation (12-5), the electrical conductivity
is

2
e rp
(12-19)

Although only the electrons near the Fermi surface contribute to the electrical current,
the density p corresponding to all electrons, even those away from the Fermi surface,
appears in Equation (12-19). This feature arises because the number of electrons that
are forced by the Pauli principle to be at the Fermi surface depends on the overall
density.
For classical particles (which need not obey the Pauli principle) Equation (12-12) is

valid. Furthermore, for such particles, the current is simply JE = — epv instead of that
given by Equation (12-14). Curiously, the combination of these two equations also

leads to Equation (12-19), even though such a simplified derivation cannot be valid
for electrons.
In order to make contact with experiment we need to specify the behavior of t in

Equation (12-19). The major effect involved in slowing the conduction electrons is

their interaction with vibrating positive ion cores in the solid. We see in Section 12-4
that if the ions form a perfect crystal, the electrons move through the lattice essentially
 12-3 The Free-Eleclron Theory of Metals 593

as an ideal Fermi gas, which has been the basic assumption of this section. It is when
the lattice ions vibrate thermally that interactions with the electrons occur. A good
picture of the process is obtained by considering an electron as absorbing and
reemitting phonons as it moves through the lattice. The relaxation time t can then be
supposed to depend on np ,
the number of phonons of frequency v present in the
lattice. We know from Section 11-5 that n v is given by

n„ = (12-20)
e
fih> _ i
•

The fewer phonons that are present, the longer t is expected to be, so that we can take

-(?")

For k B T/h » vm , a frequency characteristic of lattice vibrations introduced in Section

11-5, or equivalently for T »
Q D the Debye temperature, ,
also introduced in Section

11-5, we see from Equation (12-20) that

1 kB T
1 + fihv + ••• -1 hv

Thus, we expect t ~ T~ '

and ke ~ T~ x
. The resistivity r = 1/k £ then behaves like

r~T, T»Q D .

Hence, a metal's electrical resistance decreases with decreasing temperature.

At temperatures low compared to the Debye temperature, one can show by the
methods of Section 11-5 that

I T
L*. - T«@ D .

We might expect then that r ~ T 3

; however, there are other details of the angular
behavior of the scattering of electrons by phonons that make them even less effective

in retarding the current at low temperature so that the actual result is

t~t\ r«e D .

At very low temperature, the number of phonons may become so small that
impurities in the crystal may account for the frictional forces on the conduction
electrons. Such impurities may be foreign atoms, vacancies (absent atoms), and other
imperfections in the crystal lattice. For sufficiently small samples the boundaries of the
crystal may even be a factor in determining T. In most of these cases, this contribution
to t is independent of temperature so that r approaches a constant at the lowest
temperatures.
A somewhat similar treatment can be given to the thermal conductivity of metals.
The heat current is now driven by a temperature difference. One end of the metal
sample is hotter than the other. Although we assume that there are equal numbers of
594 Solids

Figure 12-19

Distribution of electrons in a cut through the Fermi sphere along the p. axis. The distribution is

that at a single point in real space. Particles with momentum + p. have just come from a hotter
region; those moving with momentum —p. have just come from a cooler region. These
distinctions show up in the slight differences in the spreads of the distributions around +p F .

electrons flowing in both directions along the z axis in Figure 12-16, so that a charge
does not build up at one end, those flowing from the hot end carry more energy. There
is a flow of heat in the absence of a net flow of particles. (Actually there can be a
thermoelectric effect in which temperature differences give rise to voltage differences,
but we neglect such details here.)
Again it is the electrons near the Fermi surface that are responsible for thermal
conduction. Consider the cross-sectional view of the Fermi sphere shown in Figure
12-19. The distribution function n fi
in the figure is the number of electrons having
momentum p. The
deep within the Fermi sphere have no effect on
electrons
conduction because they come in matched pairs; for every one moving toward +z
there is one moving toward — z.
The heat current density is the number of heat carriers per unit volume times the
velocity of a carrier times the heat carried per particle. The first of these factors is the
density of conduction electrons p multiplied by the fraction k B T/e F of the particles
that are thermally excited. Only this fraction can carry heat. So we have

kB T
number of heat carriers per unit volume = p .

£F

The second factor is the Fermi velocity,

velocity of a carrier = vF .

The final factor, the heat carried per particle, is a bit more subtle to compute. The
energy carried by a particle moving in the +/>. direction is of order e F + kB T+ and
that in the — p, direction is of order e F + k B T_, where T+ is a bit larger than 7'_ as
explained above. The net energy transported is then kB ST = k B (T + — T _). To
compute 8T we note that particles coming from the left are cooled down by collisions

with other particles so that they tend toward the local temperature. Particles moving
from the right are heated up by collisions. Since the average time between collisions
for a particle is assumed to be about t seconds, the distance between collisions is

/= v f t, a quantity known as the mean free path. We can assume then that a
temperature change of order 8T occurs every distance / and that the gradient in
temperature is

dT ST
~ ~~7
~~dz~ '
 12-3 The Free-Electron Theory of Metals 595

or

dT
8T = -TvF —-.
dz

Thus, the final factor we need is, in order of magnitude,

dT
net energy carried per particle ~ ~k B TV F — dz
.

Combining these results gives the heat current density

p dT
2
JT k B Trvj—. (12-21)
eF dz

If we set e F — mvF and compare with the general form, Equation (12-4), we find the
coefficient of thermal conductivity to be

kt = -k\TT. (12-22)
m

It was noted very early in the history of the study of metals that good electrical
conductors are also good conductors of heat. If we take the ratio of k t to k e from
Equations (12-19) and (12-22) we find

k
2
T
*r= -4-f
e
£ >
(12-23)

a rule named the Wiedemann- Franz law after G. H. Wiedemann and R. Franz (1853).
Over certain temperature ranges Equation (12-23) is found to be obeyed quite well.

However, the validity of the relation depends on an implicit assumption, namely, that
the relaxation times, the t's appearing in Equations (12-19) and (12-22), are the
same. It turns out that the phonon processes that relax electrons in electrical
conductivity are not identical to those involved in thermal conductivity. The t 's then
are not quite the same and the Wiedemann-Franz law often breaks down.
In this section we have investigated how we can understand some of the properties
of metals on the basis of a free-electron model. The model is found to work pretty
well. But surely electrons must interact strongly via the Coulomb force with the ion
coresand not just weakly with core vibrations. Interaction with other electrons ought
tobe present as well. How are we to understand the origins of a free-electron model?
The answer to this question is the subject of Section 12-4.

Example

Experimentally, it is found that the resistivity of copper at room temperature is

r = \/k e = 1.7 X 1CP 8 £2 m. By using Equation (12-19), we can find a value

for the relaxation time t for electrons in a metal. The average separation of
copper atoms is about 0.2 nm and each atom contributes one conduction
 -

596 Solids

electron, giving a density of p = 1/(2 X 10" 10 m) 3 . We then have

m 9.1 X 1CT 31 kg
T = 2 3
'V (1.6 X l(T 19 C) [l/(2 X 10 ,0
m) ](l. 7 X 1(T 8 B m
• 2 X 10
H s.

In Problem 8 at the end of the chapter the reader is asked to compute the mean
free path, the distance an electron travels in this time.

12-4 Energy Bands in Solids

The sodium atom has a single 3^ electron outside a neon-like closed electronic shell
^iven by Is Is 1p . When a large number
sodium atoms are assembled they form
of
a bound metallic crystal. We this result by examining a simple
attempt to understand
crystal model. Our primary result is that the outermost atomic states no longer have
the energy values found in atomic sodium but are split into bands of energy levels.
These states correspond to delocalized electrons that are no longer fixed to individual
sodium atoms but are able to move through the entire crystal. The electrons in states
of a band behave, in many ways, like free particles as claimed in Section 12-3.
We do find fundamental alterations to the free-particle picture. Between bands of
allowed energy states there are forbidden energy regions called band gaps. The
existence of these gaps leads to the possibility of understanding the nature of insulators
and semiconductors as well as metals.
Just as the quantum tunneling of an electron from one hydrogen atom to the other
results in the binding of H.j , so also the electrons hopping among the many ions of a
metal can lower the total energy of the system.
Equation (10-7) illustrates what happens to the electron energy levels when two
hydrogen nuclei are placed close together. The tunneling of the electron through the
small barrier midway between the two nuclei results in a splitting of the I* atomic
level into two unequal energy levels. The wave functions corresponding to these states
no longer describe an electron situated on just one or another atom; they are
delocalized. Nevertheless, they are, to a good approximation, combinations of the
localized atomic states. The energy banding in metals is basically the same effect;
tunneling splits the levels.

Figure 12-20 illustrates the potential energy seen by a single electron in a sodium

crystal. One of the crystal edges is shown at the right end of the figure. Note that the
potential energy inside the crystal is lower than its value at the edge or at infinity. The

Figure 12-20

Schematic diagram of the potential energy curve seen by an electron in metallic sodium. Also
shown are the atomic 2s and 3s levels of the sodium atom.

/YVY\
 124 Energy Binds in Solids 597

reduced interparticle barrier is what allows the electron to move from nucleus to
nucleus. At the edge the electron sees the higher barrier and is unable to escape from
the interior.
The 15, 2s, or 2p states, see hardly any change in the
core electrons, those in the
potential energy when the atoms are put together and so their energy levels are
affected very little. Only the 3* and higher levels are changed.
We now consider the details of a model in which an electron moves along the x axis
in just one dimension. The potential energy function centered at one site R n is the
Coulomb potential energy

V = V(x-R )= n
.
(12-24)
47teJ.v-.KI

Note that the charge on the sodium ion is just + e. The electron has a total potential
energy W{.x) given as a sum of all such Coulomb functions as

W{x) = V + V2 + x
••• +VN (12-25)

for N ions.

To an approximate wave function for an electron having this potential energy

find
we continue to take clues from the analysis of the Hg molecule in Chapter 10. There
we have used two wave functions, one of which is the sum of, and the other the
difference between, the two atomic functions. Here we assume that the eigenfunction
4>(x) for a single electron is a generalization of this. We try the form

+(x) = CrfM + C2 4> 2 (x) + ••• + CN N (x),

<j> (12-26)

where <p n (x) = $ (.v — R is the atomic 3s function for

3j n )
an electron at the ion core

centered at R n The constants C are to be determined.

.
n

If our model crystal has boundaries like a realistic one, the Cn values at and near
the right and left edges of the crystal have a fundamentally different character from
8
those near the center. In a very large crystal, say, one with 10 sites along an edge,
these boundary positions play a relatively unimportant role in determining the energy
of a given state; an electron spends only a negligibly small percentage of its time near
an edge. To remove the complications of these edges without fundamentally affecting
the physics, we use instead what are known as traveling-wave or periodic boundary
conditions. Rather than demanding that the electron wave function be zero to the left of

site 1 or to the right of site N, we assume that the wave function begins to repeat itself

when it reaches a boundary. Thus, as shown in Figure 12-21, when the electron passes
site N by one interatomic distance, denoted by a, it finds itself back at site 1.

Similarly, if the electron goes to the left of site 1 it finds itself at site N, and so on. This
arrangement can be thought of as the crystal having itself wrapped in a circle and tied
head to tail as shown in Figure 12-22. While such a circular arrangement is difficult to
visualize in three dimensions, we need not worry about it because it is only a
mathematical artifice used to make the solution easier to find. The type of boundary
condition used, as noted above, makes negligible difference to the energy levels for a
very large system; it does make a large difference in the amount of work necessary to
find the energy levels.
598 Solids

Figure 12-21

Periodic boundary conditions. An electron moving to the right of the site A

7
finds itself back at
site 1.

N - 1 N 1 2

The time-independent Schrodinger equation becomes

[T+ V + x
V2 + ••• +V„]+(x) = E+(x), (12-27)

where the kinetic energy operator is T = —(k 2 /2m) d 2/dx 2 We can make an .

immediate simplification if we use the fact that each <£„ is a 3s function corresponding
to the potential energy Vn located at R n that is, we have ;

[T+ Vn ]<t> n
= E <t>„, (12-28)

where E is the energy of the 3s state. Then when the quantity in square brackets in
Equation (12-27) acts on «f>, in \p(x), we get [E + V2 + + VN ]. When it acts on • • •

4> 2 we get [V + EQ + V3 +
x
+ VN ], and so on.
• • •

Thus, Equations (12-26) and (12-27) give us the expression

C,(£ + v2 + • + vN )* + c2 (r, + E +
x
V, + • • • + VN )ct> 2

+ ••• +CN {V X
+ ••• +VN _ + E X
)4> x
= £(C>, + C2 4> 2 + +CN N <i> ). (12-29)

What we now want to do is to develop algebraic equations for the Cn 's from this

result. The way to do this is to multiply Equation (12-29) by <j>

n
and then integrate
over all x. Other equations are found by multiplying by other <£'s. A number of

Figure 12-22

A ion cores set in a ring to give periodic

boundary conditions on the wave function of
an electron hopping from one ion to another.

N- 1
 12-4 Energy Bands in Solids 599

simplifications and approximations are possible in the resulting equations. Since, for
example, § x
is large only in the neighborhood of site 1, and V2 in the neighborhood of
site 2, and so on, we expect any integral involving more than one site to be relatively
small. These integrals are analogous to the overlap integrals encountered in Chapter
10. Integrals involving three different sites involve the "leakage" of a function into a
region two sites away so that, for example, we have

~ dx ~
f^y^ dx or /"<f>,K>4> 3 0.

Integrals involving only two different sites that are nearest neighbors cannot
normally be neglected. Thus, the integral

J = faVfadx
X2
(12-30)

is a measure of the probability that an electron hops from one site to its neighbor, and

must be kept in our equations. All near-neighbor J 's have the same value, which we
denote simply as J:

J 2=J2 =Jn»-l=J-
l i
(12-31)

There are two other near-neighbor overlap integrals that arise in the operations we
are considering. These are of the form

d= jW^i + v3 h^ 2

and

I = /<M>i dx = \<$> x §2 dx.

Q is the energy shift of a site-2 electron due to 1 and 3. /

its interactions with ion cores
arises from the terms on the right side of an interference term
Equation (12-29); it is

that occurs in the normalization integral of the eigenf unction \p. While Q and / are
corrections that ought to be included in any rigorous calculation of the electronic
energies, they do not change the basic physics and we simply drop them in this
qualitative discussion.
Finally, we assume that each of the atomic functions <f> n
is normalized as

hi dx=\,
It follows easily from the above discussion of overlap integrals that the result of
multiplying Equation (12-29) by <#>„ and integrating over x is to give the equality

Cn E +C _J+C + J =
n n
EC n

or

Cn (E -E) + (C n _ l
+ Cn+l )J=0 (12-32)

for n = 1,2, 3, ... , A/.

600 Solids

These results have a very simple structure. If J= 0, the solution for the energy- is

just E , the localized atomic energy. However, quantum tunneling of the electron to
nearest-neighbor sites is represented by the overlap integral J. Each Cn is coupled to
those of the neighboring sites, Cn _ and Cn+
,
by these small hopping terms. Equation
,,

(12-32) is easily solved. While we have N homogeneous equations in A unknowns, the

,T

usual technique of setting the determinant of the coefficients to zero is an unwieldy

way to proceed. A simpler procedure is more useful to us. We anticipate that the
electron hopping on a ring of N
sites has a solution behaving like a traveling wave.

We can guess that such solutions are provided by choosing the form

hR *.
Cn = Ce' (12-33)

The variable k turns out to be the wave vector for the electronic motion, and C is a
normalization constant. By substitution we show that this choice does indeed satisfy
Equation (12-32).
The ion sites are taken to be at 0, a, 2a, ... ,(N — 1 )a, or

R n = (n-l)a, n=l,2,...,N, (12-34)

where a is the distance between lattice sites. With the ansatz of Equation (12-33)
plugged into Equation (12-32), we find

u" "-'i)a
Ce'
,)a
(E - E) + C{e'
k(
+ e'
k "a
)J =
01

(E -E) + (e- ika + e

ika
)j = 0.

The guessed solution, Equation (12-33), has worked and the result for the energy is

E = Ek = E + 27 cos ka. (12-35)

The energy levels E k

are still close to E , but now there is a tunneling correction
dependent on /. We also have a new quantum number k that determines the precise
value of the energy level Ek When. the sodium
can be ions are far apart the electron
localized on any one of the N
There are A energy levels all with
ions with energy E .
r

precisely the same energy. This equality has now been removed by the possibility of
tunneling of an electron from one ion to the next, so that we now have N distinct
energy levels each characterized by a different value of k. Before we can further
understand the nature of these levels we need to determine the values taken on by the
quantum numbers k.
The k 's are determined by the periodic boundary conditions. When we go to site
N + 1, we assume that we are back at site 1. From Equation (12-33) this implies

oi

= 1, (12-36)

so that

k = —
277

Na
t, {= 0, ±1, ±2,... . (12-37)
 J 2-4 Energy Bands in Solids 601

Figure 12-23

Plot of the electronic energy levels Ek for a one-dimensional model of a metal. We assume

J< and find the width of the band to be 4[/|. The band is centered on the atomic energy E .

We see that for N large, the allowed k values are very densely spaced just as are the k
values of Equation (5-30) or (12-6) for a particle in a large one-dimensional box of
size L = Na. However, these k values are not precisely equal to those of the particle in
a box treated in Chapter 5. The difference is in the factor of 2 in Equation (12-37)
and the fact that negative as well as positive { 's are allowed. These distinctions arise
only because of the different boundary conditions used in the two cases. In Chapter 5
the infinite potential energy well forces the wave function to be zero at the ends of the
box, thereby producing standing waves in the box. In the present case we have used
traveling-wave boundary conditions. If we use these conditions on a free particle in a

"box," we indeed get k\ identical to those of Equation (12-37) as we find in Problem

13 at the end of the chapter. Positive ^"s give positive k's, which represent waves
traveling to the right; negative £'s give waves moving to the left. However, since in
the standing-wave case only positive f values occur, we now have twice as many f \.
Thus, the factor of 2 is necessary in Equation (12-37) to make the spacing between
adjacent k 's The overall density of k values comes out the same in the
twice as large.
two cases. enough to ensure that the properties of a large system are
This is

independent of which boundary conditions are used.

This relation between quantum numbers of a free particle and those of an electron
hopping through a crystal of ion cores is one of the bases for the success of the
free-electron theory of metals discussed in Section 12-3. Using k as a continuous
variable, we plot the values of Ek given by Equation (12-35) in Figure 12-23. Note
that we now have an energy band of allowed energy states.
Since, in the case of highly separated ions, we start out with N identical energy
levels corresponding to the electron being localized on any one of the N ions, we still

have N
distinct states when the ions are close enough for tunneling to take place.
However, there are an infinity of k values listed in Equation (12-37). On the other
hand, the energy levels of Equation (12-35) are periodic in k. What we intend to show
is that certain k values are exactly equivalent to other k values so the set given by
Equation (12-37) has multiple redundancy. To see this redundancy we take as our
basic set the values

2m{ 0,1,2,..., N/2- 1

k = (12-38)
-1,-2, -3,..., -N/2,

where we have assumed N is even so N/2 is an integer. There are exactly Nk values
 ,

602 Solids

in the set given. If k is inside this basic set, the vector k + G, with G defined by

G= —
277

a
(12-39)

is always outside the set. This is easily seen by considering several explicit choices of
wave vector. For k = we see that k + G = {2"n/Na)N corresponds to ("= N, which
is certainly outside the k set given by Equation (12-38). For k = {2m/Na)( — N/2) we
have

-N
k + G= —
277

Na
•

2
+ —277

Na
N=
277 TV

Na 2
,

corresponding to c" = N/2, which is just barely outside the set of allowed k values of
Equation (12-38). G is the width of the allowed /:-vector set. Next, consider the
eigenfunctions for the various k values. Upon substituting the Cn values of Equation
(12-33), the general eigenfunction ip(x) of Equation (12-26) is

-
4> t (x) = C[<f>, + *'% + e
i2ka
<t> 3 + +*'< JV 1
>% 1
. (12-40)

Consider this eigenfunction for a k value outside the basic set:

* 4+0 (*) = c[«, + ««* +c >ik+ ... +,'<"-'x* + o Va i

>

Since, by Equation (12-39), a typical factor in this function obeys

we see that

*a+c(*) = **(*) (12-41)

The k values outside the basic set do not lead to distinct wave functions but simply
reproduce those corresponding to k values in the basic set. Obviously, we also have
Ek + G = E k
. Additional redundant sets of k 's can be generated by considering multi-
ples of the G value of Equation (12-39).
The basic set of k values is said to be inside the Jirst Brillouin zone, a concept devised
by L. Brillouin. Other k values are in second or higher Brillouin zones. The vectors in
each zone are perfectly equivalent to those in any other. The unit G and its multiples
make up a set of wave vectors known as the reciprocal lattice that we have discussed in
Section 12-2. The values of these vectors in three dimensions are given in Equation
(12-3). The G's that we have been considering can also be defined by the relation

>g„r„
= 1, (12-42)

which is equivalent to the one-dimensional version of Equation (12-3). The fact that
the reciprocal lattice vectors, originally associated with Bragg scattering, also arise in
the study of the states of electrons in crystals is no coincidence. The relation is

explored more detail below.

in

We now examine the energy levels for an electron in a crystal a bit more closely.

The energies of Equation (12-35) are centered on the atomic energy level E ,
which in

the case of sodium metal is the 3s energy. They are spread in a band about E . If we
 124 Energy Bands in Solids 603

Figure 12-24

Energy band for k vectors in the first Brillouin

zone.

assume that this band has J < 0, the energy corresponding to k = has the lowest
energy, namely, E — 2\J\. The largest energy occurs at the two edges of the Brillouin
zone where k = +ir/a, because there we have

-2\J\cos ka = -2L/|cosw = 2L/|.

The energies for k values in the first Brillouin zone are shown in Figure 12-24.
The energy minimum around k = is parabolic so that we are able to show the
relation of our band energy to free-particle states. To see this, expand the band
energies of Equation (12-35) for k around k = 0. We use the Taylor series result

(kaY (ka]
cos ka = 1
- +
2! 4!

Keeping only the quadratic term leads to

E, = (E -2\J\) + \J\a-k\ k ~ o.

The last term has the form of a free-particle energy,

2 2
h k
(12-43)
2m'

where the electron moves as if it had an effective mass identified by the relation

2
L/l« = ir-z

or

tr
2
(12-44)
2\J\a

Note that this mass has nothing directly to do with the real electron mass; it depends
mainly on the tunneling integral J. For small k the particle moves like a free particle
but its inertia depends on the overlap of neighboring atomic wave functions and the
604 Solids

resulting tunneling rate rather than the real mass. In some circumstances the effective
mass can even be less than the true mass m. However, if the tunneling is large because
the atomic energy level happens to be very close to the top of the potential energy
barrier, the effective mass is nearly equal to the real mass m.
When the tunneling is very large it may
start off with an assumed be incorrect to
eigenf unction of the form given by Equation (12-26). Such a wave-function ansatz is
known as the tight-binding approximation in which it is assumed that the atomic energy
,

is a good first estimate of E and that the electronic wave function is reasonably close
k

to being an atomic orbital when the electron is in the immediate neighborhood of an

ion core. If tunneling is too large this approximation breaks down and one may need
to start off with the nearly-free-electron model. In this model the basic wave function is
that of a free particle and the interaction with the ion cores is considered a perturbing
effect on that assumption. Other approaches more nearly exact than either of these are
commonly used as well.
When an electron is in one of the higher energy states near the zone boundaries
(k = +7r/a), the energy E k
is again quadratic but with a negative curvature and a
negative effective mass. Pushing on the electron causes it to slow down! We can
understand such an effect much more easily in the nearly-free-electron picture. We
note that near the zone boundary the electron's de Broglie wavelength is given by

277 2lT

k ir /a

The wavelength is now commensurate with the lattice so that strong backscattering is

present, and, more importantly, the incident and scattered waves strongly interfere.
To see this, consider the condition of strong reflection from two near-neighbor nuclei,
as illustrated in Figure 12-25. Two rays of the wave incident from the right are
reflected, one from site 1 and one from site 2. There is strong reflection when the
wavelengths are such that the two waves' components interfere constructively. This
occurs when their path difference, which is 2a, is equal to one wavelength, or A = 2a.
Thus, as the electron's k vector approaches the zone boundary, the electron is more
and more strongly reflected. The effect is equivalent to an electron possessing a
negative effective mass. The electron gains energy but slows down as it does so.

Obviously, this discussion is just the one-dimensional version of Bragg scattering where
the scattering plane has reduced to a single particle. It is easy to see that the
momentum transferred to the lattice in this case satisfies Equation (12-3). Values of k
outside the Brillouin zone are not needed because every time an electron reaches a
zone boundary it is backscattered to the other end of the zone. Its k value is trapped
in the zone.
The above discussion illustrates an important point; the quantity hk of an electron
in a crystal often behaves like a momentum but really should not be considered to be
one under all circumstances. This situation arises because pushing on the electron may
cause the entire crystal, and not just the electron, to gain momentum via interference
effects and interaction with the lattice. The vector hk is often called a quasimomentum
for this reason. Nevertheless, hk behaves sufficiently like a momentum that the
free-particle picture often remains reasonable.
Up to now only a single energy band has been considered. We must consider bands
corresponding to other atomic orbitals. The energy band under discussion for sodium
has been the one spread out around the 3s state. Lower energy levels, the Is, 2s, and
 12-4 Energy Bands in Solids 605

Figure 12-25 Figure 12-26

Electron reflection from the ions of a one- Some energy bands in a one-dimensional
dimensional crystal. The waves are shown at model Note that the value of Jm
of a metal.
an angle for clarity. The rays reflected from increases with m band is
so that the higher
sites 1 and 2 are in phase when the path wider. The forbidden region between bands is
difference 2 a is exactly one wavelength. called a band gap.

Band gap

2p states, are so tightly bound that tunneling rarely takes place; the crystal energies
are almost unchanged from their atomic values. On the other hand, the higher states,
3p, 3d, and so on, are much more loosely bound. Tunneling is very large between
different sites. These states form bands that are broader than the 3s band. In general,
we have several energy bands given by

Er = Em + 2Jm coska, (12-45)

where m is the band number and refers to the atomic state, 3s, 3p, on which the
band is based.
Note that the overlap integral Jm in Equation (12-45) depends on the band
number m. This is in accordance with the idea that the tunneling rate should increase
as m increases. In Figure 12-26 we illustrate a typical band structure for two of the
bands in our simple sodium model. The higher band is broader than the lower one.
We have assumed that the sign of Jm alternates as we proceed from one band to the
next. This is not unusual but we do not justify that assumption here.
A further feature of the spectrum is the existence of band gaps. These are the
forbidden energy regions between bands. Obviously, for a single atom, the forbidden
energy regions dominate the allowed regions, which are the discrete levels. The
opposite is usually true for the higher bands in a crystal; states where hopping is easily
possible have allowed regions that are much wider than the gaps. Band gaps are of
fundamental importance to the understanding of metals, insulators, and semiconduc-
tors as we see in Section 12-5.

Example

We consider a metal for wh ich a = 0.2 nm and m* is the true electron mass.
The tunneling constant J is

2 -34
h (1 1 x 10 j •
*f
171 2
= 1.0 eV.
2 ma 2(9.1 X 10"
31
k g )(2xicr
10
m) (l.6x 10" 19 J/eV)
606 Solids

The width of the band associated with this J is then 4\J\ = 4 eV. The time It
for an electron to hop from one ion core to the next can be estimated from the
uncertainty principle as

-34
h 1.1 X 10
a' ~ (,.o.v)(..6x,o-jav)
J •
s
=- 66 x 10
"6
=w s'

12-5 The Band Theory of Metals. Insulators, and Semiconductors

In Section 12-4 we have constructed a picture of the energy spectrum of an electron in

a crystal with its bands and band gaps. When we place many electrons into these
states the nature of the resulting substance, that is, whether it is a metal, an insulator,
or a semiconductor, depends on the details of the band structure and, even more
importantly, on how the electrons fill the allowed states.
In order to investigate how the electrons go about filling the bands we go back to
our sodium model of Section 12-4. There is a single 3* electron per sodium atom for a
total of N electrons. The 3s band contains N states. Since each state can hold one spin
up and one spin down, the band is half-filled as illustrated in Figure 12-27a. If we
have two electrons per atom, the band is completely filled, with two electrons for every
state, asshown in Figure 12-276. (While we might think that this is an apt description
of magnesium, the element next to sodium in the periodic table, it does not quite work
out that way, as is explained shortly.)
If we refer back to Figure 12-18 we see that when electrical conduction takes place

the Fermi sphere is shifted slightly in momentum space. On an energy level diagram
like the ones we have been using, this shift is shown as illustrated in Figure 12-28.

There are slightly more electrons with positive k vectors than with negative k and so
there is a general drift of electrons in the positive k direction; a current is set up and
we have a metal. On the other hand, with a full band as in Figure 12-276, there is no
allowed energy region for the tilt to occur because of the gap. Obviously, materials
with full bands like this one are insulators.

Figure 12-27

Filling of bands by electrons. A solid with one electron per atom has a half-filled band as
indicated by the cross-hatching in (a). This material is a metal. If there are two electrons per
atom the band is full, as shown in (b), and the substance is an insulator.

a i
(6)
 12-5 The Band Theory of Metals, Insulators, and Semiconductors 607

Figure 12-28 Figure 12-29

Effect of an electric field on the occupation of Example of overlapping bands in which a

the energy levels of a band. The application substance with two electrons per atom turns
of the field produces a shift so that there is an out to be a metal instead of an insulator.
excess of electrons having positive k values. Generally, k a and k h are two distinct
directions in three-dimensional k space rather
than just +k and —k.

Based on this argument we expect magnesium to be an insulator when it actually

turns out to be metal, having relatively low conductivity. The explanation of this

phenomenon is found bands in magnesium. Bands can

in the peculiar structure of the
sometimes overlap in certain regions of k space. An example of such a situation is
shown in Figure 12-29. There are now a few electrons in a nonfull band that can
provide electrical conduction. Overlapping bands occur in magnesium and several
other substances that qualify as metals. On the other hand, diamond has enough
electrons to fill a band without any overlap and is an example of an insulator.
All of the above considerations are made at zero temperature. However, if a band
gap is narrow, thermal excitations from a full band may be sufficient to provide a few
current-carrying electrons. Materials with such thermally activated conductivity are
known as semiconductors. Examples of these include silicon and germanium. Because of
the great importance of semiconductors to technology, we spend the next two sections
discussing them in detail.

Example

We list the band gaps of several materials below. Excep : for diamond all are
considered to be semiconductors.

Material Band Gap (eV)

C (diamond) 5.5

CdS 2.4

Si 1.1

Ge 0.7

Te 0.3

InSb 0.2
608 Solids

Figure 12-30

Valence and conduction bands in an intrinsic

semiconductor. A few electrons are thermally
excited out of the valence band. Also shown is

the distribution function n(e). Note that the

Fermi energy falls in the band gap.

Conduction band
sc

Valence band

n(R)

12-6 Semiconductors

Perhaps no technological development has contributed as much to our lives in recent

years as the application of semiconductor physics. The entire computer revolution is

based on this technology. We discuss these applications in Section 12-7 but here we
outline some of the basic ideas of semiconductors.
Wehave seen in Section 12-5 that semiconductors are characterized by small band
gaps so that charge carriers can be thermally activated from the filled band. This
filled band contains the electrons from the outermost shells of each atom and so is

called the valence band. The normally empty band to which charge carriers can be
excited is then the conduction band.

In an intrinsic semiconductor, all the electrons in the conduction band have been
thermally excited from the filled valence band. Such a situation occurs in pure
crystals. However, semiconductors containing impurity atoms may have localized
energy normally forbidden band gaps. The activation energy of the
levels within the
electron in these states can be considerably less than that of valence electrons. Such a
doped semiconductor is said to be of the extrinsic type. While most technical applica-
tions involve extrinsic semiconductors, we first consider the intrinsic type.
The number of charge carriers in the conduction band is given by the usual Fermi
function

"*=-57—^ > (
12 " 46 )

where e F is the Fermi energy. Figure 12-30 shows the almost-filled valence band and

the partially filled conduction band. The Fermi energy is shown as lying within the
band gap. This may be a bit of a surprise since, for a gas of free particles at T= K,
the Fermi level is the energy of the highest filled level, and for T> K it is the
energy for which n h has dropped to one-half of its maximum value. But the Fermi
energy is more fundamentally the Lagrange multiplier in our statistical treatment of
Chapter 1 1, which determines that the sum over all k of Equation (12-46) comes out
to be equal to the number of particles N. We now show that this condition puts e F in

the band gap.

 12-6 Semiconductors 609

Assume that the top of the valence band is quadratically inverted downward at
k = 0, indicating negative effective mass. This could just as well be a region of a band
out near the Brillouin zone boundary as in Figure 12-276, rather than at k = as in

Figure 12-30. The results are the same. The energy e c is defined as the bottom of the
conduction band, and c„ is the top of the valence band as shown in the figure. Then
the number of particles in the condition band is

N
t
= I nk . (12-47)
k

If there are N electrons in the valence band at T = K, the number of these electrons
excited out of the valence band by thermal agitation is ./V minus the number
remaining in the band:

N. = N- £ nk = £ (1 -n k ), (12-48)
k k
(**<«) (e*<e„)

where the last equality comes from the fact that the total number of states in the
1 14
conduction band is equal to the total number of electrons in it at T= K when it is
full. In an intrinsic semiconductor all the thermally excited electrons must come from
the valence band so that we have

N C
= N V
. (12-49)

As we see next, this condition is enough to determine the Fermi energy eF .

We can evaluate N and N easily we assume that e and e

c t
,
if
c
much more than
are
k B T away from e f This often the case for real systems.
. is Since e k > e in the c

conduction band, fi{e k — eF ) » 1 so the exponential dominates the 1 in the de-

nominator of Equation (12-46). We then have

nk ^e-K*-*'\ ek >e c
. (12-50)

From Equation (12-47), it follows that

K= L «-««*-"> = «««'-*> £ «-««*-««). (12-51)

k k
(e*>«c) (e k -e >0)c

The last sum on k is easily done by changing to an integral over energy. We know
how to do this when energy depends quadratically on wave number k (like a free
particle) as it does near the bottom of the conduction band. We have measured
energies from e c so that the sum in Equation (12-51) is

Z= £,-*
£>0

which is just the classical partition function of Equation (11-18), evaluated in

Equation (11-46). The resulting formula is

2Trm ( k B T\ 3 / 2
Z = C
2V\ (12-52)
610 Solids

In Equation (12-52) we replace the free-electron mass by the effective mass m c

associated with the bottom of the conduction band and we denote the corresponding
sum by Z c
. There is an extra factor of 2 in Equation (12-52) to account for the spin
degeneracy of each energy level. We end up with the result

N t
= e^"-^Z t
. (12-53)

To treat the valence band we do a bit of manipulation of Equation (12-48). We

write

l-n t =l- -% ; = -jr. :

= — jj
:
. (12-54)

From this expression we see that the missing electron population in the valence band is

described by a sort of Fermi function, but with a minus sign in the exponential instead
of a plus sign as in Equation (12-46). However, this minus sign is rather natural since
the valence band, as we have drawn an inverted quadraticit in Figure 12-30, is

function anyway. Next, note that as e k becomes more negative, e F — e k becomes

larger positively, and if e F is much greater than e k for all e k below e v then ,

1 - n k -» *-««*-«*>

and

k
(e„-ek >0)

Changing the energy variable from e k to e„ — e k gives us precisely the same sum as for
the conduction band, except that the curvature of the band is determined by an
effective mass m v
(a positive quantity here). We get

N v
= €-*"-'•%„
where
3 /2
2irmk R T\
Z„ = 2V\
fr

Equating A^ and A^, according to Equation (12-49), gives an expression for e^:

g
P(e F -e,)2 _ g
-P(e F -t- c )2

Taking the logarithm of both sides gives

P(e F -e )+ t
\\nm c = -fi(e F -e v )
+ \ In m,

or

eF = l
,(e c + e„) + fk B T\n(m v/m t
). (12-55)

We see that if T —> K or if m = m the Fermi

v c , energy e F is halfway between the

conduction and valence bands. If m ¥= m then e F

B c
is displaced very slightly from the
halfway point at T> K. For simplicity in the following we assume that m = m
v c

and that e F is halfway between bands.

 12-6 Semiconductors Bit

From Equation (12-53), the number of charge carriers in the conduction band is

now seen to be

V - e
/;/
'/
(12-56)

where

Eg = ec -t (12-57)

is the band gap. We can see from Equation (12-56) that if E gets too large, the
number of charge carriers rapidly drops toward zero.
We might think that Equation (12-56) enumerates all possible charge carriers.
However, recall that the valence band is unable to conduct electricity only if it is
completely full. When some electrons are thermally excited out of the valence band, it
can again contribute to the conductivity. It is a curious feature that it is much more
convenient to speak of conduction not by the electrons in the nearly full valence band,
but by the holes left behind when electrons leave the band. The existence of

conduction by these holes is of vital importance to the workings of semiconductor

devices.
To begin to understand the concept of holes we again start off with a completely
filled valence band. We turn on an electric field. The current density carried by the
band is

J=-^Iv„
v
(12-58)
k

where c is a positive number representing the charge magnitude of an electron and

where \k is the velocity of an electron in state k. We need a bit of discussion about this
velocity.
The velocity of an electron having energy ek is found from the relation

vt
kx
= (12-59)
h dk x

i 1
with similar equations y and z components. When ek = h k /2m, as for a free
for the

particle, v kx = hkjm is just the normal relation between velocity and momentum.
When e k has a more complicated dependence on k, as can happen in some parts of a
band, we justify Equation (12-59) by considering the electron as a wave. The usual
group velocity of a wave is derived from the wave's angular frequency w A by

du k
Vk *
= -

~dT
x

From the usual quantum relation e k = hu k ,

Equation (12-59) follows immediately.
Going back to our discussion of the full band current of Equation (12-58) we note
that we must have

band. When the band full the total velocity vanishes. For a band energy
for a full is

no surprise
function e k having a complete symmetric shape as a function of a k, this is
612 Solids

Figure 12-31 Figure 12-32

Schematic drawing of the silicon crystal Impurity phosphorus atom in a silicon crystal.
indicating its four covalent bonds per atom. An extra valence electron is weakly bound to
the phosphorus ion.

d^^y==i

because for every positive vk there is a negative vk . It can be shown that even if the
band is unsymmetric this sum vanishes. However, if one electron is missing from
momentum state k', the current density is

J
= (12-60)
V k k
(occupied) (all)

The band conducts electricity as if there were a positive charge moving with the
velocity of the missing electron. A full band of electrons is in essence electrically
neutral. Remove one and the equivalent of a positive charge appears. The number of
charge carriers in an intrinsic semiconductor includes the holes in the valence bands as
well as the electrons in the conduction band. In an intrinsic semiconductor these two
numbers are equal.
As it turns out, an extrinsic (or is much more useful than the
doped) semiconductor
intrinsic type discussed above. A
atom has four valence electrons outside a
silicon
closed shell. The partially filled shell could, if filled, hold eight electrons. So in the
solid each atom has four covalent bonds arranged in the same crystal structure as
diamond. We show this very schematically in Figure 12-31. Silicon is a semiconductor
with a band gap of 1.1 eV. Suppose a small percentage of the silicon atoms are
replaced by phosphorus or arsenic, each having five valence electrons. Each of these
elements can form the four covalent bonds that silicon has but there is then an extra
electron left over. That electron is loosely bound to the impurity nucleus as shown in
Figure 12-32. It takes only 0.05 eV to break it away from the phosphorus or arsenic
nucleus. This situation introduces new energy states into the band structure. Suppose
we plot band energy versus the position in the crystal as in Figure 12-33. The states of
the impurity are localized, that is, they correspond to motion of the electron in a
restricted region of space. These new states are somewhat like the states of hydrogen
because the electron orbits a single ion. Since it does not take much thermal energy to
break the extra electron loose, the particle is easily excited into the conduction band
and contributes to the number of charge carriers. Because of its ability to contribute to
conductivity in this way, this impurity is known as a donor. As can be seen from
 12-6 Semiconductors 613

Figure 12-33

Energy versus position in a semiconductor

with donor impurity levels in the band gap.
The valence and conduction bands are the
same throughout the crystal and the valence
band is full. The donor is able to provide an
electron to the otherwise empty conduction
band.
Conduction band
Ek

^
^- x

Equation (12-56) the conductivity of an intrinsic semiconductor depends exponentially

on the band gap. The donor binding energy is so much smaller than this that donor
conduction easily dominates intrinsic conduction in a doped semiconductor.
There is yet another kind of doped semiconductor. Suppose the impurity is
aluminum or gallium. These elements have three valence electrons instead of four so
that in the silicon crystal structure one of the four covalent bonds is unsatisfied as
shown in Figure 12-34. Because of this unsatisfied bond, it is not too energically
unfavorable for an electron from someplace else in the crystal to hop into the void and
cause the formation of an Al~ or a Ga~ ion. Now a full set of covalent bonds is
formed. This electron must have come from the valence band, which now has a hole.
The energy levels of the impurity are shown in Figure 12-35 for aluminum and
gallium impurities. These energy levels are each about 0.06 eV above the valence
band. Because the impurity can locally bind an electron given up by the valence
band, it is known as an acceptor. Again current due to holes caused by acceptor levels
can dominate the intrinsic current.

Figure 12-35

Figure 12-34
Energy versus position with acceptor levels in
Silicon crystal with an aluminum impurity. the band gap. A small amount of thermal
One of the covalent bonds is unsatisfied.
energy can cause the excitation of an electron
to an acceptor level, leaving a conducting
hole behind in the valence band.

E
Conduction band

T»- X
 ~

614 Solids

Figure 12-36

Properties of w-type and p-type semiconductors. The Fermi level in an n-type system is closer to
the conduction band than to the valence band while the opposite is true in a p-type system. The
energies of donor and acceptor levels are indicated by e d and e a respectively. The relative ,

distributions of electrons and holes are represented by the n(f) functions and by the plus and
minus signs.

»(£)

Semiconductors doped with donor levels are called n-lype because the charge
carriers are negative electrons in the conduction band. Those doped with acceptor
levels are p-type because the charge carriers are positively charged holes. Transistors
and other semiconductor devices depend fundamentally on the existence of these two
types of semiconductor, as we show in Section 12-7.
In order to understand those devices, it is important to know how the presence of
impurities modifies the Fermi level. In an rc-type semiconductor there is clearly an
increase in the number of electrons in the conduction band. The tail of the Fermi
distribution is enhanced. However, holes in the valence band can be filled, at least

partially,by electrons dropping into them from donors. The result of this is that the
Fermi level (which still gives the energy at which the distribution function n k falls to
one-half) has moved up toward the conduction band as shown in Figure 12-36a.
Similarly, in a />-type substance the number of holes is enhanced and the number of
conduction electrons diminishes so that e F moves down toward the valence band as
shown in Figure 12-366.

Example

By Equations (12-56) and (12-52) the density of conduction electrons at room

temperature {k B X 300 K = 1/40 eV) is

3/2
V iOE* /2
2tt(9.1 X 10~ 31 kg)(l.38 X 10~ 23 J/K)(300 K)
i = 2e- 2
V 10 34
(6.6 X J •
s)

- 40E /2
= e t
(3 X 10
25
electrons/m
3
) (
Eg given in eV).

~9
For a band gap of 1 eV the exponential factor is 2 X 10 which is a
,

substantial reduction of the number of conduction electrons. However, if the gap

is reduced to 0.1 eV, the exponential factor becomes — 0.1.
 12-7 Semiconductor Devices 615

12-7 Semiconductor Devices

Except for the development of nuclear weapons, no other area of technology has had
such an impact on society as the transistor and related semiconductor devices. After J.
Bardeen, W. H. Brattain, and W. Shockley invented the transistor in 1948, small
solid-state devices soon replaced cumbersome vacuum tubes. These devices have been
miniaturized to a very small and can operate very rapidly. Microelectronics, with
size

integrated circuits having hundreds of electronic elements placed on a single chip of

silicon, has been developed to an extraordinary degree. The computer, which was slow

and monstrous before the transistor, rapidly shrank in physical size, grew in memory,
and became enormously faster. Someone has said that this electronics revolution that
we are witnessing is much more important than the industrial revolution of the last
century because the latter had amplified only human muscle power, whereas the
present revolution is expanding the range of the human mind.
Of course, it is not possible to review here more than a few of the general ideas
involving these devices. We discuss only simple p-n junctions, solar cells, light-emit-
ting diodes, and transistors.

The diode or rectifier is a system that allows current to flow in only one direction.
Such a property is obviously important when using AC to operate objects like
calculators or battery chargers that require DC. Rectifiers can also be used as
detectors in radio receivers; they aid in the separation of the modulating signal from
the carrier wave. They are used in logic circuits in computers as well as in many other
electronic systems. The p-n junction is a rectifier as we now proceed to describe.
A semiconductor doped with acceptors is placed next to a material doped with
donors to form a p-n junction. Actually, the two regions may be part of one single
crystal, which has had from the two ends, but we
different impurities diffused in
pretend that it is made up of two separate pieces just placed next to one another. Just
before the two pieces touch, the energy level scheme and the electron distribution
functions appear as in Figure 12-36. Note especially that the n end has a larger
concentration of conduction electrons than the p end and the p end more holes than
the n end. Placing the two regions together is somewhat like placing a box of oxygen
atoms and a box of nitrogen atoms next to one another and opening the connecting
wall. The original density gradient in each gas cannot be maintained; the oxygen
flows toward the nitrogen and vice versa.
Where this analogy breaks down is in the fact that oxygen and nitrogen are neutral
while electrons and holes have charge. The p region and the n region are both
electrically neutral to begin with, but the flow of electrons from the n region leaves
positively charged donor behind; the flow of holes out of the p region leaves
sites

negative acceptor sites behind. These charged regions set up an electric field that soon
halts the flow of electronsand holes. The result is a region on the face of each material
which is depleted of local charge carriers, holes on the end of the p side and electrons
on the end of the n side, as shown in Figure 12-37. These two depletion regions each
have the charge of the fixed impurities of each material. An electric field exists only in
the narrow depletion regions. This zone turns out to have a width ranging from 10 to
10 nm,
as determined by the material and the amount of doping of each region.
Wemight ask what happened to the electrons that left the n region and the holes
that escaped the p region. Note that the entire system shown in Figure 12-37 remains
neutral. The number of bare donors equals the number of bare acceptors in the
depletion regions. The electrons and holes from each side have simply recombined and
canceled one another.
616 Solids

Figure 12-37 Figure 12-38

Depletion regions in an n-p junction. Thin Electrical potential <M*) seen by a charge in
charged layers form on the contact surfaces of the neighborhood of the depletion regions.
the junction. The layer on the n side is charged The electric field E = — d<p/dx points to the
positively because the depletion of electrons right and is confined to the charged layers.
bares the positive donor ions. On the p side
the loss of holes bares the acceptor ions.

Electric
field

n type ptype \ t
Depletion
layers

Depletion
regions

The electrons or holes far from the p-n

do not see any local gradient in
interface
electron density and so have no inclinationThose close to the junction see the
to flow.
gradients in density but do not flow because the electric field opposes any motion on
their part to relieve this gradient.
In general, an electric field Ex in the x direction is related to a potential 4>(x) by

E. =
dx

Since the electric field is confined to the depletion zone, <£(*) is constant except in that
region, as shown in Figure 12-38. The energy of an electron placed in the potential is

changed from ek to e^ — e<f>(x). Thus, the band edges and the Fermi energies are
shifted relative to one another by

e<}> = e[<j>{-cc) - <f>( + oo)]

as shown in Figure 12-39. Electrons moving from an n region toward a p region now
encounter a potential barrier that most cannot surmount. Holes moving from p
toward n also find a barrier (seen by viewing Figure 12-39 upside down).
Note in Figure 12-39 that the condition of equilibrium between the two materials is
that the Fermi energy e F is the same on both sides of the junction. This is a very
general thermodynamic principle. Just as heat flows when there is a temperature
difference and volume changes when there is a pressure difference, so particles flow
when there is a Fermi energy difference. At equilibrium e F is the same everywhere.
This principle by itself tells us that energy levels readjust as shown.
We can now see how this junction acts as a rectifier. If we apply an external
voltage V to the device with the circuit shown in the inset of Figure 1 2-40, we enhance
the internal electric field and the potential energy barrier as shown, preventing
electron motion from the n side to the p side and hole motion in the opposite
direction. The system is said to be reverse biased. Very little current can flow in such
circumstances. However, if we provide forward bias as illustrated in Figure 12-41, the
 12-7 Semiconductor Devices 617

Figure 12-39

Energetics of the p-n junction. Because of the

charge layer, a potential barrier is set up by

the electric field. This raises the band edges by

e% such that the Fermi energy in each region
is now the same.

* Wo
C
fir.
F
s- H*>
e
-T-r^

external electric field opposes the internal one, the potential barrier is lowered, and
thermally activated electrons and holes can much more easily surmount the barrier.
As V increases, the barrier decreases and the current flow increases substantially.
Clearly, the system behaves as a rectifier.
It is not difficult to be more quantitative about our analysis of this effect. When
V= 0, electrons and There are as many
holes occasionally flow across the junction.
going one way as another and the net current is zero. A few electrons on the n side
have sufficient thermal energy to overcome the potential barrier and move from the n
side to the p side. This current is called the electron generation current I . If the few
electrons that are on the p side diffuse to the junction, they are swept across by the
electric field in the junction. This flow is called the electron recombination current Ier .

Because the net current is zero, we have

/.„ + /„ = 0. 12-61a)

Figure 12-40

Reverse-biased p-n junction. The potential

barrier increases by e V and very little current
flows.
Figure 12-41
In" 1 " 1

1
Forward-biased p-n junction. The barrier is

±ll 1
lowered and thermally activated electrons and
holes can easily flow across the junction.

e(<t>o + V) n p

-III
V

e(<t>o - V)

++ +
618 Solids

Similar arguments for holes give

/h? + /hr = 0. (l2-61b)

Suppose that a reverse bias voltage V is now applied. The number of electrons in
the conduction band on the n side at energy e is, by Equation ( 12-50), proportional to
the exponential factor exp[-/?(e - e F )]. When the energy is shifted by eV, 7 is
e
therefore reduced by an exponential factor according to

~ 'v
tjv) = ies (P) e p -
( 12 - 62 )

For any reasonable V this quantity becomes quite small. 7er on the other hand, , is not
affected by the biasing so that the total electron current becomes just 7er The hole
.

current also is reduced to 7 hr . In the figures 7er is to the left and 7 hr to the right so
that the effects of these two currents add to give a total current

'reverse = 'er + V (12-63)

Under forward bias the two generation currents are each enhanced by the
exponential factor so that, for example,

+/wr
IJ<V) " Ag(0)« ,
(12-64)

which dominates 7er . We then have a total forward current

'forward = ('eg + I*)*'" (12-65)

The two situations can be summarized for all V as

7(F) = 7 (^-1), (12-66)

where the factor

h= 'eg(O) + / hg (0)

is known as the saturation current. If V is positive in Equation (12-66), the exponential

dominates unity and we have Equation (12-65). If V is negative, the exponential can
be dropped; by using Equations (12-6 la) and (12-61b) we can see that the resulting
current — 7 is correctly equal to that of Equation (12-63). Figure 12-42 graphs the
I-V behavior of the p-n junction. Clearly, much more current flows in one direction
than the other, as one needs in a rectifier. We also see that the exponential growth of 7
with V given by Equation (12-66) allows the p-n junction to act as a part of an
amplifier.
The p-n junction has several other uses as well. Solar cells, known also as
photovoltaic cells, are appropriately designed p-n junctions. Light shown on the
junction region, as in Figure 12-43, produces electron-hole pairs. Electrons on the p

side and holes on the n side are swept across the junction by the internal electric field.
These excess charges provide an external voltage, the photovoltage, between the ends
of the material or between metal conductors attached to the ends. Such cells are used
to power calculators, watches, and spacecraft, and to provide commercial electricity.
The latter use is still very limited because of the high cost of fabricating solar cells.
 12-7 Semiconductor Devices 619

Figure 12-42

Current as a function of external voltage in a

p-n junction. The current for reverse bias is

the small saturation current. Under forward

bias the current increases exponentially.

An inversion of the solar cell concept leads us to the light-emitting diode (LED). By
forward biasing a p-n junction a current of electrons and holes is established across
the junction. Some electrons arising from the n side and reaching the p side recombine
with the holes there, while holes going in the opposite direction annihilate electrons.

Radiation may be released in this process (see Figure 12-44). The doped semiconduc-
tor GaAsP emits red light and is often used as a display in calculators and other
electronic instruments. It does not burn out like a regular light bulb and requires very
little power. It is to build a semiconductor device that acts as a laser and
even possible
produces coherent Such lasers are now commonly used in compact disc players.
light.

While the simple p-n junction diode is obviously an important device, a more
complicated semiconductor system, the transistor, is even more vital. While transistors
come in many forms and perform many functions, we consider only one type and one
use —
namely, the p-n-p structure used as an amplifier.
An amplifier has many uses; its role is to turn a weak signal into a strong one. In
high-fidelity equipment, this might be involved with making the very weak signal
from a phonograph cartridge into one sufficiently powerful to drive speakers.
Figure 12-45 shows a double junction, p-n-p, and its associated circuit. We show
that the AC voltage input Vm on the left junction is strongly amplified by the junction

Figure 12-43

Mechanism of a solar cell. When radiation Figure 12-44

p-n junction, electrons and holes are

strikes a Behavior of a light-emitting diode. A forward
produced. The intrinsic electric field sweeps biasedp-n junction has currents of electrons
electrons from the p side and holes from the moving to the right and holes to the left.
n side. The charges accumulate to establish a When they recombine with their opposites,
photovoltage. radiation is emitted.

- i p
n
FT"
+
+ +
+
t b)
620 Solids

Figure 12-45

p-n-p transistor and circuit to illustrate amplifier operation. The forward- biased p-rt junction
is known as the emitter; the reverse- biased side is the collector. The connector to the n region is

called the base. A small change AFm in the input voltage results in a much larger change AI* iul

in the output voltage.

Emitter Collector
v
U c

h|iHi>
-v) v„
R Base

Rr-
=^v t

on the right. The left junction, known as the emitter, is forward biased so that a large
current flows. By Equation (12-66) the current is

*E J
E0 e >
(12-67)

where VF is provided by the battery shown. What the emitter does is to remove

electrons from the n region and, more importantly, emit holes into it. These holes drift
across the n region and, if the geometry is right, most are picked up at the second
junction, the collector, before they can reach the base. The current at the collector
(which is reverse biased by the battery of voltage Vc ) is, in the absence of the
picked-up emitted part, just the saturation current ICQ Inclusion of that portion of the .

emitter current picked up by the collector gives for the total collector current

Ic = Jco + y JE * Y4> 12-6H)

where y is a geometrical factor that measures the fraction of emitter current picked up
by the collector. The final approximate equality assumes that the saturation current is
quite small. The fraction y can be very close to unity.
When the input voltage undergoes a small change AFm , it causes a change in the
emitter current A/£ given by differentiating Equation (12-67):

If we assume Vm <sc VE we have

,

AIE = IE0 f3ee^AV in

. (12-69)

By Equation (12-68), the change in the collector current is just

M ~ yME
c .
 12-8 Phonon Dynamics 621

The change in output voltage becomes

AFout = R C M C - yR c M E = yRJel^ AVm .

The resulting amplification ratio is then given as

= p,v'
T) I e 12-70)
kB T

As we see in an example at the end of this section, this ratio can be more than 100.
Note that the right side is independent of Vm in this approximation. A sinusoidal Vm
results in a sinusoidal output voltage Vonl of larger amplitude; the device is linear.

However, if V
m gets too large the approximation used in deriving Equation (12-69)
breaks down and the output voltage becomes distorted, which is undesirable in, for
example, high-fidelity applications.
Transistors have many other applications, including uses as switches and computer
memory elements, which we do not discuss here. The reader might take an inventory
of the electronic equipment in daily use to see how amazingly dependent we have
become on semiconductor devices.

Example

A familiar light-emitting diode gives off red light. From this information we can
figure out the band gap E in this material, because we know that E = hc/X.
Since the wavelength corresponding to red light is around 650 nm, we have

1240 eV •
nm
1.9 eV.
650 nm

Example

Typical values of the parameters that occur in Equation (12-70) are Rc =

10
3
fi, IE0 = 10 juA, y « 1, and k B T/e = 1/40 V. If VE is adjusted so the
exponential factor is around 10 , the voltage amplification ratio is

-5 3 _1
7j * (I0 3 fi)(l0 ^)(10 )(40F )
= 400.

12-8 Phonon Dynamics

Our discussions so far in this chapter have been concerned with systems involving
electrons. We now switch emphasis in this section to some properties of solids not
dependent on the presence of mobile electrons but
dependent rather on the motions of
the much more massive ion cores. While these atomic structures do not generally
diffuse throughout the crystal they do vibrate about the lattice sites and create
622 Solids

Figure 12-46

Potential energy of atom 2 due to interactions

with its neighbors 1 and 3. The result is equal

to the sum of the individual potential energies
Vl2 and V 23 .

fe o
,v l2 * v 23

collective wave motions that we have called phonons. In Chapter 1 1 we have seen the
influence of phonons on the thermal properties, especially specific heat, of solids.
There we use some properties of phonons that are just quoted. In this section we
provide further justification of those properties.
The Born-Oppenheimer method mentioned in Section 10-1 in the treatment of
molecules is based on solving the electronic Schrodinger equation by assuming fixed
nuclei. The electronic energy then acts as a potential energy function for the
interaction of the nuclei. This same principle is important for solids. The forces an
atom in a crystal feels from neighboring atoms are caused mainly by electronic
interactions.
Suppose we consider a one-dimensional line of atoms as a model of a crystal, as we
have done above to investigate the electronic structure. Now we want to use the model
to study the motion of the entire atom. Figure 12-46 shows the curves that might
describe the potential energies of an atom due to its two nearest neighbors in a
covalent or van der Waals crystal. The total potential energy is seen to be symmetric
and to have a minimum at the equilibrium position of the atom. Such a picture
applies to each atom in the crystal (except for the atoms on the surface whose
potential energies are not symmetric).
Generally, the motion of an atom about equilibrium is small so that it is reasonable
to expand the potential in powers of the distance from the equilibrium position. This
argument has been used to discuss diatomic molecules in Section 10-7. There the
atoms in a diatomic molecule are considered to be bound harmonically. Here the
same result is true; the bottom of the potential energy well of any particle can be fit
by a parabola. However, that parabola is determined by interaction with many
neighbors, not just one other atom as in the diatomic case.
In this way we justify, to a certain extent, the Einstein model of a crystal treated in
Chapter 1. But particles 2 and 3 in Figure 12-46 do not remain stationary; they also
1

move. So the better way to picture a crystal is as a group of particles interconnected

by springs — a network of springs — as illustrated in Figure 11-9. One particle's motion
causes a neighbor to move, and so on, so that a wave travels along.
To treat waves in our one-dimensional crystal model we again introduce periodic
boundary conditions as in Section 12-4, rather than involving ourselves with the
complications of free surfaces or container walls. The basic model is shown in Figure
 12-8 Phonon Dynamics 623

Figure 12-47

One-dimensional model of a crystal with periodic boundary conditions.

12-47. The particleon the right of the iVth is the first, and that to the left of the first is
the A^th. We can consider the entire crystal as strung out in a large circle with the
ends tied together by a spring.
We want waves on our jV-body one-dimensional
to solve for the frequencies of
system. We can do this classical equations of motion or the
by solving either the
Schrodinger equation. The allowed frequencies turn out to be identical in the two
approaches. The former approach is simpler and we proceed that way.
The spring constant is K, the mass of an atom w, the position of the nth particle
xn , and the equilibrium separation of the particles a. A particle's displacement from
its equilibrium position R n
is

un = xn -R n
(12-71)

as shown in Figure 12-48 for a particular particle.

The force on particle 2 due to its spring connection with particle 1 is

F21 = -K(x 2 - -v, - a). (12-72)

We have taken the spring to be at equilibrium (/?,, = 0) when the particles are
separated by a lattice distance a, that is, when x .,
— x ]
= a. In terms of the u 's, we
have

F2X = -K(x 2 - R 2 - .v, + #, + R2 - R - x

a) = - K(u 2 - «,).

The classical equation of motion for particle 2 is (denoting d/dt by a dot)

»w 2 = -K(u 2 - w, ) + K(u 3 - u 2 ). (12-73)

Figure 12-48

Displacement of a particle in a one-dimensional crystal. In the system shown, all particles are at
their equilibrium positions Rn except particle 2, which is displaced a distance u 2 = x., - R ,.

The nearest-neighbor spacing is a.

x7
I <h

Ba
624 Solids

Figure 12-49

Example of a sinusoidal wave at one instant of time. The equilibrium positions are indicated by
the vertical lines. The wavelength is 12 lattice spacings.

(J)
10
—^H-OJO^O-^^^H^f^T-^H— c| (J)

The plus sign in front of the last term means that the force on particle 2 due to
particle 3 is pulling it to the right when u 3
— u 2
is positive. Since x 2 = "_>• Equation
(12-73) can be written completely in terms of the u's.

There is nothing special about particle 2 or any particle in the system when
periodic boundary conditions are used. Hence the equation for the nth particle is just
like Equation (12-73) and can be written as

mu n = -K(u n -«„_,) + K(u n+1 - u„). (12-74)

We expect longitudinal waves to propagate on this chain. An example of a wave at

one particular time is shown in Figure 12-49. The particle displacements change
sinusoidally as we proceed from one particle to another. The wave pictured might be
described at that instant of time as u n = s sin(277rc/12), where n numbers the particle
and s is the amplitude of the motion. The 12 appears because the wavelength of the
wave in the figure is 12a. The time dependence is of the form sin to/ or cos to/, where
to is the sought-after frequency of the wave. More generally, we can look for
traveling-wave solutions having the form

ikR
un = se 'e-
iut
t
(12-75)

where k is the wave number and s is the amplitude. We could use sines and cosines
but the exponential form is easier.

Use R n = na and plug Equation (12-75) into Equation (12-74) to obtain

-u 2 mse iknae- iut = - Ks{e' kna - ,•"*<- »«),-««'

+ Ks(e U{n+])a - e'
kna
)e'"".

— se' na ^' wl
Dividing out e gives

cc
2
m = K{\ - e-'
ka
)
+ K{\ - e'
kn
)
= K(2 - 2 cos ka).

Using the trigonometric identity

X 1

sin
2
— = — ( 1
— cos .

2 2
we have
4 A' ka
or
2
= •

sin'
2 —
m 2

or

= 2l/-
[* ka
—
to sin (12-76)
V m 2

where the absolute value signs occur because a frequency is always a positive quantity
by definition.
 12-8 Phonon Dynamics 625

For small wave numbers (or long wavelengths according to the relation k = 2ir/\)
the discrete character of the system, that is, the fact it is made up of many individual
masses, is not noticeable to the wave. Then Equation (12-76) can be simplified by
using the approximation sin x ~ x so that

(12-77)
V m

In this long-wavelength limit the phase velocity co/A and the group velocity dic/dk
are identical and equal to

Ka 2
.
(12-78)
m

The velocity does not depend on wave number so there is no dispersion in this limit.

For shorter wavelengths the approximation of Equation (12-77) is no longer valid and
waves of different frequencies travel at different velocities; the dispersion arises

because of the discrete character of this chain of particles.

Just as in the electron case the allowed values of k, which give us the permitted
wavelengths and frequencies, are determined by the boundary conditions. With the
periodic boundaries we have

«o
= un (12-79a)

and
u N+l =u 1 ,
(12-7%)

since to the left of particle 1 is particle N and to the right of particle N is particle 1.

From Equations (12-75) and (12-79a) we have

and
ikNa
e = 1

so that

2tt
k=—{, (= 0, ±1, ±2, ±3,... . (12-80)
Na

These are precisely the same k values as those allowed by Equation (12-37) for
electrons moving through a crystal. And as in that case there are limits on k space.
Values of k out of the first Brillouin zone are equivalent to those within it. This is easy
to see by adding the vector G of Equation (12-39) to any k value:

u n
(k + G) = se
,{k + G) " a
e-'"' = (»«'*"««-«'•"
y 2 »" = u n (k).

Thus, any region of k vectors having a width G is adequate to specify all possible
waves. We choose these vectors to be those in the first Brillouin zone as given by
Equations (12-38) and (12-80).
Note again that there are exactly N of these vectors in Equation (12-80); this as is it

should be because there are N particles and one expects to find exactly N distinct
waves corresponding to the N degrees of freedom of the system.
626 Solids

Figure 12-50

Angular frequency u versus k for a one-

dimensional harmonic chain. Positive and
negative k values represent waves traveling in

opposite directions along the chain.

The k values of Equation (12-80) are spaced quite closely together because of the
larger number N in the denominator. In plotting to versus k from Equation (12-76),
we can treat k as a continuous variable. Such a plot is shown in Figure 12-50. There
are two branches, one corresponding to positive k and one to negative k. Because we
have used periodic boundary conditions, we can have traveling waves on our chain;
the waves do not meet a wall and undergo reflection resulting in standing waves.
Positive k corresponds to waves traveling in the positive direction and negative k to
oppositely directed waves.
In Chapter 1 1 , we have derived the contribution of phonons to the heat capacity of
crystals. Our discussion there considers a chain of particles connected to walls, rather
than having periodic boundary conditions. The use of wall boundary conditions
results in standing waves. Negative k has no meaning in such a situation and the
spectrum shown in Figure 11-10 has only a positive k branch. However, there are no
is only one branch in the
differences in the thermal properties because, although there
wall-boundary case, the k values are twice as densely distributed. This discussion is
identical in spirit to the one given for electrons right after Equation (12-37).
The use of a complex value for the displacement u n in Equation (12-75) may
bother some readers since displacements must actually be real. However, since

solutions for plus and minus k correspond to the same frequency, the complex
conjugate of Equation (12-75) is also a solution for that frequency. Furthermore, since
the sum or difference of two solutions corresponding to the same frequency is also a
solution, we have, for example, as another solution

ikR nB + iul
-I- se~ 2scos{kR n -at),

which is a real displacement representing a traveling wave.

In Chapter 1 1 we have also discussed another crystal property dependent on
phonons, the thermal conductivity. In a metal, the electron contribution to this

quantity dominates and thermal conductivity is determined by Equation (12-22). In

insulators, however, the phonons carry the heat. It can be shown that the thermal
conductivity of a gas of particles is

= C V V 2T, (12-81]

where Cv is the heat capacity per unit volume, v is the velocity of the heat carrier, and t
 12-9 Magnetism in Solids 627

is the relaxation time (time between collisions). We find in Problem 1 1 at the end of
the chapter that k t of Equation (12-81) reduces to the proper result, Equation
(12-22), when applied to a degenerate electron system. While phonons differ from a
usual gas of particles (such as electrons) since they can be created and destroyed,
Equation (12-81) still applies to them.
From Equation (1 1-68) we have, for low temperatures (ignoring factors of order 1),

(k B Tfk k
C vv ~ 3
(*0 '

where cs is the velocity of sound in the crystal. The heat carrier velocity in Equation
(12-81) for phonons is also cs .

The mean free path is most commonly determined by phonon-phonon collisions.

The computation of it is often quite complicated and beyond the scope of our
discussion. One case that is easy to discuss is the situation in which the density of
phonons is so low that the phonons hit the walls before they hit each other. Then the
relaxation time is the time for a phonon to travel a distance L from one side of the
crystal to another. In that case t = L/c and so s

k%LT 3
•

h\2

AT 3
temperature dependence of k t is indeed observed in insulators at the lowest
temperatures.

12-9 Magnetism in Solids

Because the atoms that make up a crystal can have electrons with unpaired spins, the
solid as awhole can have a net magnetic moment. Because the atoms are in the solid
between them can often alter the character of this magnetism
state, the interactions

considerably. The most notable example of this is ferromagnetism, in which cooper-

ative alignment among the electronic magnetic moments gives some solids, such as
iron, a net magnetic moment in the absence of any external magnetic field. Other
forms of magnetism occurring in solids include paramagnetism, diamagnetism, and
antiferromagnetism.
Suppose we have a whose atoms each have a net spin \ but do not interact
solid
with one another magnetically. The only magnetic energy in the system is the direct
Zeeman interaction of the spins with an external magnetic field. A solid having such
energy levels can have no net magnetic moment in the absence of an external field
and is said to be paramagnetic Obviously, there is nothing special here about the spins
.

being in a solid and paramagnetism occurs as well in gases and liquids.

For electrons with spin S, we have seen in Equation (8-20) that the magnetic
moment per particle is given by

where [i
B is the Bohr magneton and g s is the electron g-f actor. In a magnetic field B
the possible energies of the spin are, from Chapter 8,

(VM )=-pBa, (12-82)

628 Solids

where the magnitude of the magnetic moment is

/*= -£s/V2, (12-83)

and a = ±1 is twice the magnetic quantum number m s By Equation (12-82) and

.

(12-83), spin-down states, that is, those that have a = — 1 and are antiparallel to B.
have a lower energy than those aligned with the field. Thus, the more probable states
in a thermal distribution have more particles with spin-down states than with spin-up
states. The entire collection of electrons then has a net magnetization, which can be

detected.
The magnetization per unit volume of a collection of electrons is defined as

M= M (p + -p_), (12-84)

where p a is the density of electrons with magnetic quantum number a. In equilibrium

p_ is larger than p _,
as explained above, but since p, is negative, M comes out
positive. For sufficiently small magnetic fields it turns out that M is proportional to
the applied magnetic field or

M = X B, (12-85)

where x ls called the susceptibility.

Suppose we have a solid made up of atoms each of which has a tightly bound
unpaired electron so that each atom has a net magnetic moment. Because the
electrons do not hop from site to site, those on separate atoms really do not see much
of one another. Then Fermi statistics is quite irrelevant to their relative spin states. We
can consider the situation as one in which the electrons behave classically and obey
Boltzmann statistics.
The partition function for a single electron having energy levels given by Equation
(12-84) is

Z= £ e
frBa = e
foB + g
-frB = 2 cosh fifiB.
a= ± 1

The magnetization per unit volume M

is related to the difference in density

between spin-up and spin-down particles, p + — p by Equation (12-84). Since a is ,

-I- 1 for spin up and — 1 for spin down, we have

P+ - p_=p(o), (12-86)

where p is the density of all electrons. The average value of a in Equation (12-86) is

given, according to the general procedures of Chapter 11, by

oe foBa e
PnB _ e
-PfLB

<°> = £ — =- = ,/>„!,_,-/»,* = tanhflifl. (12-87)

So the magnetization per unit volume is

M = ixptanhBjiB. (12-88)
 12-9 Magnetism in Solids 629

For very high temperature, such that uB «: k B T, the argument of the hyperbolic
tangent is small. For small x a Taylor expansion gives

tanh.v * x, x «: 1, (12-89)

so that we get

M -> tipBuB = pycB/k B T as T -» oo (12-90)

The susceptibility, defined in Equation (12-85), becomes in this limit

X =
A
M
—
5
= —
pur

kB T
(12-91)

This expression is known as Curie 's law, after P. Curie, giving x for a classical electron

system as inversely dependent on the temperature. As T increases, thermal agitation

weakens the ability of the external field to align the spins. Many solids exhibit
Curie-law behavior.
Because the hyperbolic tangent goes to unity for large values of its argument,
Equation (12-88) gives, for low T,

M r-»o
> up,

which corresponds to all particles aligned with the field. Of course, if Fermi statistics

has become important before the low-temperature condition k B T <^ [iB has been
satisfied, the last limit is not valid.
The magnetism of electrons in a metal cannot be described according to the
treatment just given. Those electrons are highly degenerate since the temperature
satisfies T <s: TF (the Fermi temperature is 10
4
or 10
5
K in most metals). We can take
the temperature to be essentially K. With no magnetic field, any filled momentum
state contains one spin up and one spin down and then the net magnetization M is

zero. When a magnetic field is turned on, the Zeeman energy of Equation (12-82) is

lowered if some spins align along the magnetic field. But such spins cannot just flip
into a different alignment, because then there would be two identical spins in the same
momentum state. The spin that is flipping must also be promoted to a higher
unoccupied momentum As further spins are turned over by increasing the
state.

external field they must be given even more additional kinetic energy to avoid
violation of the Pauli principle. Even at T = K a degenerate Fermi system has a
finite susceptibility, unlike the Boltzmann spin system. The behavior of the magnetism

of this degenerate fermion system isknown as Pauli paramagnetism.

Diamagnetism is based not on the Zeeman interaction of Equation (12-82) but on the
effect of the Lorentz force on an electron orbit. A free electron in a magnetic field
orbits in a circle and establishes a current loop that has a magnetic moment.
Examination of Figure moment is opposed to the
12-51 shows that the magnetic
external field. Manyshow such a negative magnetization, but we should note
solids
that the fact that the electrons in these solids are bound in quantum states in atoms is
not taken into account in our simple picture but is crucial to the existence and nature
of diamagnetism. The diamagnetic effect is negligible compared to paramagnetic
effects if they are present and is seen only in materials consisting of atoms having
completely paired electron spins.
630 Solids

Figure 12-51

Lorentz force due to a magnetic field causing

an electron The resulting
to orbit in a circle.
current loop has a magnetic moment \i with
a direction opposite to the field.

aEfe.

Ferromagnetism is an important subject in human history because of the compass.

Ferromagnetic substances have received considerable attention from solid-state physi-
cists because of the magnetic phase transitions that they undergo. At high temperature
and magnetic field, a piece of iron is unmagnetized. (With a field on, the iron
in zero
is paramagnetic at high temperature.) When the temperature is lowered to a certain
value, a spontaneous magnetization begins to develop. Below that transition tempera-
ture, the system behaves as a permanent magnet. This effect arises because of a
magnetic force, having purely quantum mechanical origins, that tends to align all the
spins in thesame direction. This force is related to the interaction in a covalently
bonded molecule. We know from Chapter 10 that, because of the Pauli principle, the
singlet spin state is energetically preferred over the triplet. In ferromagnetic substances
somewhat analogous interactions give preference to the triplet alignment for pairs and
an overall parallel arrangement of the entire spin system.
For some substances the spin -spin force does prefer the singlet or antiparallel pair
arrangement like that in the diatomic molecule. At low temperatures we then get a
state of a solid in which spins on alternate sites are in opposite directions. Such
substances are antiferromagnets.

Example

The polarization P of any substance is defined as the fraction of aligned spins.

Consider any paramagnetic solid. From Equations (12-84) and (12-90) we have,
for high temperatures,

M pB
P=
HP

The electron magnetic moment is -9.3 X 10 24

J/T. At T= 100 K and
B = 1 T the polarization is

24
(9.3 X 10 J/T)(1 T)
" _23
=
"
6.6 x 10~ 3 .

(1.4 X 10 J/T)(100K)
 Problems 631

Problems

1. (a) Compute the number density in terms of the nearest-neighbor distance a for the

two-dimensional triangular lattice, the square lattice, and the honeycomb lattice

shown in the figure,

(b) Assuming only nearest-neighbor interactions of strength -e, find the energy per
particle of the three lattices in (a) and of an arbitrary two-dimensional lattice in

which each particle has z nearest neighbors.

o o o o
o o o o
o o o o
o o o o
o o o o
o o o o
o o o o

2. (a) In the triangular lattice of Figure 12-2, particles 1 and 2 are nearest neighbors, and
particles 1 and 3 are second- nearest neighbors. Each particle has six near neighbors.

How many second neighbors does each particle have? How many third neighbors?

(b) Find the ratio of total second- neighbor interaction energy to total first-neighbor

energy if the potential energy falls off like the van der Waals interaction, — l/r b . Is

it a good approximation to drop second-neighbor interactions as we have often

done?
3. Figures 12-8 and 12-9 show two different views of the FCC lattice. By explicitly-

numbering the particles in each of your own versions of the two drawings show that the
two views are equivalent.
4. (a) Find the volume per particle in terms of the nearest-neighbor distance a for the SC
lattice, the FCC lattice, and the BCC lattice,

(b) What is the energy per particle in each of these lattices if only nearest-neighbor pair
interactions, each of energy — e, are taken into account.

5. Consider a one-dimensional model of a NaCl crystal made up of uniformly spaced

alternating positive and negative charges.
(a) Write an infinite series for the energy as done for the three-dimensional crystal in

the example at the end of Section 12-1. Attempt to estimate this energy by
considering a large number of terms in the series.

(b) Evaluate the sum exactly by comparing it with the Taylor series expansion of
ln( 1 + x ).

6. (a) Show that the vector set

R= a(n,x + n2y + n 3 z),

where the n, are arbitrary integers and i,y, z are Cartesian unit vectors, gives the
 ,

632 Solids

positions of the particles on a simple cubic lattice. What lattice is represented by

R = (a/2)(n k + i
n2y + n 3 z),

with B,, b 2 ,
"i integers whose sum is even?

(b) Find the set of vectors representing all the lattice points of a BCC lattice.

7. (a) Show that the vectors

R= a( «,u + n v)

where n ]
and n 2 are arbitrary integers and u and v are unit vectors given by u = x,

v = (x + v3 y)/2, give the sites of a two-dimensional triangular lattice.

(b) The reciprocal lattice vectors for the triangular lattice are given by

G = {2m/a)(m ]
\i* + m.,v*),

where m {
and m, are integers and u* and v* are vectors defined by u* v = v* •
•

u = 0, and u* • u = v* v = 1. Find
• u* and v*. What kind of lattice does the set
of G vectors describe? What is the "nearest-neighbor distance" in the reciprocal
lattice?

(c) Prove that exp(;G • R) = 1 in agreement with Equation (12-42).

(d) A "scattering plane" in a two-dimensional lattice is a line of particles. Show that

every line of particles has a G vector normal to it as it should according to the
original definition of G in Equation (12-3).

(e) Show that every G has a line of particles perpendicular to it.

8. (a) The Fermi energy of copper is about 7 eV. What is the Fermi velocity?

(b) Given the value of the relaxation time t in the example at the end of Section 12-3,

find the mean free path of a conduction electron. Compare this with the average
interatomic spacing.

9. Show that the current density (intensity) of a particle beam (number per unit area per
unit time) is particle density times particle velocity.

10. The thermal conductivity of copper at room temperature is 400 W/m K. Use this value •

to estimate the relaxation time T. Compare with the value obtained from the electrical
conductivity in Section 12-3.

11. Show that Equation (12-81), when applied to a degenerate Fermi system, reduces properly
to Equation (12-22).
12. (a) Repeat the derivation of Equation (12-32) for the case N= 3. Here the periodic
boundary conditions require that particle 3 be a near neighbor of particle 1. Find
the energy levels and solve for the Cn 's by setting the determinant of the coefficients
in the equation to zero,

(b) What are the k values that make up the first Brillouin zone for N= 3? Using these,
compare your values for the energies from part (a) to those of the general solution of

Equation (12-35).
13. Consider a free particle in a one-dimensional "box" of length L where the boundary
condition is periodic, that is, i//(0) = 4>(L). Show that the allowed k values satisfy
Equation (12-37) with Na replaced by L.
14. Show that the product of the number of conduction electrons N c
and the number of holes

Nr
in a semiconductor is independent of the Fermi energy eF . The relation for NN
( r
is
 Problems 633

called the law of mass action. Since the relation is valid for any eF , this product is the same
independent of degree of doping. If the number of conduction electrons is increased by

adding donors, the number of holes must decrease correspondingly. Evaluate N N /V~
C V

for diamond, silicon, and germanium at room temperature by using the gap data given at
the end of Section 12-5. Use effective masses equal to the electron mass.

The bulk of solar radiation has a wavelength less than 1 fim. What is the minimum
energy gap that a solar cell should possess to take advantage of this? Is silicon ap-
propriate?

A small change AFm in the input voltage of the transistor circuit of Figure 12-45 produces
a change A/3 ,, in the emitter circuit power and a corresponding change APC in the power
delivered to the resistor R (
. Show that the power amplification ratio satisfies

APC 2y
2
fieIE Rc
APE 1+ ln(/£//£0 )

Evaluate this ratio for the conditions given in the example at the end of Section 12-7.

17. A positively charged arsenic donor ion in silicon attracts an electron much like a hydrogen
nucleus. However, the intervening silicon behaves like dielectric material having permittiv-
ity constant e = 12e , where e is the permittivity in vacuum. The electron also has an
effective mass in silicon of 0.2 times the electron mass. The ionization energy of this system

is the separation between the lowest donor level and the conduction band as shown in

Figure 12-33. Estimate this ionization energy by using the appropriately modified hydro-
genic energy levels. Compare your result with the accurate value given in Section 12-6.

What is the Bohr radius of this system?

18. Write down the set of equations analogous to Equations (12-74) for a ring of three
particles connected by springs. Substitute u n (t) = e~'"' u n (0), and solve the resulting set of

linear equations for the three possible values of co by the method of setting the
determinant of the coefficients to zero. Compare your results with the general solution

given by Equation (12-76). One of the solutions is u> = 0. To what values of the «„(0),
and what resulting motion of the particles, does this special solution correspond?

19. Using the general form of Equation (12-81), estimate the temperature dependence of the

thermal conductivity of an insulator at very high temperature (T ^> @ /; ).

In your
discussion give an argument that shows that the relaxation time is inversely proportional
to the number of phonons present in the system.

20. The nuclear magnetic moment of the

!
He nucleus is —1.1 X 10
" (>
J/T. What is the
polarization of
J
He gas in a magnetic field of 1 Tata temperature of 100 K?
21. Find the paramagnetic susceptibility of a spin-1 system at high temperature. The
magnetic energy is — p.Bm with m= 0, + 1.
 T H I R TEEN
SUPERFLUIDS
AND
SUPERCONDUCTORS

Superconductivity and superfluidity are

among the most remarkable forms of bulk behavior in matter. Substances having
these properties can carry currents of electricity or matter with essentially no resis-
tance. Such capabilities are so out of the realm of ordinary experience that when first

observed they were not recognized or were thought to be due to experimental error.
When H. Kamerlingh Onnes succeeded in liquifying helium in 1908 it became
possible to observe these effects. Soon after he reached the liquification temperature of
4.2 K, Kamerlingh Onnes was able to cool this very light and transparent material
below 2.2 K, the transition temperature to the superfluid state. He must have observed
the cessation of boiling, the most apparent signal that this new state of matter has
been reached. And yet he made no mention of the effect. It was not until 25 years
later that a comment about it finally appeared in the literature. Soon, other strange
properties were discovered, some by Kamerlingh Onnes, but most by other workers.
Kamerlingh Onnes used helium as a refrigerant in order to study a variety of
substances at very low temperatures. In examining mercury in 1911 he found that its
electrical resistance disappeared around 4 K. Although he first assumed that the result
was an experimental error, he was able to find the effect in other substances and
coined the term superconductivity to describe it.

Superconductivity occurs in many different metals and alloys. Transitions to the

superconducting state are normally found to occur at temperatures as high as about

20 K and as low as several millidegrees. The recent discovery of a series of alloys with
transition temperatures and above 100 K may lead to some very important
up to
practical applications of this phenomenon. Superfluidity, on the other hand, occurs
only in the two isotopes of helium; in 4 He, the onset is at 2.2 K, while it does not occur
3
in He until 2 mK.
There a variety of phenomena associated with these two states of matter besides
is

the supercurrents. All these effects are now understood to some degree. For superfluid
helium, there is an excellent phenomenological theory, known as the two-fluid model,

634
 13-1 Experiments I Characteristics of Super fluids 635

that successfully correlates many of the properties. Nevertheless, despite a large

amount of excellent no comprehensive microscopic
and fundamental work, there is

4
theory of superfluid He as there is for the superconducting state. While a two-fluid

model of a superconductor was used with some success for many years, in 1956 a
microscopic theory was finally put forward by Bardeen, L. N. Cooper, and J. R.
Schrieffer. This explanation, known as the BCS theory, gave such good agreement
with experiment that it was felt that the problem of superconductivity was solved.
Liquid
3
becomes a superfluid around 2 mK, as discovered by D. D.
He also
Osheroff, R. C. Richardson, and D. M. Lee in 1972. Despite the fact that this atom is
an isotope of helium carrying no charge, the transition in this case is much more like
4
that in superconductors than in He. Because much of the theory existed before the
experimental discovery, we now have a rather complete picture of this material.
Superconducting and superfluid systems are properly treated together in the same
chapter because of their many similarities. Both involve phase transitions to rather
special ordered states that allow friction-free flow. In neither case is the order a spatial
one as in a crystal; the substance remains a fluid. (The "fluid" is a gas of electrons in
the case of a superconductor.) Both transitions are macroscopic manifestations of the
laws ofquantum mechanics, and in each case particle statistics, Fermi or Bose, plays a
Both phenomena reveal themselves at low temperatures because then the
crucial role.
thermal de Broglie wavelength becomes large enough to make quantum and statistical
effects evident.

13-1 Experimental Characteristics of Superfluids

4
The properties of liquid He that we describe in this section are unique to the
substance. The reason for this is not that the fundamental causes are absent in other
substances. It is mainly that every other material freezes at a temperature higher than
the transition point to the superfluid state. Despite the seemingly wide variety of
effects that we describe here, all are shown to be closely related.
4
In the introduction we have noted one characteristic of liquid He below the
superfluid transition — namely, the cessation of boiling. In normal liquid helium and
in other liquids, local hot spots cause bubbles of vapor to be formed. Below the
superfluid transition temperature of 2.17 K, the heat conductivity of the liquid
becomes so large that the hot spots necessary for the formation of the bubbles of
boiling cannot occur. Under the proper conditions the thermal conductivity of the
superfluid can be as large as 2000 times that of copper at room temperature. A drop
in temperature of only 1 K in going from the normal liquid to the superfluid state
leads to an increase in conductivity by a factor of several million.
As the temperature is lowered in any liquid, we expect to reach the solidification
point. This is true in all substances except helium. The condensed phases of both
helium isotopes remain liquids all the way to absolute zero. The only way to make
solid helium is to pressurize either of the two liquids. At very low temperature, solid
4
He finally forms at 25 atm, and solid 3
He around 30 atm. A diagram showing the
4
phases of He is given in Figure 13-1.
Helium atoms
interact with a potential energy approximately described by the
Lennard-Jones function. Equation (10-36). The strength of the interaction (as mea-
sured by the well-depth value e/k B =10 K) is very small compared to other
substances. Also the mass of the helium atom is so small that quantum zero-point
motion is large. If the separation between atoms is a, the lowest energy of a particle is

of order E ~ tr /ma
2
, the result of considering the lowest level of a particle in a box.
636 Superfluids and Superconductors

Figure 13-1 Figure 13-2

Phase diagram of 4 He. Lowering the Specific heat of liquid He. The transition
temperature at atmospheric pressure (along temperature is called the X-point because of
the dotted line) takes the system from gas to the shape of the curve. At low pressure 7\
normal liquid to superfluid. For temperatures occurs at 2.17 K and decreases slightly at
above the critical point, liquid and gas are higher pressure.
indistinguishable. The solid does not form, C
even at T= K, until a pressure of 25 atm is

applied. The line separating normal fluid from

superfluid is known as the X-line.

Critical point

This energy is so large in helium compared to the potential energy that it melts the
solid at low pressure. When enough pressure is applied the potential energy grows
faster than this kinetic energy until the material is finally able to solidify.
When the normal fluid is cooled through the transition at 2.17 K, the specific heat
has a spectacular increase as shown in Figure 13-2. Because of the shape of the curve
the transition temperature to the superfluid is known as the X-pomt. The peak has
been studied in great detail and is thought to become infinitely high if the number of
atoms in the system is infinite. The transition is of second order since there is no latent
heat. At low temperatures the curve shows aT 3
dependence that is characteristic of
phonon systems. We know from Chapter 1 1 that the specific heat of solids depends on
temperature in this way. At somewhat higher temperatures, an extra exp( — A/k B T)
behavior is observed, a form characteristic of an excitation spectrum with a gap A, as
discussed in Problem 9 in Chapter 11.

As mentioned above, the superfluid has a very high thermal conductivity. There is

yet another closely related peculiarity; heat can flow in the form of a wave known as
second sound. Under normal conditions heat diffuses; it moves away from a hot spot
much like molecules spreading away from an open bottle of perfume. However, in
superfluid helium, a pulsed heater causes a temperature pulse to travel, largely
undistorted, across the container where it can be detected by a thermometer. A heater
that is cycled sinusoidally produces a sinusoidal temperature wave that travels across
the liquid.
The viscosity of a liquid is related to its resistance to flow. One of the standard
ways of measuring this quantity is with a torsion oscillator made up of a plate
suspended by a thin rod. As the plate oscillates about the rod axis it drags along any
viscous fluid; the rate of damping is easily related to the viscosity. This technique
applied to helium shows that the viscosity just below the X-point is about the same as
above, although it then apparently decreases toward zero as the temperature is

lowered toward zero.

 131 Experimental Characteristics ol Super fluids 637

On the other hand, experimenters using very narrow channels, such as those in very
have found that above 2.17 K the fluid is unable to flow through, while at
fine filters,
any temperature below the A transition the liquid pours through as if the viscosity
were zero. This extraordinary flow property is one of the main reasons for applying
the name "superfluid" to this substance. Narrow channels that allow superfluids, but
not normal liquids, to pass through are known as superleaks. If the flow velocity
exceeds a critical velocity v
c,
viscous drag occurs.
The two kinds of viscosity experiments seem at first sight to be quite irreconcilable,
with one showing a viscosity and the other showing none at all. Nevertheless, we see in
Section 13-5 how the two-fluid model nicely explains the problem.
When helium is in a container, the vapor above the liquid coats the walls with a
thin film that is usually several atomic layers thick. This in itself is not unusual and
occurs for any enclosed liquid. However, the superfluid film shows some unique
properties. If a breaker holding some of the liquid is raised above the general liquid
level, fluid travels via the film flow over the edge of the beaker, accumulates in drops
on the bottom, and then drips back into the main body of liquid. This continues until
the beaker is empty. This creeping film has, in effect, siphoned the bulk liquid out of the
small container.
The film can be used for another experiment that shows the amazing flow
properties of the superfluid. Suppose the film coats a ring of glass. The film can be
made to flow continuously around the ring. Once the flow has started it continues
without dissipation indefinitely. Similarly, bulk fluid made to rotate by spinning a
bucket continues to flow without friction. Such friction-free flow patterns are known as
persistent currents.

The thermomechamcal effect involves two containers of helium connected by a

superleak as seen in Figure 13-3. If one side is heated slightly the liquid level on that
side rises at the expense of the liquid in the other container. It is possible to set up an
arrangement such that the heating causes a thin stream of liquid to spray upward,
giving rise to the term fountain effect.
We attempt in Section 13-5 to give brief explanations for each of these phenomena
in terms of the two-fluid model or by more microscopic theories. Before entering into
those explanations, we examine the range of peculiar effects found in superconductors.

Figure 13-3

Thermomechanical or fountain effect. Turning

on the heater on the right causes the liquid
level on that side to rise while the other side
falls.

Heater

Superleak
638 Super fluids and Superconductors

13-2 Experimental Characteristics of Superconductors

Like superfluids, superconductors show a variety of effects. Unlike superfluids, which

involve neutral atoms, they are characterized by an array of electromagnetic phenom-
ena because electrons are the basic entities involved. The first effect, as observed by
Kamerlingh Onnes, is the sudden drop of the electrical resistivity to zero at the
transition point. Electrical currents can then be set up with no internal electric field in
the metal. Furthermore, a persistent current can be established in a loop conductor.
Suppose that a piece of superconductor is placed in a magnetic field and the
temperature lowered below the transition temperature T.. The magnetic field is
excluded from the interior of the material as illustrated in Figure 13-4. It does this by
setting up surface currents that establish an opposing magnetization canceling the
interior field. The superconductor is a perfect diamagnet. The exclusion of the field is

called the Meissner effect after the work of F. W. Meissner and R. Ochsenfeld.
If the external field is increased, superconductivity is destroyed at a critical fie Id Bc
.

Excluding the field has cost the superconductor an energy per unit volume equal to
the energy density of the excluded magnetic field 5 2 /2ju , where ju is the permeabil-
ity of the vacuum. When this energy exceeds the difference in energy between normal
and superconducting states, the system reverts back to the normal state. An amazing
~8
feature is how small this energy turns out to be, only 10 eV per atom. Consider-
ing that the various energies involving electronic interactions are all around
1 eV, including some that are not so accurately calculated, we might think it hopeless
to explain such a small effect. Fortunately, it is not.
Like helium, superconductors have a specific heat increase at the transition
temperature. However, the peak in superconductors is a finite jump as we see in
Figure 13-5. At low T the specific heat falls below the linear dependence of a
degenerate Fermi gas and is proportional to exp( — constant/ 7"). Such a dependence
is, like the situation in the superfluid, characteristic of a spectrum with a gap. If the
superconductor is placed in a magnetic field with B> B (
, the specific heat reverts to
its normal linear behavior.
Another indication of the existence of a gap in the energy spectrum is given by
absorption of radiation. A superconductor reflects radiation of frequency less than
some critical value lying in the far infrared. Radiation above that frequency is

Figure 13-4

Meissner effect, (a) An external magnetic field

penetrates a sphere of superconducting
Figure 13-5
material at T> T.(b) When the temperature
Specific heat of a superconductor. The curve
is lowered below T the field is expelled from
shows a jump at the transition
finite
the interior of the sphere.
temperature Tc The exponentially decreasing
.

heat capacity drops below the linear behavior

of the normal state at low temperatures.

(a)
 13-2 Experimental Characteristics of Superconductors 639

absorbed. If there is a gap in the electronic energy spectrum, an electron cannot

accept energy unless the light is able to give it a sufficient amount to overcome the
gap-
A seemingly minor property that was crucial in unraveling the mystery of
superconductivity is the isotope effect. The critical temperature for a set of metals, each

of which is made up of one isotope of the same element, depends on the atomic mass
M of the isotope according to

T. ~ AT",

where a is often about i. The Debye temperature of a substance is also proportional

to M~ 1
/ 2 ascan be determined from several of the formulas of Chapter 11. This led
theorists to the suggestion that the interaction of electrons with the phonons might
have something to do with superconductivity.
Another indication along these same lines is that normal systems such as copper
and silver, that are good conductors of heat and electricity, generally become
superconductors only at very low temperatures or not at all. Poor normal conductors,
such as tin, lead, and alloys, readily become superconductors. We know that the
resistivity of a metal depends on the interaction of the electrons with phonons.

The seeming flaw in this argument is that the superconducting transition tempera-
ture is generally orders of magnitude lower than the Debye temperature. Nevertheless,
we see that an effective force between electrons caused by lattice vibrations acting as
intermediary is indeed basic to the occurrence of superconductivity.
One of the most exciting periods in the history of condensed matter physics began
in late 1986 and continues to the present: high-temperature superconductivity has been
discovered in certain oxides. In order to keep up with fast-breaking advances in the
subject physicists have had to read current news releases as well as physics journals. At
present, the highest critical temperature liesabove 100 K and occurs in materials
having a layered structure containing planes of copper and oxygen atoms. Such high
transition temperatures are technologically remarkable because they can be reached
easily and cheaply by using liquid nitrogen, at 77 K, rather than liquid helium at 4 K.
This opens the door to a myriad of applications. Room-temperature superconductivity
is by no means out of the question.

Example

The critical magnetic field of aluminum is B =

c
0.01 T. The magnetic energy
density corresponding to this is

2
(0 01 T)
= 40 J/ m3 .

2fi j 2(477 X 10" 7 N/A2 )

28
Because the density of aluminum is 6 X 10 atoms/m 3 ,
this becomes

40 J/m3
28
= 4 < 10" 9
eV/atom
(6 X 10 atoms/m3 )(l.6 > 10- 19
j/eV)
640 Super fluids and Superconductors

Example

We list a table of elements along with their superconducting transition tempera-

tures T c
and their normal-state electrical resistivities. Note that there is a
relation, although not a perfect correlation, between high and high Tc
resistivity .

~4
Element rc
(K) Resistivity ( 10 Q / m)
Ag — 1.6

Cu — 1.7

Au — 2.4

Mo 0.9 5.7

Ga 1.1 17.4

Al 1.2 2.8

Sn 3.7 11.5

Ta 4.4 15.5

Pb 7.2 22.0

Nb 9.2 12.5

Prior to the discovery of the very-high-temperature superconducting oxide

materials the highest recorded transition temperature had for many years been
23 K in an alloy.

13-3 Superflow and the Energy Gap

We have noted in Sections 13-1 and 13-2 how certain experimental data, including
the specific heats of both superfluid helium and superconductors, indicate the ex-
istence of an energy gap in the energy spectra of each of these substances. Such an
energy gap leads to the possibility of friction-free flow and persistent currents.
The explanation is basically quite simple. Suppose we consider a sphere moving
with velocity v through a fluid. The sphere feels a drag when immersed in a normal
fluid. This is equivalent, by the principle of Galilean relativity, to the typical
experimental situation in which the fluid flows with friction at velocity —v past some
stationary object, in this case the sphere. The frictional forces arise from the transfer of
energy from the moving sphere to the liquid. When there is a gap in the spectrum,
then, for sufficiently small velocities, no energy can be transferred — because there are
—
no fluid states available and we have a superfluid. For sufficiently large velocities,
enough energy can be transferred to the liquid that the gap can be surmounted. Then
frictional forces are felt by the sphere.
In superfluid flow the walls of the channel through which the helium flows, or other
obstacles, play the role of the sphere. For superconductors phonons and impurity
atoms can cause drag on the electron fluid.
To make the issue more quantitative, we use a discussion similar to one by L. D.
Landau. Denote the energy excitations of the fluid by e^ as a function of momentum
p. (In a gas of free particles we have, of course, e^ = p /2m; we consider other
2

functional forms as well.) Let the mass of the sphere be M. When the sphere causes an
excitation, its velocity changes to v' and the liquid absorbs energy e and momentum
p
 13-3 Super/low and the Energy Gap 64

p. Conservation of momentum and energy give

My = My' + p (13-la)

and

\Mv 2 = \Mv' 2 + e
p ,
(13-lb)

where v' is the final sphere velocity. Solving Equation (13-la) for v' and substituting
into Equation (13-lb), we obtain

2
P
e„ + v •
p =
H 0.
" 2M
Since M is a macroscopic mass the second term is negligible and

vp = e, (13-2)

is The question then becomes whether

the condition for the excitation to take place.
there is and a corresponding value of e p such that Equation (13-2) is
a value of p
satisfied for the given value of v. If so, energy and momentum can be transferred to

the fluid, which is then viscous. If Equation (13-2) cannot be satisfied, the excitation
does not occur and the sphere moves through the fluid without friction.
With the cosine of the angle between v and p, frictional flow requires that
jti

i>ii= —. (13-3)

The quantity e
p /p
is a characteristic of the fluid and, since it is always positive, takes
on values extending from some minimum Suppose the minimum value is to infinity.
larger than zero. Then, if v\i is smaller than this minimum, Equation (13-3) cannot be

satisfied and no excitation of the fluid can take place. With ju set at its largest value,
namely unity, there is some smallest value of v, call it vc for which there can be an ,

excitation of the fluid. This critical velocity is given by

vc = minimum of — . (13-4)

For e = p 1 /2m, this gives

P
vc = minimum or(( \ ,

\ 2m I

which, of course, is zero for p = 0.That is, a normal gas of free particles is not a
superfluid; excitations can be created at any velocity.
Suppose, however, that there is a gap in the spectrum. For example, suppose

A
P
"
2m'
642 Superfluids and Superconductors

Figure 13-6 Figure 13-7

Excitation spectrum with a gap. The system Excitation spectrum for superfluid He. At
behaves as a superfluid at velocities less than small momenta the curve is linear,
the critical velocity, which is given by the corresponding to phonon excitations. The
slope of the line through the origin tangent to sound velocity is denoted by cs . At larger
the curve. momenta there is a minimum with gap A.
G, The excitations here are called rotons. The
dotted line shows the critical velocity-

construction.

where A is a constant. Then the minimum of t /p

p
is easily seen to be

2A

In general, the minimum of e

p /p satisfies

2
P dp P
>i\

de
p
V (13-5)
" dp

Figure 13-6 shows a hypothetical curve of e versus p. Equation (13-5) is the equation
p
of a straight line passing through the origin and yet somewhere tangent to the
excitation curve as indicated by the dotted line in the figure. The critical velocity vc is

the slope of this tangent line.

There is no need for the lowest energy of the excitation spectrum z to occur at

p = as it does in Figure 13-6. Indeed, the actual excitation spectrum of superfluid

helium has its gap at finite p as shown in Figure 13-7. The spectrum has a linear
region in which e = c p, where cs is a constant, followed by a minimum at an energy
p s

A. Despite the existence of states between zero and A, the tangent construction still
gives a nonzero critical velocity. The linear region of the spectrum is typical of a
phonon spectrum with cs the sound velocity, as we have seen in our discussion of solids
in Chapter 12. Why there are phonons and no single free-particle modes is fundamen-
tal to understanding the nature of superfluidity and is discussed in Section 13-5. The

excitations in the region of the minimum of £

p
are called rotons.
 13-4 The Bose- Einstein Condensation 643

For superconductors the excitation spectrum has the form

A2 + {p 2 /2mY

This form looks much like that shown in Figure 13-6. There is obviously a nonzero
critical velocity.

Example

The excitation spectrum of helium shown in Figure 13-7 has the parameter
valuesA/k B = 8.65 K and p /h = 19 nm The sound '. velocity is cs = 238
m/s. The critical velocity is then approximately

A (8.65 K)( 1.38 X 10~ 23 J/K)

~p~
= 60 m/s.
" X 34 9
m')
(1.05 10 J -s)(19 X 10

This critical velocity is rarely observed in actual experiments. Much lower

values, on the order of a few centimeters per second, are usually found. The
reason is that there is another kind of excitation, the vortex, that can be created
at these low velocities. The statistical weight of these vortex excitations is so
small that they do not contribute to the specific heat and Landau was not aware
of their existence when he presented his criterion for superfluidity.

13-4 The Bose - Einstein Condensation

As mentioned in the introduction, superfluids and superconductors have the common

feature that there is some kind of condensation to a new form of order at the transition
temperature. Furthermore, this new order is not spatial as in the liquid -solid
transition. What other kind of order is there? As we demonstrate in this section, at

least one other kind of order can occur — in momentum space. The Bose-Einstein
condensation of an ideal gas involves a sudden collapse of a macroscopic number of
particles into the lowest single-particle momentum state.

The system to be considered here is a collection of N noninteracting Bose particles.

We discuss such a system because it is an easily solvable model showing this peculiar
momentum condensation. We do not suggest it as an explicit model either for
superfluid helium or for superconductors; unfortunately, things are not so simple in
either case. Nevertheless, in the 1930s, London drew attention to this condensation of
Bose particles that had been discovered by Einstein and, in a series of papers and in a
book, he showed how certain analogies between the ideal Bose gas and the phenomena
in liquid helium could be used to understand the latter. Landau, who approached
superfluidity from a different point of view, including the use of the ideas presented in
Section 13-3, disagreed strongly. London eventually won the argument and we
attempt later to show qualitatively how the two views may be reconciled.
Chapter 11, Equation (11-26), tells us that the Lagrange multiplier a and the
number of particles in a Bose system are related according to

N=I t
n (l ,
13-6)
644 Superfluids and Superconductors

and
= (,*,+« - I)"
1

. (13-7)

The expression for n

p
,
the number of particles having momentum p, differs from the
similar one for fermions by only the minus sign in the denominator; but what a
difference a sign makes!
Let us first consider the occupation number n corresponding to the lowest
single-particle energy e (which is zero if we use traveling-wave boundary conditions).
We have

« = (e*- 1)"'. (13-8)

Obviously, we must have a > so that n is finite and positive for bosons. (Recall
that for fermions at low temperatures a is negative since it is proportional to minus
the Fermi energy.) If a is very small, and in particular if a = a/N, where a is a
number of order unity, a Taylor series expansion of the exponential shows that

A"

That is, the number of particles in the lowest allowed state of energy and momentum

can be a substantial fraction of the entire set of particles. Bosons, as we have shown
previously in Chapter 1 do not avoid one another like fermions; they actively prefer
1 ,

to be in the same state. What we are going to show is that, while for high temperatures
n is no larger than any other occupation number, when we lower the temperature

below a value Tc a becomes of order jV~ and the lowest state fills until it contains a
,
'

substantial fraction of the total set of particles. We then have had a transition to a
phase that is partially or, at T = K, completely condensed into the zero-momentum
state.

It is easy to show that n for any state other than the ground state, is very much
smaller than n . This is true even for the first excited state as shown in Problem 3 at
is

the end of the chapter. Although any individual n is small compared to « the sum ,

of all of them is certainly of order N for any value of a.

Thus, for all values of a we can segregate the sum into two parts:

N= n + £'n,,
P

where the prime on the sum means that we omit the ground state. Since, in the sum,
no single state is significantly larger than the rest, it is possible to change from the sum
into an integral by using the standard technique of the density of states function. (It is
always a good approximation to change a sum into an integral if the summand does
not vary much from one term to the next. This is the case once we remove « This .

process is clarified in Problem 3.)

By using the function D(e) of Equation (11-44), we have

£ ••• -> / deD(e) = AV dee l/2

where V is the volume of the system and the constant A is defined by

 13-4 The Base- Einstein Condensation 545

We can then write

/•OO

N=n + AV
•'n
dee l/2 (e fic
+a
I)"
1
-

Next, define the new variable

z = fie

so that

/2
N= n + AV(k B Tf G(a), (13-9)

where
+a - l)~\
G(a) = (™ dzz^2 {e* (13-10)
Jo

For very large a it is easy to show that this integral becomes

G(a) -—<-". (13-11)

For a = the integral can also be evaluated. It can be shown that

V7T
G(0) = 2.612. (13-12)

When a is of order l/N, it is so small that G(a) is essentially equal to G(0) in

Equation (13-12). In this case Equation (13-9) gives

,,, fr
nQ = N-AV{k B TY"—
3/
2.612 (13-13)

ut

3/2

« = iV (13-14)

where

J !

_'.V 277^'- i

rs (13-15)
A-
fi \ ^^(2.612) kBm \ 2.612

with p the density N/V.

The behavior of n /N as a function of temperature is given by Equation (13-14) as
shown in Figure 13-8. At T= K, n = N; all the particles are in the ground state as
we might expect. However, the surprising feature is that, as the equation and the
figure show, the number ground state remains macroscopic (of order N all the
in the )

way up to a certain temperature T. At that point n becomes small and is no larger

than the rest of the terms in the sum. Then the solution, Equation (13-14), which is
based on the assumption that a is of order l/N, is no longer valid, and we need to
646 Superfluids and Superconductors

Figure 13-8 Figure 13-9

Occupation number n for the lowest energy Plot of the Lagrange multiplier a for an ideal
state of the ideal Bose gas. At T= K, Bose gas. This quantity is of order \/N below
n = N; macroscopic occupation continues up T {
but takes on values of order unity above
to a critical temperature Tc
. Above T, n is that temperature. The discontinuous nature of
negligible compared to the total number of its behavior in the limit of an infinite system
particles and is shown as zero in the figure. is characteristic of a phase transition.

solve for a by using

3/2.
N= AV(k B T) ^G(a)

Here, we have used the fact that n Q is very small (of order 1) and have dropped it

from Equation (13-9). The reader is asked to show in Problem 5 at the end of the
chapter that the result for very large a is just the classical high-temperature, or ideal
gas, case (equivalent to that of Equation (11-30)).
Figure 13-9 shows how a behaves over the entire temperature range. The im-
portant point is that it has a discontinuity (in first derivative) at Tc
. This is a sign that
a phase transition occurs at this temperature. As the temperature is lowered through
T c , the transition is one in which particles begin cascading into the zero-momentum
state. This is the Bose-Einstein condensation. It is an ordering in momentum space
and not in real space.
Other thermodynamic quantities of this ideal Bose gas system have discontinuities
at T(
. The specific heat C/N is shown in Figure 13-10. At the transition C has a cusp
of finite height. The temperature dependence of this quantity below Tc
is T ' .

If we put in the parameters appropriate to helium, as we do in the example below,

we find Tc = 3.1 K, which is quite close to the superfluid transition temperature of 2.2
K. While the Bose-Einstein condensation may be an appealing model for the
behavior of liquid helium, there are a number of reasons why things cannot be so
simple. First of all, a lot of details are not right. For example, the specific heat is finite

at the transition and is proportional to T 3/2 below it; the specific heat of helium has
an infinite peak at 7\ and is proportional to T s
at low temperature. The ideal Bose
transition is of first order — since it has a latent heat — rather than second order as in
helium.
More importantly, the ideal Bose gas does not exhibit superfluidity. The spectrum
of excitations depends quadratically on momentum corresponding to free particles. As
we have seen in Section 13-3, this gives a zero critical velocity.

The atoms in helium are constantly interacting with one another and certainly
cannot be considered an ideal Bose gas. It is impossible that n could ever be equal to
 / 3-5 The Two-Fluid Model of Superlluid Helium 647

Figure 13-10

Specific heat of the ideal Bose gas. C is finite

at T c
but has a discontinuous derivative. At
low T, C is proportional to T 3/2 . It

approaches the classical value ZNk B /2 at very

high temperature.

N, even at T = K. The wave function corresponding to all particles in the

zero-momentum state is a constant as a function of all the particle coordinates. (For
one particle, we have exp(*p r/h) = 1 for p = 0.) However, because of the highly
•

repulsive core of the potential energy curve, we know that the wave function for liquid
helium cannot be a constant but must vanish whenever any two particles approach
too closely. Nevertheless, it is possible to have a partial Bose condensation into the
zero-momentum state in liquid helium. Theoretical calculations predict that n /N «
0.1 at absolute zero. Experiments to detect n are very difficult and have often been
controversial; however, recent results tend to confirm the theory.
Although the ideal Bose gas is not a good model for liquid helium, the Bose nature
of the helium atom and the presence of a condensation are thought to be responsible
for the characteristic behavior of the superfluid. We discuss this point more fully in

Section 13-5.

Example

For the atomic mass and density of helium, Equation (13-15) gives the Bose
condensation temperature as

2w(l.05 X 10~ 34 J •
s)" 2.2 x 107m 3 \ 2/3

-23 -27 3.1 K.

(1.38 x 10 J/K)(6.65 X 10 kg) 2.61

13-5 The Two-Fluid Model of Superfluid Helium

While liquid helium cannot be described as an ideal Bose gas, it is commonly believed
that the Bose character of the helium atoms is fundamental to the nature of the
superfluid state. Although there is as yet no truly comprehensive microscopic theory of
helium, numerous theoretical calculations have indicated how important it is to
include Bose statistics in the description. We describe briefly and qualitatively some of
the approaches that have been used. Unfortunately, most of the details of these
theories are beyond the level of this text; however, there is a less fundamental
648 Super fluids and Superconductors

phenomenological description, the which correlates many features of

two-Jluid model,
the data. We try to explain the basis of the model and then show how it makes sense
out of the experiments discussed in Section 13-2.
While Landau disputed the view that the Bose condensation was vital to the nature
of the superfluid, his countryman N. N. Bogoliubov was able to prove a very
fundamental result that supports the view quite strongly.- He showed that if a weak
interaction is turned on in a previously noninteracting Bose gas, the spectrum of
excitations changes from the quadratic free-particle behavior (e = p 2 /2m) to linear
p
for small momenta. The linear spectrum, e = c p, is just that of sound waves similar
p s

to those appearing in the small-momentum region of the plot in Figure 13-7. This
behavior is what allows a nonzero critical velocity so that superfluidity can occur
according to the Landau argument of Section 13-3. Weak interactions and the
existence of a large condensate are essential to the Bogoliubov approach so that this
theory, while very suggestive, is not directly applicable to helium either.
It is perhaps not too hard to understand qualitatively why the single-particle
<x< itations, which would destroy superfluidity, are no longer present in the interacting
Base gas. Bosons prefer being in the same state with one another, so that if one atom is
pushed on by an external force, all the particles within a de Broglie wavelength A
(which is large at low temperature) want to move in the same way. The collective
motion of a sound wave allows this while the single-particle motions are frozen out by
this tendency.
R. P. Feynman was He showed on the basis of mathemati-
able to go even further.
cal as well as physical arguments that helium should have a phonon spectrum and
moreover that the roton spectrum, the region of the minimum in Figure 13-7, is just a
natural continuation of the phonon part. The excitations in the phonon region are
longitudinal compressional waves, but the rotons are pictured as mini-vortices. The
wavelength X = h/p corresponding to a roton is small, about 0.3 nm, which is

approximately the average interparticle distance. Thus, a roton very likely involves a
small number of particles. One model has them moving in a way somewhat analogous
to a microscopicsmoke ring. Feynman's calculations of the spectrum are in good
agreement with experiment and so this aspect of helium is thought to be well
understood.
Superfluid helium is condensed into an ordered state in momentum space although
we have shown that it cannot be a state with nil particles in the lowest single-particle
level even at 7=0K. However, at absolute zero the entire system is certainly in its

many-particle ground state and is a perfect superfluid. Any experiment to measure

viscosity finds it to be zero as long as the critical velocity is not exceeded.
At T> K phonons and rotons are excited. Any one of these excitations is not
separated by a gap from other excitations of the liquid. It can collide with the walls
and deposit energy or take up energy and thereby cause friction. At low temperatures
this "gas" of phonons and rotons is not very dense and many of the superfluid

properties remain. In fact, it is reasonable to think of helium, when it is below 7\, as a

mixture of two fluids, one a perfect superfluid and the other a normal fluid. The normal
fluid, composed of the gas of excitations, has viscous flow and carries heat. The

superfluid is nonviscous and carries no heat. The percentage of superfluid present goes
from 100% at T = K to 0% at and above Tx .

The two kinds of viscosity experiments mentioned in Section 13-1 are now easily-

understood. The torsion oscillator experiment actually measures not simply viscosity
but the product of density and viscosity. As the plates oscillate in the fluid they feel no

friction from the superfluid component but the normal fluid has density p„, which
 / 3-5 The Two-Fluid Model of Superlluid Helium 649

Figure 13-11
4
Superfluid density p of liquid He as a
%

function of temperature. At T = K, p is (

equal to the total density and drops to zero at

exerts a drag and is carried along as the plates oscillate. This drag diminishes as the
temperature is lowered because the normal density decreases; the result is an apparent
decrease in fluid viscosity. By a slight modification of the torsion oscillator experiment,
the Russian physicist E. L. Andronikashvili was able in 1946 to measure directly the
normal density p n The superfluid density is
. given by p = p — i p„, where p is the total
and can be plotted as shown in Figure 13-11.
density,
Two misconceptions must be avoided here. First, despite the similarity between the
curve for ps in Figure 13-11 and that for n in Figure 13-8, the two quantities are
quite different. Recall that at T= K perhaps only 10% of the particles in real

helium are condensed into the zero-momentum state, and not 100% as in the ideal gas
of Figure 13-8; however, the entire helium system is superfluid then, so that p = p.
s

Second, it is incorrect to think of the superfluid and the normal fluid as made up of
two different sets of atoms. Because a phonon is a collective motion, it involves many
atoms throughout the liquid, and these same atoms can also be involved in the
superfluid component.
The second kind of viscosity experiment discussed in Section 13-1 involves flow
through a small channel known as a superleak. The superleak is so small that the
normal fluid is almost unable to move through the channel; however, the superfluid
flows readily. Since almost everything that gets through is superfluid, this measure-
ment of viscosity gives zero. Normal fluid carries the heat and is largely left behind.
This fluid is now and shows an increase in temperature if the
deficient in superfluid
entire system is not maintained at a given value by the external refrigerator. Because
of the removal of the excess heat, some of the normal fluid is quickly converted to
superfluid, which then flows through the superleak. The observer gets the impression
that none of the liquid has viscosity.
The thermomechanical effect also involves having a superleak that allows the
superfluid through but not the normal fluid. When the heater in the chamber on the
right side of Figure 13-3 is turned on, the rise in temperature creates normal fluid at
the expense of the superfluid on that side. There is then a mismatch of superfluid
concentrations on the two sides of the apparatus. This is as though a gas is on the left
at a certain pressure and a partial vacuum of the same gas is on the right. Superfluid
flows through the superleak from left to right. There is also a mismatch in concentra-
tions of normal fluids on the two sides, but since normal fluid cannot readily flow
650 Superfluids and Superconductors

through the channel, it remains out of equilibrium. The result is an accumulation of

the total amount of extra fluid on the right as shown in the figure. We have used heat
to pump superfluid from one side of the system to the other!
The creeping film can also be explained as a kind of superleak. The vapor of any
fluid coats the inside walls of the container and those of any other vessel inside. The
normal fluid is clamped to the wall, but, because the -superfluid component moves
without friction, the film can act as a siphon, which can, for example, empty a small
beaker held above the level of the main liquid reservoir.
The peculiarities of heat conduction can also be analyzed on the basis of the
two-fluid model. In this system heat travels mainly by convection. The normal fluid
and superfluid can move relative to one another. Normal fluid readily flows away
from a hot spot carrying heat with it, while the superfluid flows toward the hot spot so
that the overall mass density remains unchanged. The fact that the superfluid
backflow carries no heat makes this an efficient technique. Since the normal fluid is
made up of the gas of excitations, we can look at this process as a drift or streaming of
this gas.
As ordinary sound corresponds to variations in the overall density of a fluid, second
sound is a density wave in the gas of the phonon-roton excitations. When the density
of excitations is larger than average, there is an excess of normal fluid and the
temperature is a bit higher there. WTiere the density is lower, the temperature is lower.
In this way second sound is a temperature wave. The overall density of the fluid is a
constant everywhere; this is maintained by having normal and superfluid densities
oscillating exactly 180° out of phase.
Since phonons exist in solids as well as in liquid helium, we might expect that
second sound could be found there. In most situations second sound in solids is so
highly damped out by various mechanisms that it does not occur. However, it has
been observed in certain specially prepared samples.
We have now seen, at least qualitatively, how some of the phenomena of super-
fluidity can be interpreted. In Section 13-6 we try to do the same thing for
superconductivity.

13-6 Cooper Pairs and the BCS Theory

The microscopic theory of superconductivity developed by Bardeen, Cooper, and

Schrieffer has been remarkably successful. Its good agreement with experiment has
caused the general opinion that superconductivity is a well-understood phenomenon.
Since the theory is quite advanced and mathematically complex, our treatment is
limited to a simple description of some of the theoretical results.
Cooper made the preliminary discovery that electrons can form bound pairs when
there is an attractive interaction between them. It was this result that stimulated the
further work that led to the full theory. It may be rather surprising that an attractive
interaction can occur between electrons when we know that two isolated electrons
always feel a repulsive Coulomb force. The attractive force arises because the electrons
are in a crystal lattice.

As the electron passes through the lattice it attracts the neighboring positive ions
toward it. Another electron nearby sees the positive grouping and is attracted to it.
The resulting attraction can even overcome the bare electron -electron Coulomb
repulsion so that the net interaction is attractive.
There is an equivalent alternative view of this interaction. When an electron passes
by a positive ion core it interacts with it via the Coulomb interaction and can set the
 13-6 Cooper Pairs and the BCS Theory 651

Figure 13-12

Interaction of two electrons caused by the

exchange of a phonon through the crystal
lattice. If a pair of electrons with zero total
momentum exchanges a phonon of
momentum q, the final momenta are 1 = p -

q and — respectively.
1,

p +q = -I
I =p -
q

Electron 1 Electron 2

ion vibrating about its site. This in turn sets up lattice waves so that the electron can
be said to have emitted a phonon. The vibrating ions can affect the motion of a second
electron; the second electron absorbs the phonon. A simple diagram representing this
process is drawn in Figure 13-12. As is shown in Chapter 16, analogous diagrams can
be drawn for every force that occurs in nature, especially the fundamental ones like

the Coulomb force. The force that results from phonon exchange is attractive and
allows the formation of bound pairs of electrons.
In order to understand the various terms that occur in the final results we look at
the effective interaction between electrons a bit more closely. Consider the wave
function corresponding to a pair of free particles, the first having momentum p, and
the second momentum p2 . Call it (f». Jr,,^), where r, and r 2 are the coordinates of
the two particles. The total momentum of the system is P = p, + p>, which corre-
sponds moving with a center-of-mass
to the pair velocity through the crystal while
they are orbiting around each other (if indeed we find that they are bound together).
For the moment we can just consider the situation in which the center of mass is at
rest, that is, P = 0, so that p 2 = — p,. The resulting pair wave function can be
represented by the simpler notation

(Of course, Cooper pairs can have P =£ 0; indeed, as we see below the pairs are
responsible for carrying the supercurrent, so such moving states are essential.)
If the effective attractive interaction between the electrons is written as Vn —
F(r,,r 2 ), an important quantity is given by

eP = fjM &P dx \
(13-16)

It turns out that it is this quantity that is actually represented by the diagram in
Figure 13-12. A pair of electrons in momentum state [p] = (p, — p) exchanges a
phonon that carries momentum q. The momentum of the one electron goes from the
652 Super fluids and Superconductors

value p to t= p — q, while the other electron that absorbs the phonon goes from — p
to — p + q = —{. The final pair state is then [f\ = (t, — t) as shown. (Because of V(p ,

the simple momentum state 4> is no longer an eigenfunction. The true eigenfunction is
p
a sum of all the different <£ 's combined in a manner representing a localized bound
state.)
The magnitude of Vf depends on a variety of things. For example, it certainly
depends on the strength of the interaction an electron has with an ion that must be
wiggled to get a phonon excited. Furthermore, we know that the two electrons that are
interacting must be near the Fermi surface. Otherwise, their interaction with one
another does no good. That is, when one electron interacts with another it feels a force
and normally might then change its momentum. However, if it is deep within the
Fermi sphere a small kick has no effect because the electron cannot go anywhere in
momentum space because of the Pauli principle; all the nearby momentum states are
already occupied by other electrons. However, the maximum energy that can be
transferred from one electron pair to another by the phonon exchange interaction is

on the order of the characteristic phonon energy given by

where 0^, is the Debye temperature. Phonon energies are quite small compared to the
Fermi energy; S D is a few hundred kelvins, while TF is of order 10 5 K. Thus, only
electrons very near the top of the Fermi sphere can interact successfully with one
another.
Therefore, we might write

v = I~ F >
e, and e, in the interval [e F , e F + e^]
(13.17)
I 0, otherwise,

where F is a positive constant that represents, among other things, how strongly an
electron is coupled to the ions. The minus sign signifies an attractive potential. This
interaction allows electron pairs to interchange energy with one another only in a very
small band of energies around the Fermi surface.
Cooper put all these ideas together, solved the Schrodinger equation, and found
that therewas a bound state for arbitrarily small F. If E is the pair energy then, when
there is no interaction, we expect E = 2e f since both electrons are at the Fermi
,

surface. A bound state has an E less than this by a bit. The binding energy- can then
be defined as

E = c
2e F - E

and is found, for small F, to be

2 R F
E = (
2e D e- / » ,
(13-18)

where R is the density of particles per unit energy (Equation (12-15)) evaluated at
the Fermi energy e = e F This says that the binding energy can be much smaller than
.

the energy e D transferred in the exchange of a phonon. The possibility of having a

binding energy much smaller than the phonon energy is crucial to the theory of
superconductivity since we have already seen that the transition temperature, which
must be of order Ec is usually two orders of magnitude smaller than the Debye
,

temperature. The exponential factor easily accounts for that size reduction.
 / 3-6 Cooper Pairs and the BCS Theory 653

The BCS theory goes far beyond the consideration of just Cooper's treatment of a
pair of electrons. It takes into account the cooperative nature of the pairing. At T>
K single electrons are thermally excited into momentum states above the Fermi
surface. Because of the Pauli principle, these states are then not available to be
involved in the formation of pair states. As the temperature rises, there is a cooper-
ative blocking of the formation of the bound state causing the binding energy to be
temperature dependent. At some temperature T c,
the binding energy E. goes to zero.
This is the transition temperature for the superconducting state.
In the superconducting system the pairs are in a highly coherent state; the
formation of a few encourages the formation of others in a cooperative way. This
tendency is quite analogous to what happens in a Bose condensation. However, the
average radius of the Cooper pair state is quite huge, on the order of 1 /im. This
means that the centers of approximately a million other Cooper pairs sit inside the
volume encompassed by one of them. While an even number of bound fermions often
behaves like a boson, as in the case of the helium atom, the severe entanglement of the
Cooper pairs implies that we cannot very well think of the superconducting transition
simply as a Bose condensation of Cooper Such a picture would be valid only if
pairs.

the Cooper pair radius were small compared to the average interpair separation.
The BCS theory predicts that the ground state involves many electron pairs
occupying states in the shell of states about the Fermi surface. A single-particle
excitation has an energy (measured relative to this ground state) given by

ep = n+A .

where £ = p /2m and

2
p

which bears a strong resemblance to Equation (13-18) for the Cooper pair binding
energy. When a pair is broken, two electrons are excited so that the smallest energy
involved in an excitation is the energy gap,

1/R " F
2k = 4e D e- . (13-19)

There are no states between the ground state and this energy. However, there is a
continuum of states above this energy. In this way superconductors differ from
superfluids, which have the phonon modes all the way to zero energy.
For T > K, the gap becomes temperature dependent, as we have mentioned
above, and diminishes until it finally reaches zero at T. This transition temperature is
given by

F
kB T = lA4e D e- l/R
c
«
.
(13-20)

In Section 13-2 we have pointed out that the isotope effect hints at T being
proportional to the Debye temperature. From Equation (13-20) we see that this is

indeed the case through £D .

The newly discovered high-temperature (~ 100 K) oxide superconductors dis-

cussed in Section 13-2 may operate by mechanisms quite different from those in the
BCS theory. Alternative theories for the new materials are being examined at the
present time. It can still be said, however, that the BCS theory continues to hold for
superconductors with low transition temperatures.
654 Superfluids and Superconductors

We have now briefly seen a few of the elements of the theory of superconductivity.
In Section 13-7 we take a closer look at the theoretical interpretation of the
experimental data.

Example

The superconducting transition temperature in aluminum is T = 1.2 K. The

Debye temperature is QD = 420 K. With eD = k B€) D , Equation (13-20) allows
an estimate of the dimensionless interaction constant R F. We get

1 1

~
ln(7yi.l40 o ) " ~ ln(l.2K/1.14 X 420 K)
~

A simple form of the BCS theory, the weak-coupling case, gives the results
quoted in this section. This case holds when R F is less than unity, as occurs for
aluminum. The combination of Equations (13-19) and (13-20) gives us a simple
relation between two experimentally measurable quantities, T and the gap 2 A.
We find

2A 4
3.51.
kB T
c
1.14

Experimentally, this ratio is found to range from 2.8 to 4.6. For aluminum
2A/k B is 4.2 K so that the ratio is 3.4.

13-7 Theoretical Interpretation of Superconducting Experiments

In Section 13-3 we have seen how the existence of an energy gap explains superflow in
liquid helium. The condensation of Cooper pairs also provides a spectrum with an
energy gap so that we can discuss nonresistive flow in superconductors in a very
analogous way. (We point out, however, that this argument is not complete and the
question of nonresistive flow and persistent currents is more complicated than we have
indicated. However, we are unable to go into the details here.)
The energy gap, equal to 2 A, also gives rise to the experimentally observed specific
heat dependence, which has roughly the form exp( — A/k B T) below T The theoreti- (
.

cal values of A give good agreement with the experimental results from specific heat
and radiation absorption experiments.
Because a magnetic field above a critical value B(
can destroy superconductivity,
the energy density of the critical field, given by the value B 2 /2jx
c , must represent the
difference W Q in energy densities between normal and superconducting states. It is

easy to calculate the value of this in terms of the energy gap. We make use of methods
similar to those used in Chapter 12. Since the pairing involves electrons in a thin shell
of states at the Fermi surface, the density of pairs is one-half the number R of
particles per unit volume per unit energy interval times the width of the energy shell,
given by the gap parameter A, or

/? A
pair density =
 / 3-7 Theoretical Interpretation of Superconducting Experiments 655

In the superconducting state, each of the pairs is lowered in energy by — A, so that the
total reduction in energy density is

W =-^=-2R eD
2 e-VW ( 13 . 2 1)

By setting this equal to the magnetic energy density, we can evaluateB as we do int

an example at the end of this section. The results are quite good. The amazing thing is
8
that Wq is so small, ~ 10 eV, as calculated in Section 13-2. There are many

energies in normal metal physics that are known to much less accuracy than this. It is

only that those effects are the same in both normal and superconducting states that
allows us to ignore them and focus on this small but obviously vital superconducting
effect.

We next look into some of the physics of the Meissner effect. Our discussion
involves the use of the differential version of Maxwell's equations in electromagnetic
theory.
The Meissner effect is the expulsion of the magnetic field from the interior of the
superconductor as shown in Figure 13-4. Surface currents are set up that establish a
magnetic field opposing the external field. The field deep inside is canceled out
exactly. It turns out that it is not sufficient just to assume that the system is a perfect
conductor. A perfect conductor has the property that once a field is established the
internal magnetic field is unchanging in time. Thus, it is trapped at the value it had
before the material went superconducting; it does not necessarily vanish as the
Meissner effect requires.
In Section 12-3 we have treated an equation for the particle velocity of a charge in
a resistive medium. In the case of no resistive forces , Equation (12-9) combined with the
definition of current density, J =~pe\, gives

dj pe*
-T- = E.
dt m

If J is
X, the induced current density in the superconducting sample, this equation
must be modified because the charge carriers are Cooper pairs; e is replaced by 2e
and m by 2m to give

17 = E. (13-22)
dt m

Since we consider an external field to be present, there must also be a current density
J, that acts as a source for that field. The total field is given in terms of both sets of
currents according to the Maxwell equation

V XB = /i
(J, + J,). (13-23)

We are interested in the value of the field at the position of the superconductor; we
assume that the external currents J, are zero there and need not appear further in our
equations.
 .

656 Superfluids and Superconductors

The electric field in Equation (13-22) obeys the Faraday law

V XE= -— dt

The substitution of E from Equation (13-22) into the last equation gives the result,

valid for a substance with zero resistance:

d m
i7(
(
B+
^ vx *)= \
' (13 - 24)

This relation is what the Maxwell equations require. Simply having a perfect
conductor obviously requires only that the quantity in parentheses be constant in time.
We see in Problem 10 at the end of the chapter that this also causes the field in the

interior of the superconductor to be constant in time rather than to vanish as the

Meissner effect requires. London proposed that an equation more restrictive than
Equation (13-24) must hold for superconductors. This London equation is

m
B+ ^~F V x l= °- < 13 " 25 )
2pe~

We accept this equation without proof, and next we see how the Meissner effect
follows from it. The BCS theory does indeed give Equation (13-25). The term
containing J can be reexpressed
t
in Equation (13-25) by use of Equation (13-23).
(Remember that J, is zero at the positions we are considering.) Then we use the
mathematical identity

V X (V X B) = V(V • B) - V 2
B.

By yet another Maxwell equation, we have V •

B = 0, so that Equation (13-25)
reduces to

B = X2 V 2
B, (13-26)

where
m
X2 =- -. (13-27)
2MoP*

We solve Equation (13-26) in the special case in which the superconductor is a

semi-infinite block whose face is at x = as shown in Figure 13-13. The external field
B = Bz is in the z direction, parallel to the face of the block. The variation of B is in

the x direction only so that Equation (13-26) reduces to

£(*)=A 2
—V- ax

The solution of this equation has B = constant on the boundary at x = 0, while for
x > 0, inside the material, the solution is

B(x) = B(0)e~ x/x . (13-28)

This result says that the field decays exponentially as one goes into the superconductor
 / 3-7 Theoretical Interpretation of Superconducting Experiments 657

Figure 13-13

Expulsion of the magnetic field in a semi-

infinite block of superconducting material.
The field, in the z direction, decreases from
its exterior value according to exp( — x/X),
where A is the penetration depth.

^x

and vanishes deep in the interior. So the Meissner effect is not perfect at the surface;
the field actually extends approximately the penetration depth A into the material. Since
A can be as large as 0.1 jum very thin films having a field extending all the way
through can be made. Since these systems do not expend much energy expelling the
field, they have very high critical fields.

We show via Problem 1 1 at the end of the chapter that the supercurrent J also (

resides on the surface within a penetration depth. For later use we note that this result,
together with Equation (13-22), implies that the electric field E always vanishes in the
interior of a superconductor.
The unusual properties of superconductors make them useful in many different
applications.The recent discovery of oxides that superconduct at high temperature
may mean the practical possibility of superconducting electrical transmission lines,
magnetically levitated trains, and a host of other uses. In Section 13-8 we see further
properties and some of the devices that can be made based on another effect in
superconductors.

Example

By setting the ground-state energy density W given by Equation (13-21) equal

to the magnetic field energy density, we can find the critical field:

Bf R tf

2(i 2

where the density of particles per unit energy at the Fermi surface (e = eF ) is

shown in Equation (12-15) to be

2e F
658 Superfluids and Superconductors

Thus, we obtain

/3, oP
B c
'

V 2£ F

We recall from the example after Section 13-6 that, for aluminum, \/k B =
2.1 K. Also, since p = 6 X 10
28
atoms/m and 3
/k B =
eF 1.4 X 10
5
K, we have
"
1/2
23
'

1.5(477 X 10
7
N/A 2
)(6 X 10
28
m~ 3 )
B = (1.38 X 10" J/K)(2.1 K)
X 10" 23 J/K)(l.4 X
c
5
(1.38 10 K)
= 7 x 10
3
T,

a result in fairly good agreement with the experimental value of 10 X 10~ 3 T.

Example

The penetration de 3th of the magnetic field into a superconductor is given by

Equation (13-27). F or aluminum we find

1/2
m 9.1 X 10~ 31 kg
, /
2 2
28
V 2/i P' 2(477 X 10~ 7 N/A 2
)(6 X 10 m~ 3 )(l.6 X 10~ 19 G)
= 1.1 X 10 8
m = 1 1 nm.

This is in only qual itative agreement with the experimental value of ~ 50 n m.

13-8 The Josephson Effect

Superconductivity has given rise to the possibility of a variety of devices. Some of

them are based on a very interesting discovery due to B. D. Josephson. The Josephson
effect is worth studying in detail because it illustrates the high coherence of the
superconducting state. It is also interesting because it involves a purely quantum
mechanical effect, quantum tunneling, in a basic way. Josephson junctions, as the
elements are called, have been used in a number of applications, such as in the very

sensitive measurements of voltage and magnetic field, and as computer memory

elements.
In a Josephson junction two pieces of superconducting material are separated by a
thin insulating oxide layer as shown in Figure 13-14. Electron pairs in a superconduct-
ing state are separated from other pairs in a slightly different state on the other side of
the oxide barrier. If the barrier is thin enough, pairs can tunnel, via quantum barrier
penetration, from one side of the layer to the other. If the two states differ, or are

made to differ by the application of a voltage, a net current arises. The existence of
this current not only reveals the existence of quantum tunneling but dramatically
illustrates theremarkably coherent character of the superconducting state.
Back Chapter 5 we have learned that an energy eigenfunction for a single
in
particle corresponding to energy E can be written, for one-dimensional motion, as
 / 3-8 The Josephson Ellecl 659

Figure 13-14

Josephson junction. Two pieces of

superconductor are separated by a thin oxide
layer of thickness 2a.

-Insulating oxide layer

Superconductor %%> Superconductor

-x^- I

-5>- x

where to = E/h and 4>(x) is the time-independent part of the wave function. Because
of the highly ordered nature of the many-particle superconducting wave function, we
are able to define a similar quantity that is a function of a single variable (in three
dimensions it is a function of vector position r). This quantity behaves like a
single-particle wave function; but it actually describes the behavior of every particle
— actually every Cooper pair — simultaneously. It is called an order parameter. Such a
function is possible only because the condensed pairs of electrons are so coherent; we
cannot push on one without affecting all of them.
2
In this interpretation |i//(*)| , which in a normal wave function is the probability
density, here becomes the density of superconducting pairs

!*( ft
•

a real quantity while \p(x) itself can be complex. Quite generally we can write

where <p Q is the phase of the time-independent part of the order parameter. The full

time-dependent order parameter then has the general form

*(*,o = pyv'*, (13-29)

where the phase <j> is

In Chapter 5 a probability current is also introduced as

j= — 2im
h (

\
**-
3*
ox
d**
—*
ox
\

. (13-30)

When ^ is the superconducting order parameter, this expression multiplied by the

electronic charge gives an electric current density. Remember that we are talking
about a current carried by Cooper pairs so that we must really multiply by - 2e (e is
taken as a positive quantity) and replace m by 2m, where m is the mass of a single
660 Superfluids and Superconductors

electron. The two factors of 2 cancel so that the electric current density is given by

J= ~ej.

Next, we show that the current is dependent on the spatial variation of the phase of
the order parameter. We then show how that phase can be controlled by applying a
voltage in order to generate a tunneling current. Suppose that ps in Equation (13-29)
is independent of x. Then combining Equations (13-29) and (13-30) gives

7=—
m
y-.
ehp t
dd>

ox
(13-31)

If we put a voltage V across the junction, the resulting change in electronic energy
then affects the time-dependent phase. We take the zero of potential at the center of
the gap, x = 0, in Figure 13-14. Then the left side of the junction is described by

*,U,0 = pyV<\ (13-32)

where now

<J» 1 =<f, +L + y)l. (13-33)

The potential on the left side is — V/2, which is multiplied by ~2e, the pair charge,
to get the associated potential energy given in Equation (13-33). The order parameter
on the right side of the gap is described by an equation analogous to Equation
(13-32), with 1 replaced by 2 and with the phase on the right side given by

4> 2 = + w- '— \t. (13-34)

4>o I

We assume Cooper pairs p and the constant phase

that the density of are the same s <f>

on both sides of the junction. We have also assumed that the zero-potential frequency
to is the same on both sides of the junction. What the potential V has done is to alter

the frequency in a different way on the two sides of the gap so that the phase has a
gradient; a current is then established according to Equation (13-31). Since the phase
difference is time dependent, the current is AC. The only reason that we can maintain
such a voltage is because the oxide layer is insulating.
Is any current that might want prevented from doing so by the insulating
to flow
layer? For thick layers gap is thin enough quantum tunneling through
it is, but if the
it allows the current to proceed. We assume that the oxide layer represents a constant

potential energy barrier. We have treated penetration of such a barrier in Chapter 5

and from that treatment we know that within the oxide layer the left-hand-side order
parameter decays exponentially so that

¥,(*,*) = P y e-
2 !

^e- aix + a \ x> -a. (13-35)

The decay constant a is determined by the size of the potential barrier as shown in
Chapter 5. Similarly, pairs originating on the right side of the gap are described by

/2 + a(x - a)
%(*, = pl e-'^e ,
x < a. (13-36)
 13-8 The Josephs on Effect 661

Figure 13-15

Exponential decay of the order parameters 4'

1

and ty, in the potential energy barrier of the

oxide layer in a Josephson junction.

>X

This function decays as we move from x = a to smaller x values. The values of ^P,

and ty, are shown schematically in Figure 13-15.

We expect, from our treatment of the binding of the diatomic molecule in Chapter
10, that an electron pair capable of being in each of two regions has an overall wave
function in the intermediate region given by either of the two functions

*±= (*, ± %)/y/2

(13-37)

We can work with either of these functions; both give the same result for the current.
We use ty + .

We find the current in the gap by substituting ^ + into Equation (13-30). After a
small amount of algebra we reach the result

J =7o sin0, 13-38)

/here

2eV
(13-39)

and
ap/h
7o
=

The details of the calculation are left to Problem 12 at the end of the chapter.
There are several things to note about the Josephson current density of Equation
(13-38). If the potential V vanishes, there is no current. (We have assumed that <p is

the same on both sides of the gap. If it is not — and we have no control over this phase
— there is a DC current dependent on the difference in the two <J>
values.) If V is not
zero an AC current results. The frequency of this current is

2eV
V = (13-40)
J ~h~'

For V= 1 juV, this frequency is 484 MHz. Microwave radiation originating from this
oscillatory current has been detected. This phenomenon is known as the AC Josephson
effect.
662 Superfluids and Superconductors

Figure 13-16

Behavior of a ring of superconducting material when the ring is placed in a magnetic field and
the temperature is lowered below Tc
. If the field is then turned off, magnetic flux is trapped.
The path of integration for Faraday's law is shown in (a). The trapped flux is illustrated in (b).

(a) (b)

Josephson junctions provide the best-known measurement of the fundamental

constant ratio e/h; they can also provide very sensitive measurements of voltage. A
well-known company spent many millions of dollars developing a computer based on
the Josephson effect only to abandon the project in favor of the continued use of
silicon. The Japanese are maintaining efforts to develop a Josephson computer.
The AC effect is the result of applying a DC potential difference. If an AC
potential is applied then, curiously enough, a DC current results when the applied
frequency is v..

A very interesting device can be made from the Josephson junction. Before
considering it, we need to look at the phenomenon of flux quantization. Suppose we
form a ring of superconducting material, place it in a magnetic field, and then reduce
the temperature below Tr While the Meissner effect excludes the field from the
superconducting material itself, the field is still able to thread through the hole in the
ring. If the external field is turned off, the flux through the hole is unable to decrease.
The reason is Faraday's law. The rate of change of flux $ through an area is the
integral of the electric field E around the perimeter of the area:

^E •
dt- (13-41)
~Jt

If, as illustrated in Figure 13-16a, we take the circuit of integration around the ring
within the material, then, since Ewe must have
is zero inside any superconductor,
d<b/dt = 0. That is, the flux is trapped as Figure 13-166 indicates. It is maintained
by the flow of surface currents in a thin layer of depth A in the surface of the
superconductor. An important feature here, that we have not derived, is that the
amount of flux threading through the ring is quantized. It is known that

2irnh
<D =

where n is an integer and q is the charge on the carrier of the supercurrent. Since the
charge carriers are Cooper pairs, the value of q is 2<\ The result, that the minimum
 13-8 The Josephson Effect 663

Figure 13-17

Superconducting quantum interference device.

The SQUID is a ring of superconductor
interrupted by a Josephson junction.

Josephson junction

value of the quantized flux is

7rk
(13-42)
e

and not 27rh/e, has been verified experimentally. London originally predicted this
effect before the BCS theory and assumed q = e. The result q = 2e is thus a strong
element in the verification of the BCS theory.
Quantized lines of flux can also be trapped within the interiors of certain forms of
superconductors. The Meissner effect is not really violated here because the "hole"
through which the field is threaded is a line of normal material. Such superconductors
are designated as type-II. The critical fields in these materials are much higher than in
the usual type-I form of superconductor, which does not allow such penetration by
magnetic fields without destruction of the superconducting state.

Suppose we now introduce a Josephson junction somewhere in the ring as pictured

in Figure 13-17. The resulting object is the superconducting quantum interference device or
SQUID. Analysis shows that the current density in the ring, which necessarily involves
tunneling through the junction, has the form of Equation (13-38). Now, however, the
phase difference 8 depends on the magnetic field and is given by

277$

«IV

where O is the total magnetic flux through the loop. This total flux is made up of the
flux due to any external field as well as that resulting from any surface currents in the
ring. We do not enter into the details of the theory or the use of this device, but only
mention that it has become a very useful tool in condensed-matter physics as well as in
other areas. It can provide an extraordinarily sensitive measurement of magnetic
fields. A flux may be measured to within 10~ $
4
which is equivalent to a sensitivity
,

of order of 10" 13
T!
As we have seen, Josephson junctions are illustrations of fundamental principles in
solid-state physics and quantum mechanics, and at the same time are extremely
practical devices.
664 Superfluids and Superconductors

Example

The frequency involved in the AC Josephson effect obeys the relation

19
2e 2(1.6021 X 1(T C)
v,
—
V
= — = T
X 10" 34
.
= 4.836 X 10
14
Hz/V = 483.6 MHzAiV. ^
h 6.6256 J •
s

The basic unit of quantized flux is just the inverse of this:

h V 1

*o
= = 2.068 X 10" 15 Wb.
2e Vj 4.836 X 10
14
Hz/V
~6
For a loop of radius — 1 mm and area 10 m 2
this corresponds to a magnetic
field of magnitude

2.068 X 10~ 15
— Wb -9
B = 5
= 2.068 X 10 T.
10" 6
m 2

13-9 Other Superfluid Systems

4
Other substances, besides He, have the potential for superfluidity. As we have
already mentioned, most boson systems solidify before they have a chance to become
4
superfluid. The only other commonly available material, which, like He, does not
solidify even at T= K, is
3
He. Although
3
He is a fermion system it is found to have
a superfluid transition, but at a temperature of 2.7 mK, almost three orders of
4
magnitude lower in temperature than the transition in He. There is also an
"artificial" substance, atomic hydrogen, which is now being studied in hope of finding
a Bose condensation. We do not intend to describe either of these substances at length
but instead present a brief qualitative picture of each.
3
In 1972 Osheroff, Richardson, and Lee were running an experiment on solid He
and found two "glitches" in the melting curve. These were ultimately attributed to the
transitions to two different superfluid states in the liquid. After 70 years, superfluidity
4
was no longer restricted to just He.
3
The He system is a set of fermions as are the electrons in a metal. The onset of
3
superfluidity in this system involves the pairing of He atoms analogous to the
superconducting phase change in metals. There is little relation to the A transition in
4
He. However, there are some considerable differences from the superconducting state.
Obviously, 3 He atoms do not carry any charge and so electrical supercurrents do not
exist; instead, the viscosity of the liquid is considerably reduced. In superconductors
the electron pairs are in an = singlet state. However, in 3 He, the pair state has a
c"

nonvanishing angular momentum; it is an f= triplet state. The introduction of this 1

new vector into the problem makes this state quite complex. The ( vectors of the 3 He
atoms can align so that the liquid develops a directional quality known as texture.
More than one kind of pairing can take place so that there are two superfluid
states, one as described above and the other isotropic. In an external magnetic field a

third superfluid state is formed. Because the possibility of € = 1 superconductivity had

been considered long before the discovery of superfluidity in He, this system was very '

quickly understood theoretically. The microscopic description of He is now probably

more complete than that of He.
Hydrogen gas is made up of tightly bound diatomic molecules, so that atomic
hydrogen is highly unstable to the formation of H>. The electrons of H 2
are in a
singlet state; the spins are antiparallel, as we have seen in Chapter 10. Thus, two
 Problems 665

atoms of hydrogen, approaching each other with antiparallel spins, feel a very strong

attraction.
On the other hand, it turns out that two hydrogen atoms approaching one another
with parallel spins (the triplet state) feel at most a very weak van der Waals attraction
at a distance of several Bohr radii (weaker even than the He-He attraction) and a
strong repulsion at short distances. A gas of hydrogen atoms all with parallel electron
spins is called spin-polarized hydrogen or H[ . The interatomic force is so weakly binding
that, like helium, no solid forms, even at T= K. Even more astonishing is the
prediction that the liquid state does not condense at any temperature; the material is

expected to remain a gas all the way to absolute zero at low pressures.
Furthermore, the hydrogen atom, because it is a combination of two fermions, is a
boson. In principle then, it is possible to cool HI until it undergoes a Bose
condensation. Because this system is a dilute gas, its theoretical description is a much
simpler problem than that for the dense He liquid. Much of this theory already
exists.

The experimental problem with atomic hydrogen is stabilizing all the atoms into
the parallel-spin state. A strong magnetic field is used to align the electronic spins.
(The electron spin has its lowest state in the direction opposite to the magnetic field;
this is the reason for the downward pointing arrow in H J, .) Unfortunately, there are
several interactions in the gas and on the container walls that can flip spins leading to
the destruction of H J,
through the formation of H2 . For this reason the highest density
24
achieved to date is only about 5 X 10 atoms/m 3 which , is two orders of magnitude
too low to have the Bose condensation at the convenient temperature of 1 K. For
temperatures much lower than this the gas becomes adsorbed onto the container walls
where it rapidly recombines. To overcome these problems experimentalists are devel-
oping magnetic and away from walls
laser "traps" that confine the particles to regions
and simultaneously provide unusual cooling procedures. Considerable interest has
been shown in this system and there is a continuing effort to reach the conditions
necessary to observe the Bose condensation and the presumed accompanying transi-
tion to a new superfluid state.

Problems

1. In the neighborhood of the roton minimum the He excitation spectrum is given by

( p - PoY
rotun
= £ +

4
with &/k H = 8.65 K, p /h = 19 nm" ', and ju. = 0.16m m = ( the He atomic mass). Use
this form to find the numerical correction to the approximation vc ~ &/p = 59.8 m/s for
the critical velocity calculated in the example at the end of Section 13-3.

2. Suppose some superfluid system has an excitation spectrum given by

=A 1
-
*P
A, / I Ao

in which A/k B = 10 K, p /h = 10 nm ', and p > 0. Calculate the critical velocity by

graphical means. Repeat the calculation analytically.

3. In considering the Bose condensation of an ideal gas, we argue that n is of order N for
T< T c , while n, , n2 , . . . are all much smaller so that we can separate off n and treat the
 .

666 Superlluids and Superconductors

sum of the remaining terms as an integral. Using the expression in Equation (12-6) for the

momentum and assuming the form a = a/N, show that the occupation numbers n, , n2, . .

for the very low excited states are all of order N 2/i . This is indeed much less than N
when N is very large. How many terms having this size are there and of what order is

their net contribution to the integral?

4. Compute the total energy and heat capacity for the ideal Bose gas for temperatures less

than the Bose condensation temperature T

c
.

5. (a) When a is large the exponential of Equation (13-10) is much greater than unity.
Show that Equation (13-11) follows. In this case n can be neglected compared to

the second term in Equation (13-9). Show that the result for a is that of the classical
ideal gas of Equation (11-30).

6. An early form for the excitation spectrum of rotons, due to Landau, was

/'
£
roton = A +
2p.

Compute the heat capacity implied by this spectrum when kB T «c A. Note that rotons,
like phonons, have a Bose distribution n = (e^ 1 ? — 1)"'.
p

7. The radius of a Cooper pair state is about 1 \im. By using the data for aluminum given in

the text, calculate how many other Cooper pairs have their centers within the volume
occupied by one pair.

8. The superconducting critical temperature of tungsten is 12 mK and the critical field is

10~ 4 T. The mass density of tungsten is 19.3 g/cm3 and its Debye temperature is 310 K.
(a) Evaluate the energy gap 2 A. (b) Evaluate the energy density of the superconducting
state by two different methods: (i) compute B^/2fi and (ii) evaluate W in Equation
(13-21). To carry out (ii) you need to estimate eF by an appropriate formula from
Chapter 11.

9. Evaluate the penetration depth A of tungsten by using the data given in Problem 8.

10. The London equation of BCS theory, Equation (13-25), leads to the Meissner effect,

Equation (13-26). Show that the simpler assumption of perfect conductivity, as embodied
in Equation (13-24), leads instead to the result

B = A'v'B,

where B = dH/dt. Prove that this implies that the field value becomes fixed at the value
it had when the material became a perfect conductor rather than at zero.

11. By using the relations developed in Section 13-7, prove that the current in a superconduc-
tor resides within a penetration depth A of the surface. (You also need the equation of
continuity V '
J,
= dp /dt,
f
the right side of which vanishes in a steady-state condition.)

12. Carry out the steps needed to derive the Josephson relation, Equation (13-38).
13. The flux through a superconducting ring is <I> , the basic unit of quantized flux. To what
average magnetic field does this correspond, if the ring has a diameter of 2 mm?
14. When a time-dependent potential is placed across a Josephson junction, the phase eV t/h
is replaced by ejV(t) dt/h. Suppose that V(t) = V + fcos^yi, where v «: V . Use the
Josephson relation, Equation (13-38), and the approximation sin(x + 8x) ~ sin x +
8x cos x (for Sx «: x) to show the DC Josephson effect. That is, show that J has a
nonzero time average if the impressed frequency is y = 2eV /h.
24
15. Spin-polarized hydrogen has been concentrated to a density of 5 X 10 m~ 3 What . is the

Bose condensation temperature for this density if you assume this system is an ideal gas?
 FOURTEEN
PROPERTIES
AND
MODELS
OF
THE
NUCLEUS

The first investigations of the nucleus were

conducted by Rutherford, the founder of nuclear physics. His contributions became
influential in the years following the discovery of natural radioactivity. He interpreted
this phenomenon as a transformation of matter within the atom, resulting in the

emission of two new forms of radiation, and he gave the names alpha and beta to the

two types of emitted particle. His studies of a radiation identified the a particle as a
doubly charged helium ion. These emissions were used as beam particles to probe the
atom before the coming of the accelerator. The decisive experiments on the scattering
of a particles by atoms began in 1909 under Rutherford's direction. The results
established the existence of the nucleus and supported the nuclear model of the atom.
Subsequent experiments in Rutherford's laboratory found that protons were pro-
duced when a particles collided with the nitrogen atoms in a gas target. These
observations of the splitting of the nucleus came in 1919 and gave the first indications
of nuclear substructure. Rutherford drew upon this evidence to propose the existence
of the neutron, a neutral particle supposed to occur along with the proton as a second
fundamental constituent of the nucleus. He and his associate J. Chadwick undertook
an experimental search for the neutron in order to verify his bold prediction of a new
type of nuclear particle. Rutherford's laboratory was dedicated to these explorations
of the nucleus at a time when other investigators were focusing their attention in
another direction toward the understanding of the quantum theory.
Rutherford's foresight was rewarded when the neutron was finally discovered by
Chadwick in 1932. Several other important discoveries also came to light in the same
"miraculous year." The chemist H. C. Urey identified the deuterium atom as a heavy
form of hydrogen. The deuterium nucleus, the deuteron, provided the simplest

667
668 Properties and Models of the Nucleus

proton-neutron system for the study of the force between nuclear particles. Accel-
erated beams of protons were employed for the first time to cause the disintegration of
the nucleus. Accelerators made it possible to probe the structure of the nucleus at
controlled energies higher than any obtainable from radioactive sources of a particles.
Thus, in a single year, the second constituent of the nucleus was detected, the basic
two-body nuclear system was found, and the examination of the nucleus at increasing
energy was begun.
Inquiry into the experimental and theoretical problems of nuclear physics quick-
ened after 1932. The pioneering Rutherford passed his inspiration along to the next
generation whose leaders included Bohr, Heisenberg, and especially Fermi. These
proponents of the quantum theory of the atom advocated the extension of quantum
mechanics to the theoretical treatment of the nucleus. It was realized that the nuclear
particles were governed by an unknown interaction, and it was believed that the
properties of the unknown force could be deduced from experiments on nuclear
scattering and nuclear binding. The lack of an underlying theory drove the investiga-
tors to adopt a phenomenological approach where models could be used to interpret
the accumulation of experimental facts. Several of these models have enjoyed a degree
of success within their limiteddomains of validity.
Nuclear models have developed on two separate levels. The basic force between
nuclear particles and the application of the force to complex nuclear structure fall into
separate areas of speculation. Progress has been made in these areas through the use of
different kinds of models. A truly fundamental theory of the nuclear force is only now
beginning to germinate by way of an underlying theory of the elementary particles.

The purpose of two chapters on nuclear physics is to examine the main

of this first

properties of the nucleusand the nuclear force. We take advantage of our experience
with atoms and apply our knowledge of quantum mechanics to introduce some of the
prevailing models. The phenomenology continues in our treatment of nuclear decays
and nuclear reactions in Chapter 15. The specific nature of the fundamental force
between the constituents of the nucleus remains submerged until the question can be
brought back to the surface in the final chapter on elementary particles.

14-1 Nuclear Particles

A preliminary picture of the nuclear size, charge, and mass was in existence by 1920.
The a-particle scattering experiments found the radius of the nucleus to be of order
10 '
m, four orders of magnitude smaller than the size of the atom. Moseley's
analysis of characteristic x rays established the connection between the nuclear charge
and Mendeleev's atomic number Z. The smallness of the electron mass meant that
almost all the mass of the atom was concentrated in the nucleus. It was recognized
that the atomic mass was close to a whole number of hydrogen mass units, and it was
also noted that this mass number A was approximately twice as large as the correspond-
ing charge number Z for most atoms.
The first tentative nuclear model assumed a bound structure of protons and
electrons, the only known It was thought that the nucleus contained A
particles.

protons to account for the observed mass number, and A — Z electrons to give the
total charge of the system the value

Ae — (A — Z)e = Ze.

The electrons were believed to be present in the nucleus because the /?-ray process was
known to involve the emission of electrons from the core of the atom.
 14-1 Nuclear Particles 669

Figure 14-1

Chadwick's neutron-detection experiment.

5 MeV
Paraffin
detector

The proton -electron model had several fatal flaws. It was difficult to understand
why the magnetic moment of a nucleus containing electrons should have an order of
magnitude equal to the nuclear magneton instead of the Bohr magneton. It was also
impossible to reconcile certain nuclear spins with the spin- ^ properties of the proton
and electron. (For instance, the N atom was known from studies of molecular nitrogen
spectra to have an integer-spin bosonic nucleus, while the mass and charge numbers
A = 14 and Z = 1 called for a nuclear constituency of 14 protons and 7 electrons.
The odd total number of fermions was not consistent with the existence of a composite
boson.) Finally, it was unrealistic to suppose that the electron could be localized in
such a small region of space because of the large kinetic energy implied by the
uncertainty principle. Rutherford's proposal of a massive uncharged nuclear particle
opened the way for a satisfactory picture of the nucleus, and Chadwick's discovery of
the neutron removed the electron from consideration as a permanent nuclear particle.
These developments made it necessary to regard the emission of /?-ray electrons as a
separate phenomenon unrelated to the binding of the nucleus.
The discovery of the neutron required a special technique for detecting neutral
particles. (Neutrons would not leave visible tracks in a material medium because they
would not interact electrically with the atoms in the material.) Chadwick's method
relied on the observation of the secondary charged particles that appeared when the
primary neutral particles reacted with the atoms in the medium of his detector. His
experiment used a radioactive polonium source to generate a beam of 5 MeV a
particles and employed a beryllium foil to provide a target, as shown in Figure 14-1.
Neutral "Be radiation" emerged from the target and passed through sheets of
paraffin, ejecting protons from the hydrogenous material with kinetic energies as large
as 5 MeV. At first the neutral particles were hypothesized to be photons so that the
process in paraffin was presumed to be the Compton scattering of y rays by protons.
The kinematics of the Compton process implied that the incident y energy must have
been as large as 50 MeV to explain the ejection of protons with the observed 5 MeV
kinetic energy. Chadwick did not accept the view that a 50 MeV photon could be
emitted in the collision of a 5 MeV a particle with a Be nucleus. He also rejected the
y-ray hypothesis because the detection of protons in paraffin greatly exceeded
predictions based on the cross section for Compton scattering. He argued instead that
the energetic protons were ejected by an unknown form of Be radiation consisting of
neutral particles with mass approximately equal to the mass of the proton. This
alternative hypothesis enabled him to conclude that the 5 MeV a particles produced 5
MeV neutrons in beryllium and that these neutrons then transferred their energy to
protons in the paraffin detector. Similar studies were also performed with nitrogen gas
substituted for paraffin. Tracks of recoiling nitrogen nuclei were detected in this
version of the experiment, making the y-ray hypothesis even more untenable and
670 Properties and Models of the Nucleus

leaving the neutron as the only satisfactory interpretation for the unknown Be
radiation. These investigations were convincing enough to establish the existence of
the neutron.
Ever since the discovery of the neutron, the accepted view of the nucleus has been
to treat the proton and neutron as the basic nuclear particles and to regard the
existing species of nuclei as bound configurations of various numbers of these
constituents. The positively charged proton and the uncharged neutron are spin-^
fermions with only slightly different masses:

M p
= 938.27231 MeV/c 2 and M„ = 939.56563 MeV/c 2 .

In fact, most of the nuclear characteristics of the proton and neutron are identical, and
so the generic name nucleon has been given to the two particles.
Each nucleon has a magnetic moment associated with its spin. These two quantities
are known from experiment to have the values

Hp = 2.792847386 n N and nn 1 .91304275 fi N

in terms of the nuclear magneton defined in Equation (8-56). Let us recall that the
general relation between the nuclear magnetic moment ji
7
and the corresponding
nuclear spin I is expressed in Equation (8-57) as

In the case of the proton and the neutron we use the vector I to denote a nucleon spin
with quantum number '= ^, and we quote the results for the magnetic moments as
i

expectation values of the z components of \i

p
and \i
n , evaluated in the spin-up state.

The nuclear g-factors of the nucleons are therefore given by the values

— = 2.792847386 and - = -1.91304275.

2 2

(The proton g-factor has already come up in our discussion of hyperfine structure in
Section 8-12.) These experimental results for the proton and neutron are rather
different from the g-factor for electron spin, g s/2 = 1.001 .... and are also quite
different from the values predicted for charged and neutral spin- particles in Dirac's -,

relativistic quantum theory:

n p
— = 1 and — = (Dirac theory).

The magnetic moments may be taken as evidence that the nucleons are structured

particles, unlike the electron, where the structure is not simply described by the Dirac
equation.
The force that binds nucleons together in the nucleus is very different from the
electrostatic force responsible for the structure of atoms. It is clear that the nuclear
force must be very complex to explain the observed size, shape, stability, level
structure, and reaction behavior of all nuclei. The interactions among the nucleons
can be associated with a complicated two-particle potential energy acting between all
 14-1 Nuclear Particles S7I

Figure 14-2

Qualitative scales of atomic and nuclear size.

Atom

pairs of constituent particles. It is known that the nuclear forces between proton and
proton, proton and neutron, and neutron and neutron are essentially identical. Evi-
dence for this important simplifying property of the nuclear force has been gathered
from proton-proton and neutron-proton scattering experiments and from many other
sources. The small size of the nucleus is a qualitative indication that this two-body
force has a very short range. Figure 14-2 shows a highly schematic (and dispro-
portionate) comparison of the orders of magnitude for the atomic radius, the nuclear
radius, and the internucleon range.

Figure 14-3

Potential energy for a system of two nucleons.

V(MeV)

k r(fm)
672 Properties end Models of the Nucleus

It is obvious that the attractive force between nucleons must be very strong at short

range because the nuclear force between protons overwhelms the destabilizing Coulomb
repulsion of like charges. The strength of the two-nucleon interaction varies with the
separation of the particles and can also depend on such other variables as the
momentum and spin of each nucleon. The graph in Figure 14-3 describes a possible
model of the nuclear potential energy for a pair of protons in a state with zero total
spin. The figure also shows the Coulomb potential energy to indicate the dominance of
nuclear attraction for ranges smaller than a few fermi. (The natural scale of length in
nuclear physics is defined by the unit 1 fm = 10" 15
m. This length is written as one
femtometer and is read as one fermi.)
The units on the vertical axis in Figure 14-3 indicate a nuclear interaction energy 7

in the MeV range. Excitations of the states of nuclei require similar amounts of energy
to reach levels much farther apart than those involved in the analogous atomic
processes. This upward adjustment in the scale of energy is commensurate with the
reduction in the scale of distance suggested by the descent from the atomic to nuclear
size in Figure 14-2. The change of the scale of energy has certain physical implica-
tions. We witness the excitations of atoms in the optical phenomena of ordinary life,

but we observe the excitations of nuclei only under extraordinary circumstances such
as high-energy collisions or high-temperature environments. Our initial discussion of

the nucleus is restricted accordingly to the properties of the lowest energy state.

Example

Let us calculate the electrostatic repulsion between two protons and compare the
two effects shown in Figure 14-3. We express the Coulomb potential energy in
terms of the fine structure constant as

ahe
Vcouiir)
AttEqT r

and we introduce nuclear physics units for the combinations of constants

he = 1240 MeV •
fm and he = —=
he

277
197.3 MeV •
fm.

A 1 fm proton-proton separation gives a Coulomb energy of magnitude

1 197 MeV •
fm
*o™.i
= = L44 MeV -
0,1,1
137 1 fm

The figure shows that Vnud dominates V^^ at 1 fm by almost two orders of
magnitude.

Example

We can use the de Broglie wavelength to demonstrate the relevance of the wave
nature of nuclear particles. A proton with mass M p
and kinetic energy K has
wavelength
h h he
\= - = . = .

P fiMp K pKM/~
 14-2 Nuclear Systematic* 673

For K= 5 MeV and 25 MeV we obtain the results

1240 Me V- fm
\ = = 12.8 fm
/2(5 MeV)(938 MeV)

and

/
— (12.8 fm) = 5.72 fm.

These values are of the same order as the nuclear radius, so that a proton beam
with kinetic energy in the range 5-25 MeV is expected to undergo appreciable
diffraction in collisions with nuclei. Note that X represents a scale of distance for
probing the structure of the nucleus, and recall that this scale diminishes with
increasing beam energy. The calculation also tells us that protons with kinetic
energies of order 5-25 MeV can be bound in nuclei by attractive potential
energies of realistic strength, since the wavelengths of the wavefunctions fit

within the nuclear diameter.

14-2 Nuclear Systematics

The nuclei of atoms exist in a multitude of different species known as nuclides. These
systems cannot be charted on the periodic table of the elements because the assign-
ment of atomic number alone does not suffice for a classification of nuclei. Every
element corresponds to a specific atom with a particular number of protons, and each
may have any one of several possible nuclei with different numbers of constituent
neutrons. Nuclides are called isotopes if they bear this relation to one another. These
varieties of nuclei have different values of the mass number A for the given choice of
atomic number Z.
The isotope concept was proposed in 1913 by F. Soddy, another of Rutherford's
many colleagues. The name "same place" in the
implied that atoms could occupy the
periodic table and acknowledged that atoms could be chemically identical and still be
physically distinct. Soddy's idea was put forward, almost 20 years before the discovery
of the neutron, in an effort to understand why different types of radioactive behavior
should be observed for the same element.
The numbers A and Z are used to systematize the properties of the nuclides. We
identify the mass number A and the charge number Z for a given nucleus as the
number of nucleons and the number of protons, and we define N to be the number of
neutrons in the nucleus according to the relation among the three integers

A = Z+ N. (14-1)

The designation of a particular nuclear species is then expressed by the notation

674 Properties and Models ol the Nucleus

where X is the chemical symbol for the atom with atomic number Z. Of course, it is
redundant to employ all four symbols since X and Z convey the same information,
and since A, Z, and N
satisfy Equation (14-1).

The best-known source of nuclear data-at-a-glance is the publication entitled Chart

of the Nuclides. This compendium displays the salient properties of all existing nuclei in
^X notation on a plot of proton number Z versus neutron number N. The chart
shows the isotopes of all the elements as horizontal entries for each of the various
values of Z. A stylized version of this information is constructed in Figure 14-4. We
are also interested in subsets of nuclides assembled according to common values of the
mass number A. These species with the "same mass" are called isobars. Their locations
appear on the plot of Z versus N
along diagonal lines defined by fixed values of
Z + N. We show a few of the lower-lying groups of isobars in Figure 14-5.
Stability properties are quoted on the nuclear chart to indicate whether individual
nuclides are stable or radioactive. The latter unstable varieties undergo some type of
decay, which may be either naturally occurring or artificially induced. A measured
half-life is identified for every radioactive nucleus, defining the time interval in which a

sample of the unstable nuclei decays to half of its original population. A naturally
occurring radioactive isotope has a measurable abundance on Earth and must either
decay with a very long half-life or exist as part of a disintegration chain originating
from some other long-lived decaying nucleus. We include a few half-life data in
Figure 14-5 to convey a sense of the enormous range of variation of this quantity.
Let us return to Figure 14-4 and note that the most conspicuous property of the
plotted nuclei is the near equality in the numbers of protons and neutrons. We explain
this trend later on when we apply the exclusion principle to the nucleus. The figure

also shows a secondary tendency for nuclides to fall below the line Z = toward the N
region where the neutrons outnumber the protons. This preference for neutrons stems
from the Coulomb repulsion between protons and grows with increasing nucleon
number. The Coulomb effect causes protons to experience less nuclear binding than
neutrons, particularly in the larger nuclei where the nucleons are more likely to be
farther apart.
The locations of the stable nuclides are clearly marked in Figure 14-4. (By
convention, a nuclide is said to be stable if there is no known decay, or if there is an
extremely long half-life expressible only by a very large lower bound.) We see at once
that the radioactive entries are in the majority and that the stable species cease to
occur at beyond a particular mass number. The first stable nucleus on the chart is
all
209
'H, the proton, and the last is Bi. The figure shows that the stable nuclei occupy

central positions in each isotopic or isobaric family, while the radioactive members of
the family lie to either side. We can visualize by drawing an
this distribution
imaginary valley of stability through increasing values of the mass number from A = 1
to A = 209. The stable-nuclide path between 'H and
209
Bi has two noteworthy gaps,
at A = 5 and A = 8. We interpret the nonexistence of stable candidates for these

Figure 14-4

Distribution of stable and radioactive isotopes. Data are taken from Chart of the Nuclides, 13th
edition.
 14-2 Nuclear Syslematics 675

J^
100 -

^n
i 1

90-

80
130 140 150

J c
j£r
I
J LU-

/(i

"I

60- -cz r
n_c

50 £="
Trrr
80 90 100 110 120

n_q n

40;-

TT'

30 ^ :
:••
:••
-
•
i
>-

H 1
•
-r

H 1
• :•- m I

• • • •

20-
F=F
I

10 " , F a Stable

^=^~ Radioactive

,i", i u

10 20 30 40 50 60 70
TV
676 Properties and Models of the Nucleus

Figure 14-5

Stable and radioactive isobars at low mass number. Isotopic abundances are quoted for the
stable nuclides, and radioactive half-lives are given for the unstable isobars.

io
c . . .

19.3 s
io B

199

10
Be

. . .

1 6*10 6 y

-Percentage of isotopic abundance

3
He
000014

Radioactive half-life

s = second
m = minute
y = year

mass numbers as qualitative indications of the unusual stability of the A = 4 nuclide

'He. The two gaps tell us that it is not favorable to add one more nucleon to the
A = 4 system or to bind two such systems together.
We learn several interesting lessons just by counting the nuclides according to the
following four possible combinations of proton and neutron numbers. Of the 268
existing stable nuclei (including those that are extremely long-lived), there are

159 with even Z and even TV (even-even),'

53 with even Z and odd A r
(even-odd),
odd A even A
50 with odd Z and even N (odd-even), i

and 6 with odd Z and odd N (odd-odd).

The stable odd-A nuclei exist in roughly equal numbers of even-odd and odd-even
varieties. This observation is a hint that the nuclear force does not distinguish between
protons and neutrons. The distribution of the stable even-A nuclei is more remarkable
 14 -2 Nuclear Syslematics 677

since almost all these nuclides fall into the even-even category. The odd-odd entries

are rare enough to be identified by name:

2
H, 6
Li,
10
B, and l4
N at low A

together with the extremely long-lived members

r,0
V and l80
Ta at higher A.

We take the imbalance between even-even and odd-odd nuclei as evidence that the
nuclear force has a pairing property. The evidence tells us that the force between
nucleons in the nucleus has a strong preference for paired-proton and paired-neutron
configurations. This feature of the nuclear force must be incorporated in the building
of nuclear models.
Figure 14-4 suggests another numerological exercise that also has implications for
model building. If we distribute the 268 stable nuclei over approximately 100
elements we find that an average of two or three stable isotopes is expected for each
element. In fact, an inspection of the nuclear chart reveals some very marked
departures from this expectation. If we follow the valley of stability in the figure we
encounter unusually large stable populations of nuclei along the succession of lines

N= 20, Z= 20, N= 28, Z= 28, N= 50, Z= 50, and N= 82. The most striking
occurrence of stability is seen at Z= 50 where the element tin is found with ten stable
isotopes. These patterns of exceptional stability in nuclei are reminiscent of the shell
closures observed in atoms. The numbers 20, 28, 50, and 82 are among the magic
numbers associated with the shell structure of the nucleus.
We might wonder whether any stable nuclei exist beyond the range of the current
nuclear chart. Nuclear stability tends to terminate with increasing numbers of
nucleons because of the destabilizing influence of Coulomb repulsion among the
growing numbers However, the shell theory of the magic-
of protons in the nucleus.
numbers indicates the possible existence of an "island of stability" off the chart, at
coordinates given by the predicted magic numbers 114 and — 184. New Z= N
superheavy elements ought to exist in this vicinity if these predictions are correct. No
trace of any such element has yet been found in any samples of naturally occurring
material. An attempt to synthesize superheavy products in nuclear reactions is also
underway using accelerated beams of heavy ions (such as 48 Ca or even 2iH \J) incident
on heavy targets (such as 248 Cm). These studies have not produced any positive
evidence in their early stages of investigation.

Example

Let us translate Chadwick's experiment into the language of nuclide notation.

We describe the process in which incident a particles produce Be radiation
(neutrons) by the nuclear reaction

4
He 2 +*Be 5 - 12
,C f) +X-
Note that conservation laws are imposed on the sum of the charge numbers and
the sum of the mass numbers to identify the carbon nucleus in the final state.
678 Properties and Models of the Nucleus

The reaction can be expressed in briefer notation as

4
He+ 9 Be^ ,2
C+V
or in even more streamlined fashion as

9 12
Be(a,rc) C.

We include the superfluous left and right subscripts Z and N in the first version
of the reaction to draw attention to the conservation laws for the total charge
4 9
and the total number of nucleons. Let us also note in passing that He, Be, and
l2
C are stable nuclides and that the only unstable participant in Chadwick's
experiment is the neutron itself. This instability causes the neutron to decay and
transform into the proton via the /2-radiation process. We see from Figure 14-5
that the transformation is between isobars and that the quoted half-life is 10.5
min.

Example

The observed bosonic property of the nitrogen nucleus 14

N is consistent with the
assignment of proton and neutron numbers Z = 1 and N= 1 . The total
number of fermions is even, and so the collection of nucleons can exist in the

form of a composite boson, as determined by experiment.

14-3 Electron Scattering and the Nuclear Radius

The first determinations of nuclear size came from the Rutherford scattering experi-
ments. These estimates of the nuclear radius were obtained by observing deviations
from the Rutherford cross section and attributing a deviation to the effect of a nucleus
of definite volume.
More refined measurements of nuclear structure became feasible with the develop-
ment of accelerators. These machines were able to produce beams of particles with
de Broglie wavelengths small enough to probe the details of the nucleus at short range.
Protons, deuterons, a particles, and other ions could be accelerated in primary beams,
and neutrons could be extracted in secondary beams, all for the purpose of bombard-
ing nuclei at variable energies. The accelerators came into use, along with the
different kinds of detectors, to provide the "microscopes" for a systematic exploration
of the stable nuclei.
All the probes just mentioned are nuclear particles whose reactions with nuclei are
governed by the nuclear force. Such beam particles are ideally suited for the
unknown interaction. On the
investigation of this other hand, studies of nuclear size
and composition are more clearly interpreted if the electron is chosen as the beam
particle because the interactions of the electron are dominated by the well-known
electromagnetic force. The probing electrons see mainly the protons in the nucleus
since the main effect is the electrostatic force between charges. (Electrons also have a
weaker magnetic interaction with the neutrons in the nucleus. This effect can be
observed in domains where the electric interaction is suppressed.) Unique information
about the distribution of the nuclear charge is obtained by performing diffraction
 14-3 Electron Scattering and the Nuclear Radius 679

Figure 14-6

Schematic plan of Hofstadter's electron-scattering experiment.

Electron accelerator

nator
Collimator ^^>/^
Magnet

Scattering chamber
Slit -
==-/— Target
(^ J
Magnet

Shielding Spectrometer

experiments in which electrons are scattered by the nucleus. These data can be used to
determine the nuclear radius.
The electron-scattering experiments had to wait for the construction of high-energy
electron accelerators. A comprehensive series of investigations of nuclei was finally

undertaken by R. Hofstadter and his associates in 1953. Eventually, these studies were
extended to include measurements of the internal electromagnetic structure of the
proton and the neutron. Thus, the whole range of electron-scattering experiments gave
a description of the constituents of the nucleus as well as the nucleus itself.

Figure 14-6 shows a sketch describing Hofstadter's means of observation of the

elastic-scattering process

e + X -» e + X.

The equipment includes an electron accelerator and deflecting magnets to prepare the
high-energy electron beam, a scattering target of species X, and a spectrometer to
detect electrons scattered elastically in directions given by the indicated scattering
angle 6. This apparatus constitutes an elaborate high-energy device for the study of
electron diffraction, since the angular distribution of the scattered electrons has the
appearance of a diffraction pattern. We represent these observations by means of the
differential cross section do/dSl for elastic electron scattering, an angle-dependent
quantity analogous to the Rutherford cross section for the scattering of a particles.
Experimental values of do/dQ, are plotted in Figure 14-7 for a single beam energy
and for several nuclear targets. We see the characteristic features of a diffraction
pattern in each of the graphs, as the cross sections fall rapidly from the forward
direction at 6 = and exhibit small peaks at other angles.
The behavior of do/dQ, is similar to the diffraction of light by a spherical obstacle
with a dense interior and a diffuse surface. A good characterization of electron
scattering can be given in these terms by adopting a spherical model of the nucleus in
which the nuclear charge density has the form

p{r) = (14-2)
1 + e
(r-*)Ai
Kr
680 Properties and Models of the Hucleus

Figure 14-7

Differential cross sections for elastic electron scattering at 183 MeV. Data are plotted versus
scattering angle 6 for calcium, indium, and gold targets.

do
(barn/sr)
-2
10

10

10

10

10

10

10 8 (deg)
r
30 ,0 70 90 110

This expression is like a Fermi distribution in which the two parameters R and z,

control the r dependence. The coefficient p, is proportional to the central charge

density

P(0)
=
R/z
1 + €

so that p, and p(0) are approximately equal for R » zv We can interpret the
significance of these features with the aid of Figure The illustrated charge
14-8.
density falls through the value p,/2 at r = R, dropping from 90% to 10% of the
maximum density over a small distance given by the indicated surface thickness t.

The latter quantity is directly related to the parameter z t

in Equation (14-2). We
leave the derivation of this relation to Problem 3 at the end of the chapter.
The treatment of electron-scattering data for different beam energies and various
nuclei leads to the deduction of charge densities like the ones shown in Figure 14-9.
We select these particular results to correspond to the cross sections plotted in Figure
14-7. The graphs indicate a decrease of the central charge density p(0) and an
increase of the radius parameter R as nuclei of increasing nucleon number are
considered, while the surface thickness remains essentially unchanged. This analysis
determines a nuclear radius R that grows with mass number A according to the
 14 -3 Electron Scattering and the Nuclear Radius 681

Figure 14-8

Parametrization of the nuclear charge density

p(r)/p

-Surface
thickness
t

formula

R = R A X/3 (14-3)

and produces constant parameters with the approximate values

/ = 2.4 fm and R = 1.07 fm

over the whole survey of nuclei. Other methods of determining the nuclear radius
confirm the A dependence of Equation (14-3). In general, these techniques employ the
parameter R alone and yield values of R in the range 1.18-1.40 fm.
The decrease of the central charge density p(0) is a noteworthy feature of Figure
14-9. This behavior opposes the tendency for neutrons to outnumber protons with

Figure 14-9

Nuclear charge densities deduced from electron scattering. The cases illustrated correspond to
the nuclei considered in Figure 14-7.

p(10" C/fm 3 )

r(fm)
682 Properties and Models of the Nucleus

increasing values of A. We can blend these two opposing effects and obtain an
effective nucleon density with practically the same central value for all nuclei. We define
this quantity by noting that the density of protons in the nucleus is p(r)/Ze and by
assuming that protons and neutrons have the same distributions. The result is a
density of nucleons given by the expression

A
-p(0-
Ze

The approximate uniformity of the central value (A/Ze)p(0) over all nuclei suggests
the approximate uniqueness of the mass density for all forms of nuclear matter.
The same conclusion can be drawn from the A l/3 behavior of the nuclear radius in
Equation (14-3). If we compute the nuclear volume as

t^7tR — -^ttRqA

and identify the mass density as

M p
A 3 Mp
'
3
±77/? 477 R%

we find that our final result is independent of the number of nucleons.

Example

The following two computations of the nuclear mass density illustrate our
conclusions. We take 0.17 nucleons/fm
3
as a reasonable estimate of the central
nucleon density, and we multiply by the proton mass to obtain

A
—
Ze
p(0)M b
=
,

(0.17 fnT 3 )(l0 15 fm/m)

,
( 1 .67 X 10" 27 kg)

= 2.8 X 10
17
kg/m 3 .

Alternatively, we use the result obtained from the A x/Z behavior of R to find

3 M 3 1.67 X 10~ 27 kg
4tt R6
h
f
=
4tt (i.07 x 10" 15 m)
%= 3.25 X 10
17
kg/m3 .

By either reckoning we estimate a nuclear density of order 3 X 10

1
'
kg/m 3 an
,

3
enormous value compared to the representative figure 10 kg/m for ordinary
atomic matter.

14-4 Nuclear Mass and Binding Energy

Thomson's measurements of e/m were able to detect a difference in mass between

different positive ions of a given element. These earliest indications of isotope mass
splitting showed specifically that neon atoms could have either of the two mass
numbers A = 20 or A = 22. The notion of atomic weight had been introduced (as
 14-4 Nuclear Mass and Binding Energy 683

Figure 14-10

Layout of a typical mass spectrometer.

Electron bombardment source

V applied voltage
Pump •

magnetic field

Ion collector
Amplifier
3»i:!=rrs^-~Jfr. and
recorder

inaccurate terminology) to denote the average mass of any naturally occurring element.
It was possible to use Thomson's neon masses along with an estimate of the two

abundances and obtain an average atomic mass of 20.2, a value consistent with the
known atomic weight of neon. Eventually, the isotope concept was put forward and
the meaning of atomic weight was made clear. It was found that the atomic weight of
any element could be explained by averaging over the abundances of the correspond-
ing stable isotopes.
Thomson's experiments employed the acceleration and deflection of positive ions by
electricand magnetic fields. An improved version of his apparatus was developed in
1919 by F. W. Aston in the design of the first mass spectrograph. The instrument
separated isotopes according to their masses and gave accurate mass determinations
for the observed ions. Aston used these mass spectra to analyze the isotopic composi-
tions of more than 50 elements. He showed that the isotope masses were nearly equal
to integral multiples of the hydrogen mass, and he found that the small deviations
from whole-number multiples could also be measured in more refined experiments.
Measurements mass provided direct information about properties of the
of the atomic
nucleus. The measured deviations from whole numbers proved to be especially
significant as clues to the binding of the nucleus. Mass spectrometry flourished in the
1930s because of improvements in detector design and vacuum technology. The mass
spectrograph demonstrated its practical value as a separator of isotopes in 1935 with
the discovery of the rare long-liveduranium nuclide 235 U.
Figure 14-10 shows the design of a mass spectrometer for the isotopic analysis of
gaseous elements. The apparatus admits a sample of gas at low pressure and
bombards the atoms with electrons to convert the sample into positive ions. Electric
and magnetic fields guide the charges to an ion detector where the ions are collected
separately according to mass. The ions are accelerated to speed v by an applied
voltage V and are then deflected in a circular path of radius R by a magnetic field of
strength B. Nonrelativistic ions with mass M
and charge e acquire a kinetic energy

M
— 2
v = eV
2
684 Properties and Models of the Nucleus

Figure 14-11

Mass spectrum of xenon indicating the relative abundances of the nine stable isotopes.

Xe

134
136

128
126 124
A. A —k—

and experience a centripetal force

Mv'
= Bev.
~R~

The ion speed can be eliminated between these two equations:

Ml — e
v = BR - BR
M M
The quantity of interest in the last equality is the mass-to-charge ratio

M (BR)
2

(14-4)
t IV

The mass spectrometer operates at fixed values of B and R and employs a varying
voltage V in order to collect ions with various M/e ratios. This technique produces
mass spectra like the one sketched in Figure 14-11. Note that the output signal from
the ion detector provides a measure of the relative abundance of each isotope.
Masses can be measured more precisely by comparing unknowns with certain
carbon-bearing calibration standards. Let us illustrate by considering a sample

containing atomic and molecular ions of hydrogen, deuterium, carbon, oxygen, and
methane. The resulting mass-spectroscopic lines include the following three M/e
doublets:

+ + + +
('H'H) - 2H + , (
2
H H 2 2
H) - 12
C++ , and (
12
C H H'H H) - 16
, 1 1
,

+
where the symbols ( • • •
) refer to singly ionized molecules. We note that the two
 144 Huclear Mass and Binding Energy 685

members of each doublet have the same nominal value of M/e, and we find that a
small line splitting appears in the mass spectrum at the location of each pair. We can
measure these three splittings and use the results to deduce the masses of 'H, 2 H, and
16 12
relative to the mass of C. Problem 5 is included at the end of the chapter to
illustrate this procedure.
These investigations of ions in mass spectrometry provide the means of determining
the masses of neutral atoms, each with its full complement of atomic electrons. A
representative listing of atomic masses is provided along with other pertinent nuclear
data in Appendix A. By convention, the quoted values have atomic mass units (symbol
I2
u), defined such that the commonly occurring neutral carbon atom C has the
ground-state mass value

M{ X2 C) = exactly 12 u.

The rest-energy equivalent of this unit of mass turns out to be

2
uc = 931.49432 MeV.

These numbers are discussed somewhat further in the examples below.

The relativistic concept of rest energy plays a major role in the behavior of nuclei,
unlike the situation in the case of atoms. We recall that the rest energies of the nucleus
and the electrons are discounted ab initio in the analysis of the energy states of the
atom. We cannot argue that these contributions are negligible, for in fact the rest
energies of the constituents of the atom are much larger than the excitation energies of
the atomic levels. Instead, we note that atomic processes are low-energy phenomena in
which the constituents of the atom cannot transform into different species. Since the
masses and rest energies maintain their identities, it is consistent to leave these
quantities out of the analysis. The same argument does not hold for nuclei because
nuclear excitation and nuclear transformation involve comparable energies. We must
reinstate the rest energy when we define the nuclear binding energy, and we must take
account of changes in mass when we apply the conservation of energy to processes of
nuclear transformation.
Binding energy is a property of any aggregate of particles bound together by
attractive interactions. The rest energy Mc 1
is identified as the total relativistic energy
of such a system in its center of mass frame. This energy consists of the rest energies
for the constituent masses M along with the kinetic and potential energies of the
system. The total potential energy must be attractive to bind the particles and may be
defined to vanish for particles at infinite separation. The energy of separated con-
2
stituents at rest therefore consists only of the total rest energy L,M (
<: . This quantity
must exceed Mc* if the mass M corresponds to a bound state, and so the difference
between these rest energies determines the binding energy of the system:

Eb =Y,M c -Mc t
2 2
. (14-5)

In practical language, the quantity E b

represents the difference in energy between the
disassembled and the assembled collection of particles.
Let us apply the general formula for binding energy to atoms first and then return
to nuclei. For a neutral atom with Z electrons we have

£ 6
(atom) = [Af(nucleus) + Zm - M(atom)]c 2
r
. (14-6)
686 Properties and Models of the Hucleus

This atomic binding energy has values like 13.6, 13.6, and 79.0 eV for hydrogen,
deuterium, and helium and becomes as large as hundreds of keV for atoms of much
larger Z. In all cases we can justifiably ignore such comparatively small quantities
whenever we examine the binding properties of the corresponding nuclei. Equation
(14-5) tells us that the binding energy of a nuclide with Z protons and A r
neutrons is

given in terms of the masses of these constituents as

£ A
(nucleus) = [ZMp + NM n
- M( nucleus) ] c
2
. (14-7)

We can eliminate the nuclear mass between the last two relations and replace the left

side of Equation (14-6) by zero in the process to get

£ 6
(nucleus) = [ZMp + NM n
+ Zm - M(atom)]c 2
e
.

The combination M p
+ m can e
be set equal to the mass of the hydrogen atom since it

is safe to neglect the small 13.6 eV of atomic binding energy. The final formula for
the binding energy of the nuclide
A
X then assumes the following explicit form:

E b(
A
X) = [ZM('H) + NM n
- M^X)]^, (14-8)

in which the symbol M{ A X) refers to the mass of the neutral atom. This version of the
formula expresses the desired quantity in terms of masses found directly from mass
spectrometry. These atomic masses are listed as neutral-atom properties in Appendix
A. We can extract the corresponding nuclear masses if we wish by simply subtracting
the masses of Z electrons.
Figure 14-12 illustrates an interesting systematic property of the nuclear binding
energy. The graph shows the binding energy per nucleon E /A
b
for the various nuclides,
plotted as a function of the number by the fact that an
of nucleons. We are struck
approximate plateau is reached around the value 8 MeV per nucleon for all nuclei
beyond A = 16. This behavior indicates a saturation phenomenon that reflects the
short-range nature of the nuclear force. A long-range force would subject a nucleon to
binding interactions with all the other A — 1 nucleons in the nucleus and would cause
the binding energy of each nucleon to grow with A. Instead, the binding energy per
nucleon saturates around a particular energy and tells us that each nucleon experi-
ences binding interactions with only a limited number of nearest neighbors in the
nucleus. We also observe a slight decline in the plateau at larger values of A. This
secondary feature indicates the growing effect of the Coulomb repulsion between
protons to reduce the nuclear binding in larger nuclei. We have already seen such
behavior in the tendency for neutrons to outnumber protons at the higher values of A
in Figure 14-4.

The formulas for the binding energy can be employed to introduce the useful
concept of neutron separation energy. This quantity is defined as the binding energy of
the last neutron in the assembly of nucleons

A- I

X + n^iX.
We adapt Equation (14-5) to this definition and write the separation energy accord-
ingly:

~l
E„(
A
X) = [M( A X) + M n
- M( A X)]c 2 . (14-9)
 144 Nuclear Mass and Binding Energy 687

Figure 14-12

Binding energy per nucleon versus nucleon number. A smooth curve is drawn through the
plotted points indicating the positions of several of the stable nuclides. Values of E b
are taken
from tables compiled by A. H. Wapstra and K. Bos.

%Mev) 56 84
40 Ca
JX Kr 120 Sn

197
Au 208p b

o 3 He

o2H

40 8i 120 160 200

Note that the species X maintains its identity throughout since Z does not change with
the removal of a neutron. We can use Equation (14-8) to convert the formula for E n
into the difference of nuclear binding energies for the two isotopes:

EH ( A X) = {[ZM( H) + l
(A - 1 - Z)M,y - Eh (
A - l

X)} + M n
c
2

- {[ZM('H) + (A -Z)M n
]c
2
- Eb ( A X)}

= Eb ( A X)-Eb ( A - l
X). (14-10)

Both formulas for E n are of some interest. The second version is a clear statement of
the distinction between the binding energy of the last neutron and the nuclear binding
energy. The statement tells us that the latter quantity is the larger of the two energies.

Example

2
The atomic mass unit i i is defined in terms of the carbon standard as £Af(> C).
Let us convert the unit to kilograms with the aid of Avogadro's number:

1 12 g/mole
u = (io-
3
kg/g) = 1.6606 X 10"
21
kg-
23
12 6.0221 X 10 /mole
688 Properties and Models of the Nucleus

The corresponding rest energy is

ik
2 =
(1.6606 X 10" 27
1.6022 X 10" 13 J/MeV
8
kg)(2.9979 X 10 m/s)~
^-p: — = 931.50 MeV.

This conversion factor is used over and over in nuclear physics calculations.

Example

Carbon appears on the nuclear chart with the following data for the two stable
12
isotopes C and 13 C:
atomic mass (u) exactly 12 13.00335482
isotopic abundance (%) 98.90 1.10

We can calculate the average atomic mass by combining these numbers as

follows:

0.9890(12) + 0.0110(13.00335482) = 11.868 + 0.143 = 12.011.

This result agrees with the quoted value for the atomic weight of carbon.

Example

Equation (14-8) may be used in conjunction with the atomic masses in Appendix
A compute the binding energy for any
to of the tabulated nuclei. In the case of
4
He we take Z = N = 2 and obtain

£ 6(
4
He) = [2(1.007825) + 2(1.008665) - 4.002603] (931. 5 MeV)
= 28.30 MeV.

For
12
C we take Z= N= 6 and get

£,(
12
C) = [6(1.007825) + 6(1.008665) - 12] (931 .5 MeV) = 92.16 MeV.

Note that large cancellations take place inside the square brackets and that both
calculations employ the conversion from uc~ to MeV. The binding energies per
nucleon in the two cases are

E b
28.30 MeV
= = MeV
T( 4He )
A 4
7.075

and
92.16 MeV
= 7.680 MeV.
A 12

These results appear to be well on their way toward the approximate universal
4
value 8 MeV. (Actually, the He figure is unusually large, lying well above the
rising portion of the data plotted in Figure 14-12.)
 14-5 The Semiempirical Mass Formula 689

Example

Finally, let us illustrate the idea of neutron separation energy by applying the
formulas to some of the isotopes of cadmium. Equation (14-9) is particularly
suitable because the relevant masses are listed in Appendix A. We consider the
separation energies for the two cadmium nuclides
113
Cd and 114
Cd. For A = 113
we find

£„(
113
Cd) = [M( 112 Cd) + M n
- M( 113 Cd)]c 2
= (111.902758 + 1.008665 - 112.904400)(931.5 MeV)
= 6.542 MeV,

and for A = 1 14 we find

£„(
1,4
Cd) = [M( 113 Cd) + M„ - M( ni Cd)]c 2
= (112.904400 + 1.008665 - 113.903357)(931 .5 MeV)
= 9.043 MeV.

We use these two results again when we continue this illustration at the end of
Section 14-5.

14-5 The Semiempirical Mass Formula

The binding energy of a nucleus defines the position of the ground state on a nuclear
energy level diagram. This state, and all the higher excited states, should be de-
terminable from a theory of the nuclear force. We recognize, however, that any
attempt to solve the quantum problem of the binding of many nucleons would be a
most ambitious undertaking. Our approach takes a more deliberate course and turns
first to some rather elementary models. We aim these models at the nuclear ground

state and direct our attention to the systematic features displayed on the nuclear chart.
Let us begin with an early model, introduced von Weizsacker, in in 1935 by C. F.

which the nucleus is compared to a classical liquid droplet A certain resemblance exists .

between the two systems since the density and binding energy per nucleon are
essentially independent of the number of nucleons in the nucleus, while the density
and latent heat of vaporization do not vary with the number of molecules in the
liquid. Weizsacker's model also takes account of the Coulomb forces among the
nucleons as well as the quantum effects associated with nucleon spin and fermion
antisymmetry. The end result is a parametrization of the atomic mass as a function of
A and Z. The predictions pertain to the nucleus as a whole without reference to the
individuality of the nuclear constituents.
We construct the Weizsacker formula by identifying five different contributions to
the nuclear binding energy E The
b
. first effect is analogous to a heat of vaporization,
written as Lv M mo]ecul(,n, where n denotes the number of molecules in a drop of liquid
with latent heat per unit mass Lv . In the case of the nucleus we associate a similar
number dependence with the plateau behavior of E /Ab
in Figure 14-12, and we write

E = b\
a \
A

as the leading term in the binding energy. This piece of E b

is called the volume energy
 ,

690 Properties and Models of the Nucleus

since the linear dependence on A is related to the volume of a sphere whose radius
varies as A i/3 in the manner of Equation (14-3).
We
have already interpreted the A independence of E b /A in terms of a fixed
number of internucleon bonds for a nucleon in any nucleus. The nucleons on the
nuclear surface are not surrounded by as many of these bonds, and so the binding
energy is reduced by a surface correction of the form

Eh2 = -a 2 A 2/\

This dependence on A corresponds to a quadratic behavior in R describing a

correction term proportional to the spherical surface area of the nucleus.
These two bulk-liquid contributions to E h must be supplemented by the Coulomb
energy due to the repulsion between protons in the nucleus. We use the formula for the
potential energy stored in a uniform sphere of charge Ze and radius R,

(Zef 3
V= +-- — (14-11)
5 47TE R

and we turn again to the relation between R and A in Equation (14-3) to obtain

Z2

as the electrostatic contribution to E h

. (The derivation of Equation (14-11) is given as
Problem 7 at the end of the chapter.) Note the change in sign between the quantities V
and EbV
The classical nature of these first three terms is immediately apparent. It is also
clear that the construction of E b
is not yet complete since the three terms alone predict
that the most stable nuclei should occur for Z= and A = N. We must include
another effect associated with the fermionic properties of the nucleons. Figure 14-4 has
told us that the existing nuclides lie near the line Z= N, corresponding to equal
numbers of protons and neutrons. We have attributed this systematic feature of the
nuclear chart to the influence of the exclusion principle. Let us continue to defer the
interpretation of the effect and use empirical grounds to introduce another term called
the symmetry energy:

2
(A/2- Z)
*4
= ~° A '

The numerator of this expression behaves as (N — Z) and reduces the binding

2

energy as nuclides deviate to either side of the line Z = N, while the denominator
preserves the necessary linear dependence on A. We develop a special model in
Section 14-6 to explain this term in context with the meaning of the line Z= N.
Wehave also noted the overwhelming preference for stable even-/l nuclides to
occur in the even-even, rather than the odd-odd, category. This observation has been
taken as evidence for the pairing property of the nuclear force. Let us provide for
pairing in phenomenological fashion and include a contribution to E b
called the
pairing energy, which applies only for even A and favors specifically the even-even
 14-5 The Sent/empirical Mass Formula 691

nuclei. We introduce such a term by adopting the following expression:

'5 even-even
± ^3/4 odd -odd
Ebb £5

even -odd and odd even.

It has been found that this formula gives a good empirical representation for the A
dependence of the pairing effect.
The nuclear binding energy is assembled from these five terms:

E b(
A
X) = a x
A - a2A
2
^- a3
Z2
-^ - a,
(A/2-Zf
— + e5 . (14-12)

If we combine this expression with Equation (14-8) we obtain a simplified semiem-

pirical version of Weizsacker's formula for the atomic mass:

M( A X) = ZM('H) + (A - Z)M„
(A/2- Zf 2
2/3
{
A - a2 A - «3^T7J - aA /c . (14-13)

(Actually, the fifth term in the binding energy is a more recent addition to the original
model.) The formula is called semiempmcal because the various constants are de-
termined by securing a best fit to the atomic masses and not by invoking any further
theoretical arguments. An excellent fit is obtained with the following parameters:

a, = 15.76 MeV,
a2 = 17.81 MeV,
a3 = 0.7105 MeV,
a4 = 94.80 MeV,
a5 = 39 MeV.

Remarkably, this five-parameter prescription for A/(

4
X) is accurate to a few MeV
with only occasional exceptions across the whole nuclear chart. The exceptional
deviations are significant in their own right as indications of shell structure in nuclei.
We can isolate the Coulomb term Eb3 from the other contributions to Equation
(14-12) by considering the binding energy of the two isobars

A
Xy and *YX .

These species are related by the interchange of proton and neutron numbers Z and iV
and are known as mirror nuclides. The interchange operation Z <-> N affects only the a 3
term in the formula for Eb and so the difference of binding energies turns into the
,

expression
2 2

Eb ( A X)-Eb { A Y) = a/—^-. (14-14)

Hence, the difference in binding energy is the same as the difference in Coulomb
692 Properties and Models of the Nucleus

energy for any pair of mirror isobars. Furthermore, the nuclei in question have equal
radii corresponding to the given value of A. We can take advantage of this
observation and determine the common radius by using measurements of E b
in
conjunction with the formula for the Coulomb energy in Equation (14-11). We
illustrate the procedure in the second example at the end of this section.
The mass formula offers many useful insights into the stability properties of nuclei.
We can establish a criterion for stability if we organize the nuclides as isobars and
examine the variation of the masses with regard to the (A, Z) dependence predicted
by the formula. We select a set of isobars by choosing a fixed value of the mass
number A, and we note that the chosen nuclides have nearly equal masses. Equation
(14-13) describes these species by a quadratic function of Z, which minimizes as Z
varies for constant A. The minimum is determined by the vanishing of the partial
derivative

dM . . Z Z-A/2
-c 2 =
,1/
[Af('H) - M„]c 2 + 2a 3 -^
A l/3
+ 2a,-

The minimizing charge number has the value

A a4 + [M„-M( l
H)]c 2
Z = ZA = (14-15)
a4 + a^A 2/z

Thus, we predict a stable isobar at ZA , where the lowest isobar mass occurs for the
given mass number A. Of course, this minimizing value of Z should not be expected
to coincide with a true integer-valued atomic number. The actual state of affairs is

illustrated for three consecutive choices of A in Figure 14-13. The e5 term makes no
contribution to the formula when A is odd, and so Equation (14-13) represents a
single parabola opening upward on the corresponding graph of versus Z. When A M
is even the e5 term adds a constant shift to the other contributions on the graph,
lowering the even-even masses and raising the odd-odd masses relative to the central

Figure 14-13

Isobar masses versus atomic number for three consecutive values of the mass number. The
stable isobars are ™Mo and ™|Ru for A = 98, ^Ru for A = 99, and '$Mo and '^Ru for

A = 100.

M M M

97.92 - 9892 99 92-

even^ odd
V v-odd
-even

97 91 - 9891 9991
V\Tc
Mo " Ru
A = 98 A = 99 A = 100
1 1 l
1 ,
1 1 I I III z
38 40 42 44 39 41 43 45 40 42 44 46
 14-5 The Semiempirical Mass Formula 693

parabolic curve.The figure employs two parabolas in this case to show how the
measured masses hop sequentially between the even-even and odd-odd isobars. The
minima on the curves lie close to the indicated integer values of Z at which the stable
nuclides occur.
Equation (14-13) determines a mass surface in the variables A and Z. Figure 14-13
shows three slices at constant A through the surface, with minima corresponding to

the quantity Z 4 (Obviously, there are three surfaces: one for odd A, and two more for
.

the even-even and odd-odd varieties with even A.) These graphs furnish a clear
picture of the valley of stability to supplement our previous discussion of Figure 14-4.
Let us conclude our observations about stability with the following incidental
remarks. We note that nuclides of technetium appear in all three parts of Figure 14-13
and that none of these species is stable. In fact, no stable jTc nuclide exists for any
value of A. Technetium at Z = 43 and promethium at Z = 61 are unique in this
respect since these are the only elements with no stable isotopes in the domain of
stable elements below bismuth at Z= 83.

Example

The constant a 3 is the only parameter in the mass formula to be associated with
a specific theoretical prediction. If we compare Equation (14-11) to the expres-
sion for E h3 and use Equation (14-3), we find

3 ahc
,1/3
5 4we R A*
/:i
5 4ire R 5 R

(The fine structure constant has been introduced here to simplify the numerical
work.) Since a 3 is regarded as known from the empirical fit, the relation yields a
determination of the radius parameter:

3 ahc 3 197.3 MeV •

fm
A\ = 1.216 fm.
5 a3 " 5 (137.0)(0. 7105 MeV)

This one-parameter evaluation of the nuclear radius is judged to be in good

agreement with the result R = 1.07 fm obtained from the two-parameter
electron-scattering method of Section 14-3.

Example

The A = 15 mirror nuclides 'yNg and 's0 7 have atomic masses 15.000109 and
15.003065 u, respectively. The difference of binding energies is obtainable from

Equation (14-8):

A = £ A ( 15 N) - £„(
15
0)
= [7Af('H) + 8M - M( n
,5
N)]c 2 - [8M( H) + l

lM - M( l5 0)]c 2
n

= {[Mn - M( H)] + [M( O) l {b

-M( 15
N)])r 2

= (0.000840 + 0.002956)(931.5 MeV) = 3.536 MeV.

694 Properties and Models of the Nucleus

We have identified this quantity with the difference in Coulomb energy. Let us
consult Equation (14-11) and take Z= 1 and 8 to get

3 e cchc
V8n - V = -(64
V n
7
- 49) = 9
5 477e tf R

as an alternative expression for the quantity A. Note that R has the same value
for the two isobars since R depends only on A. We calculate the radius from the
result obtained for A,

atic MeV-fm 197.3

R = 9—
A
= 9-
(l37.0)(3.536MeV)
= 3.666 fm,

and we then predict the radius parameter R from Equation (14-3):

R =
()
—Rl/3
7-R =
3.666
m— l/3
fm
= 1-487 fm.
A 15

Other pairs of mirror nuclides also give values for R in the vicinity of 1.5 fm.

Example

We can get an approximate isolation of the pairing term E b5 if we examine the

binding energies of three isotopes with consecutive mass numbers A — I, A, and
A + 1 ,
provided we take the central mass number A to be odd and the common
atomic number Z to be even. Under these conditions E h ( A±i X) includes the
contribution +a b /(A ± 1)
3//4
, while E b(
A
X) contains no e5 term. We can then
prove to first approximation that the three binding energies obey the relation

\[E b{
A
^X) + i^X)] - £,('
4
X) = -^ + ... .

(The proof is left as Problem 1 1 at the end of the chapter.) The left side of this
relation can be written in terms of two particular neutron separation energies as
follows. Equation (14-10) gives the equalities

E„(
A + l

X) = E b (
A+
>X)-E b(
A
X) and E„(
A
X) = E ( A X) - E ( A ~
b b
l
X),

and subtraction of the two quantities gives the result:

H^ + ,

X)-£„('4 X)] =i[£A (^ + 1

X)+^- 1
X)] -E b(
A
X).

Thus, our two conclusions lead us to a determination of a 5 using neutron

separation data. We refer back to our cadmium calculations at the end of
Section 14-4 and find

-[£„(
.
U4 Cd) - EB ("'Cd)] =
. 9.043
~ — - 6.542
-MeV= 1.251 MeV=
T ^
a5
7?
.

The result, a b = 43.35 MeV, is a bit larger than the average value given for this
constant in the text.
 14-6 The Fermi Gas Model 695

14-6 The Fermi Gas Model

Nucleons behave as fermions and obey the Pauli principle. Hence, the protons and
neutrons in the nucleus are influenced by the same constraint of fermion antisymmetry
as the electrons in the atom. We know that the Coulomb force and the exclusion
principle determine the structure of the atom, and we suppose that a similar
construction works just as decisively in the case of the nucleus. Nuclear binding is a
very different dynamical problem since the constituents attract each other with a
strong short-range force and the system as a whole has no obvious center of attraction.
Nevertheless, we are able to adopt an independent-particle central-field approach as
one of the avenues in our study of the nucleus. We find that this familiar outlook
enables us to draw several important phenomenological conclusions.
Let us begin with a qualitative argument to explain why the nucleus prefers a
composition of equal numbers of protons and neutrons. The nuclear force is not
needed in any detail since the exclusion principle is the main ingredient in this

explanation. We know that the Coulomb repulsion between protons distorts the
systematic Z=N property in favor of neutrons for the larger nuclei, so let us consider
the smaller nuclei and ignore the Coulomb effect. An individual proton or neutron is
then subject to the same average force arising from all the other nucleons. Figure
14-14 shows a short-range central potential energy to represent the influence of this

force on a single nucleon. Also shown are the resulting single-particle energy levels,
analogous to those found in the central-field model of the atom. (We ignore the
angular momenta of the levels since these additional properties do not affect our main
conclusion.) The exclusion principle allows us to fill each level with no more than two
protons and two neutrons corresponding to spins up and down. The example in the

figure describes two occupation schemes for A nucleons with different assignments of
Z and N. We see that the binding energy of the last nucleon is greatest for the

Figure 14-14

Independent-nucleon potential energy and qualitative energy levels in a central-field model of

the nucleus. Coulomb effects are ignored and orbital angular momentum considerations are
suppressed. In an A = 21 system, the neutron separation energy E n is greater for the (Z = 10,
N= 1 1) configuration than for the neutron-laden (Z = 6, N= \5) case.

. , .

&
vy
fn\ f^l
~\nj-\nj

-<&-

-<£H?M»H|)- —(J)-(n)
—(p> -®" —®~~®—
{P)—{P) —(n)—(n) —(p> -0- —®~~vV—
—(p> -®- —©-vy
Z=10 N=ll z = 6 N= 15
 :

696 Properties and Models of the Nucleus

configurations closest toZ = N, and we conclude that these circumstances are the
most favorable for nuclear stability.
We can employ fermion antisymmetry, and little else by way of input, to justify the
expression given for the symmetry energy in Section 14-5. Our procedure retreats
temporarily from the independent-particle picture and takes an average over the
detailed dynamics of the nucleons. The nucleon number A
assumed to be rather is

large for this purpose so that the nuclear system becomes vast enough to warrant the
use of quantum statistics. We treat the nucleus as a large collection of protons and
neutrons moving freely in a spherical enclosure defined by the nuclear volume, and we
describe the system as a degenerate Fermi gas in which the nucleons occupy their
lowest energy states consistent with the exclusion principle. To be specific, we let the
zero-temperature Fermi-Dirac distribution function be the sole vehicle for the descrip-
tion of the nuclear particles. The proton and the neutron are distinguishable from
each other, and so the exclusion principle and the methods of Fermi-Dirac statistics
apply to the two types of nucleon separately. Thus, the resulting nuclear system is
regarded as a mixture of proton and neutron Fermi gases.
We can adapt this picture to the independent-nucleon point of view with the aid of
Figure 14-15, in which we introduce a constant potential energy well for the free
motion of each individual bound particle. Since A is large we must incorporate the
effect of Coulomb repulsion for the proton and employ wells of different depth for the
two types of nucleon. A large number of energy levels is assumed in each case, and all

are presumed to be fully occupied by the gases of neutrons and protons up to the
indicated Fermi energy levels. Note that the Fermi energy and the number of particles
are larger in the case of the neutrons because the Coulomb effect diminishes the
nuclear attraction and elevates the well in the case of the protons.
The Fermi gas model of the nucleus follows directly from our zero-temperature
results of Section 11-6. We only need to modify the formulas for separate application
to neutrons and protons. The nucleus has a spherical volume determined by the mass
number A
V = \mFO = \mR\A.
We express the nucleon numbers in terms of the respective Fermi energies as in

Figure 14-15

Neutron and proton potential energy wells in the Fermi gas model. The proton potential energy
is elevated by the effects of Coulomb repulsion.

Vn (r) Vp (r)

Neutron gas Proton gas

 14-6 The Fermi Gas Model 697

Equation (11-72):

i/2
(2M)
z= .,.
3
Ve 3 / 2
for protons (14-16)

and

(2M) V2
N= , Vs
3
/ 2
for neutrons (14-17)

(The proton and the neutron are assigned the same mass throughout this M
discussion.) We
then introduce our expression for the nuclear volume and invert these
relations to solve for the Fermi energies:

b
> 2M
I 3v 2 h 3
V
z\
\

J
2/3

= —
h

2M\
2

-A
I

-.
—^z\
3tt

±itR
3
2

A
\
2/3

977 Z \
2 /3

(14-18)
2MRl\ 4 A

and

!r , 9v7 A \
2/:)

" = jm?\t^) < 14 - 19)

Equation ( 1 1-74) gives the total energy of the particles in each gas as a function of the
number of particles and the Fermi energy. We use this result to obtain

2 2/3
3 3 h (9ttZ\
Ey=
z —ZipF = -Z\
5 " 10 MR 2
\ 4 A

-V 3 2 5 /3
3 / 977 \ h I Z\
10 \ 4 / MR~ \ A

for the proton gas, and

3 / 977 \
2/3
h
2
IN\
v
~ To t) A/^f It

for the neutron gas.

We are concerned with the symmetry energy of the nucleus due to the deviation of
the proton and neutron numbers from the equality Z= N= A/2. Let us introduce a
new variable £ accordingly by defining

A A
N= - + £ and Z= - - £
698 Properties and Models of the nucleus

and evaluate the relevant factors in Ez and EN by the following binomial expansions:

+
n 5/3
/ 2f\
5/3
/ 2f\
5 /3

1
" ^ + l+
a) U) 2 J [I j [ AJ
M 5/3
r 5 2i
+
5/2f\ 2

2/ [
" 3 A 9\T
5 2f
+ 1 +
3 A
+ -
9\ A
5 /
—
2f\

2 3 2
1\ / / 20 f
1 + +
2 \ Ta->

The total energy of the system of nucleons then takes the form

2 2
3 / 9tt\ 2 / 3 k ( 1\ 2 / 3 / 20 £

2
3 ,„ h 20 £*
-(9tt);
V3 A + (14-20)
40 MR* 9 /I

to second order in f. This quantity contributes to the rest energy of the nuclide ^X
and must therefore appear in the mass M( A X.) as parametrized in Equation (14-13).
We use f = A/2 — Z and rewrite the second-order term in Equation (14-20) in the
form
/J
(9irr h
2
(A/2-ZY
MR*

This final result reproduces the contribution of the symmetry energy to the atomic rest

energy M^X)*: 2 A . numerical exercise is provided in the examples below to complete

the comparison.
In closing let us offer some justification for the independent-nucleon theory of the
nucleus and indicate especially how the exclusion principle supports this point of view.
The any two nucleons is strong enough at short range to cause a
interaction between
rapid transfer of energy and momentum between the nuclear particles. It would seem
that a given nucleon must undergo a prompt dispersal of its energy in nuclear matter
and have little opportunity to experience the smoothly varying interaction suggested
by Figure 14-14. A competing theory would argue that the behavior of any given
particle disappears at once from the memory of formation of a nuclear state, so that
the nucleus should be treated as a whole compound instead of a collection of
distinguished constituents. In fact, for a low-energy system like the nuclear ground
state, the exclusion principle inhibits these energy-transferring rearrangements by
preventing the particles from moving into the fully occupied low-lying states. Under
such conditions the independent nucleon sees the nucleus as a medium which the
in

strong nucleon-nucleon interaction is moderated by the effects of fermion antisymme-

try. The alternative compound-nucleus point of view becomes more important in

nuclear reactions, where the higher energy permits access to the unfilled higher states.
 14-7 The HucleonHucleon Interaction 699

Example

2
Let us connect the £ term in Equation (14-20) with the a 4 term in Equation
(14-13) by identifying the constant coefficients in the two expressions:

2 3
(9tt)

MR*'

If we set R = 1.2 fm and take Mc 1 = 939 MeV, we find that our statistical
model predicts

.2/3
/3
(Sir)"* (he)' (9ttY (197 MeV -fin)'
4
- = 44 MeV.
a \a-1d2
Mc'Rq 6 (939MeV)(l.2fm)'

Recall from Section 14-5 that the atomic masses are fit with a A = 94.80 MeV.
The agreement is only qualitative, as befits the crudeness of the model.

Example

If we ignore the £ dependence altogether and set Z = • N= A /2, we find from

Equations (14-18) and (14-19) that the nucleon Fermi energy is independent of
A:

* 977 \
2 ^
. -
F I
2MRl\

The numerical value of this quantity is

2/3
(9tt) h* 3
Ef ~ ~ -a 4 = 33 MeV,
8 MRl

using the result of the previous example, Figure 14-15 then tells us that the
depth of the potential energy well must be of order 40 MeV if a typical nucleon
has separation energy around 7 MeV.

14-7 The Nucleon Nucleon Interaction

The models in the last two sections are concerned with the global properties of all
nuclei and not with the details of nuclear structure. Let us set these first observations
aside now and take up the structural approach, beginning with the most primitive
nuclear system.
The fundamental problem of nuclear physics is the determination of the force
between two nucleons. We can probe the basic two-nucleon system to study this
unknown interaction by scattering nucleons from a proton target and by examining
the properties of the nucleon-nucleon bound state. The deuteron is the only existing
A = 2 nuclide in the latter category. This bound system of proton and neutron is
unique since there are no excited pn structures and no analogous pp or nn counter-
700 Properties and Models of the Nucleus

parts. We find that several important features of the nucleon-nucleon interaction can
be inferred from the deuteron, while many other details of the force can only be
learned from the higher-energy processes of nucleon-nucleon scattering.
Let us compile the following principal characteristics of the deuteron (symbol d)
and interpret the various properties afterward:

binding energy /H) = 2.225 MeV

nuclear spin and parity i" = 1
+

magnetic dipole moment V d = 0.8574 n N

electric quadrupole moment 10~-33
= 2.82 X 10 barn
Q
Q. d e

nuclear radius Rd = 2.1 fm

Each of these quantities is known from a number of experimental sources. One way to
measure the deuteron binding energy is by observing the energy of the y rays emitted
in the np capture reaction

n + p -» d + y.

The deuterons are formed in this process when slow neutrons from a reactor are
absorbed by protons in a hydrogenous target. The small value of Eb corresponds to
just over 1 MeV per nucleon, the lowest point plotted on the graph in Figure 14-12.
The nuclear spin and magnetic moment are determined from measurements of atomic
hyperfine structure and from magnetic-resonance experiments. The quadrupole mo-
ment is obtained by other applications of the beam-resonance technique. We define
the quadrupole moment below and interpret the quantity as an indicator of the
nuclear shape. The nuclear radius is measured in electron-scattering experiments as
discussed in Section 14-3. Recall that these measurements also provide a picture of the
nuclear charge distribution.
We assemble the nuclear spin vector of the deuteron by adding the spins of the
proton and neutron to the orbital angular momentum L of the proton-neutron sysem:

I = L + S, + S„. (14-21)

A highly schematic picture of this construction is shown in Figure 14-16. Note that S.
and S„ are nuclear spin vectors themselves, each with quantum number i = | (or,

equivalently, s = r,), while the deuteron has nuclear spin quantum number 7=1. We
can generalize Equation (14-21) immediately and give the following formula for the
nuclear spin of any nucleus consisting of Z protons and neutrons: N

1= £(L, + S„)+ L(L + Sj.

4
n< (14-22)
k=\ k=i

We already know that the vector I and the quantum number are related by the rules i

of angular momentum quantization. Thus, the I 2 eigenvalue defines i by the

equation

I
2
= h
2
i{i+ 1),

and the I, eigenvalues define 2i + 1 quantized orientations of I by the property

Iz = hm l
with m = — i,l
. .
.
, i:
in integer steps.
 14-7 The Hucleon- Hucleon Interaction 701

Figure 14-16

Nucleon-spin and orbital contributions to the

spin of the deuteron. The quantized angular
momentum vectors are represented
symbolically, as in the vector model of Figure
8-23.
I

M
L

(-)

This construction endows a nuclide with half-integral spin if A is odd or integral spin
if A is even. We include a listing of nuclear spins in Appendix A, and we observe that
the deuteron is an even-A nuclide with three quantized spin orientations for nuclear
spin i=l.
We recognize the expressions in Equations (14-21) and (14-22) as exact analogues
of the formula for the total angular momentum J in the theory of complex atoms. We
know from Section 9-8 that we can describe an atomic state in the LS-coupling
scheme by the notation 2s f '£,, provided we can regard / and s as good quantum
numbers for the total orbital and spin vectors L and S. It is valid to adopt the same
spectroscopic notation for nuclei, under analogous dynamical conditions, and simply
substitute the quantum numbers i and m in place of j and m t
•.

The nuclear magnetic moment fi is also composed of contributions from the

constituents of the nucleus. In the case of the deuteron we expect a term due to the
orbital motion of the proton and another two terms due to the two nucleon spins, as
suggested again by Figure 14-16. The general result for a magnetic dipole moment is

quoted experimentally as an expectation value of fi z evaluated in the state of ,

maximum I, where m = i. This measured quantity is a source of information about

l

the state of the bound nucleons, although the interpretation in terms of nuclear
structure is likely to be quite complicated for most nuclei. We can interpret the result
for the deuteron at once, however, by noting the near equality between \i d and the
sum of the magnetic moments of the proton and neutron:

Ax^ = 0.8574 ju
A . and /i, + ju„ = 0.8798 fi N .

(The data for the second figure are taken from Section 14-1.) It would appear that
almost all of the deuteron moment can be explained by assuming a parallel-spin s = 1

configuration for the proton and neutron in an tf= orbital state. The /=
assignment is expected if the ground state of the two-body system is governed by a
central force. The combination of (= with s = 1 is also consistent with the known
value i = 1 for the nuclear spin. If we can treat ( and s as good quantum numbers
+
particles subject to the nuclear force, then we can invoke the notation
:

for two L,
+
and refer to the 1
3
deuteron as a 5, two-nucleon state. Note that the /=
assumption agrees with the assignment of positive parity.
702 Properties and Models of the nucleus

Two spin- nucleons can form states with total spin quantum numbers s = and
-,

s = 1. The nuclear interaction between the two particles is evidently spin dependent
since an / = bound state exists for s = but not for s — 0. To model this situation
1 ,

we might assume a central interaction for the main part of the nuclear force and add
an extra spin-dependent piece to make the nuclear attraction greater for parallel
spins. The added feature is analogous to the hyperfine effect discussed in Section 8-12.
We have seen how the interaction of spin magnetic moments in Equation (8-58)
reduces to a spin-spin coupling, and we might consider the adoption of a similar
coupling here. An expression of the form S^, • S„ can produce the desired energy
splitting for the two total spins s = and 1 in the (= proton-neutron state. Of
course, the situation at hand is not exactly like the atomic hyperfine splitting since the
underlying dynamics is not of electromagnetic origin.
An {° = orbital state describes a spherically symmetric probability distribution
and a spherical shape for the corresponding nucleus. The small deuteron quadrupole
moment d implies a small deformation of the basic spherical shape of this nuclide.
Q
Let us explore these observations with the aid of the relevant classical and quantum
formulas.
We define a classical electric quadrupole moment in terms of a given charge
density p by the integral

(1= j(3z 2 -r 2 )p(r)dr. (14-23)

It is clear that () has dimensions of charge times area, and it is convenient to express
Q, for nuclei in e • barn units. We can interpret Equation (14-23) more readily if we
rewrite the polynomial in the integrand as

2
/ x +y—2
3z
2
-x -y 2 -z 2 =
2
2\ z
2

This expression samples the shape of the charge by weighting the amount distributed
along the z axis against the amount distributed around that axis. A positive (or
negative) value of Q. ' s therefore an indication an elongated (or
of flattened)
deformation. We add some further classical remarks about the form of Q in the
example at the end of the section.
The quantum mechanical electric quadrupole moment is defined by the expecta-
tion value of the quadrupole polynomial, taken in the state of maximum /,. In the
case of the deuteron the coordinates in the polynomial are those of the proton:

<Q> = ej**(3z; - r
2
)^dT = - jV(3z 2 - r
2
)*dr. (14-24)

(We relate the two-body coordinate r and the proton coordinate r

p
as in Figure 14-17,
and we then deduce the extra factor of \ in Equation (14-24) from this relation.) The
equation expresses the asphericity of the probability distribution and has the same
interpretation as Equation (14-23) with regard to the distribution of charge.
An C° = state produces a vanishing result for the quadrupole moment (Q,)- (The
proof of this assertion is left as Problem 17 at the end of the chapter.) Hence, the small
observed value of Qd can be explained only if the deuteron wave function is assumed
 14-7 The Nucleoli- Nucleoli Interaction 703

Figure 14-17

Proton and neutron coordinate vectors and

the two-body separation vector. Equal masses
are assumed so that the center of mass lies

midway between p and n.

to have a small /^0 portion supplementing the 3S l

composition of the 1
+
state. We
reject the possibility of an /= 1 contribution because this choice would enter with the
wrong parity. We turn next to c° = 2 and conclude that the deuteron state must be a
combination of S and 3 D Note that the spin-triplet property must be maintained so
3
} 1
.

that s = 1 and c* = 2 can combine to preserve the = 1 quantum number for the i

nuclear spin. The assignment of a small probability to the t°= 2 correction results in a
fit for Qd and also accounts for the small discrepancy between the magnetic moments
\>-
d and \i
p
+ [i
n
.

We
have remarked in Section 14-1 that the interaction between two nucleons is the
same for pp, nn, and pn pairs of particles. We have just learned, however, that the
deuteron stands alone as a pn bound state. These seemingly inconsistent observations
are reconciled by the Pauli principle. We note that the deuteron is in a spin-symmetric
state because of the s = 1 assignment and is also in a space-symmetric state because of
the admixture of the two even values of /. The Pauli principle forbids this combina-
tion of symmetries for the identical-fermion pairs pp and nn but has no immediate
bearing on the deuteron since the pn system iscomposed of distinguishable particles.
The admixture of c° = and /= 2 in the wave function of the deuteron has
interesting implications for the nucleon-nucleon interaction. Since the physical state is

not characterized by a unique value of (" , it follows that c° is not exactly a good
quantum number fundamental pn interaction must not be due to a purely
so that the
central force. We conclude that an additional L-nonconserving effect, called the tensor
force, is also present in the dynamical problem. We have already cited the evidence for
a two-nucleon force involving the spins of the two nucleons. The new tensor interac-
dependence on the angles between the nucleon spins and the
tion introduces a further
two-body coordinate vector r. All these complicated aspects of the nucleon-nucleon
interaction are apparent in the properties of the primitive A = 2 bound system.
We identify other properties of the interaction when we probe the two-nucleon
system at higher energy in processes such as pp and np scattering. An experimental
finding of some interest is the existence of a large spherically symmetric component in
the distribution of protons scattered from protons. This effect is attributed to a strong
repulsive core at very short range in the nuclear interaction between the two particles.
Figure 14-3 shows how such a repulsive interaction dominates the attractive nuclear
potential energy of two protons at small values of r. We see this strong short-range
phenomenon in spherically symmetric c*= states, and we find that the effect is

masked by the repulsive centrifugal potential energy in states with nonzero c".
Signs of a repulsive core are also revealed in electron-scattering studies of the
deuteron. A pronounced dip is observed at the center of the deuteron charge
distribution, unlike the situation for the larger nuclides in the range considered in
704 Properties and Models of the Nucleus

Figure 14-9. This electron-scattering view of the proton-neutron bound state indicates
a strong tendency for nucleons to repel and avoid each other at very close range.
It is obvious that a very complex interaction exists between two nucleons. We treat

this basic nuclear force by means

models and acknowledge that the force might be
of
too complex to be regarded as fundamental. We might even suppose that a truly
elementary interaction is operative and somehow governs the observed nuclear
particles at a level beneath that of their revealed behavior.

Example

Let us offer the following construction as background for the classical quadru-
pole formula in Equation (14-23). First, consider a point charge e at the origin
and recall the well-known formula for the electrostatic potential at distance r:

•Mr)
47TE r

Next, consider an electric dipole configuration consisting of a charge e at

(0,0, d/2) and a charge — e at (0,0, —d/2). The corresponding potential is the
sum of the two point-charge potentials:

•Mr)
47T£ 2 _
+y 2 + (z- J /r>\ 2 2
+ y2 +
rl
[ p
,/ , .,2 , /
d/2) ]jx (z + d/2)

where x 2 + y 2 + z
2
= r
2
. We expand this expression for d <^ r and obtain the
following result to first order in d:

ell zd
l \ -1/2
zd d2 \
->/*,
+ +
4we„r
0' \ r
z
\r^ 7< ^) )

Attest
(I
l\
\ \
1 + —+ Zd

2r ^
zd
+
-)>^
\\

477e
ed z

r
o
J
1

Let us denote the electric dipole moment by the quantity p = ed and express the
dipole potential by the familiar formula

P z
"
*(0 = J-
477e r

Finally, consider two such dipoles with opposite signs and separate locations,
taking p to be at (0,0, d/2) and -p to be at (0,0, -d/2). The resulting
potential is the sum of the two dipole potentials:

~ d/ 2
fS =
<Mr)
Pi z z + d/ 2 \

- d/2) 2 /2 2 2 V2
4^o 1 [x
2
+y + 2
(z
Y [x
2
+y + (z + d/2) \
 14-8 A Simple Model of the Deuleron 705

Figure 14-18

Simple distributions of point charges. An

arbitrary charge distribution can be assembled
in the form of a series whose first three

contributions are monopole, dipole, and

quadrupole configurations.

Monopole Dipole

Again, we expand to first order in d:

" 3/2
( zd d2
shir\ '
1
- - + —A \

477e r
J
\\ -J) {
i

r
2
4r'/

1 d\( zd d 2 ]' 3 ^]
+ + +
i' 2)l
1
^ 4?) )
"/ \"
3 zd \ ( 3 zd
p !
3
477e r \

d \

--[(! + .
..) + (l + .v)]j

pd t z
2
\ pd 3z
2
- r
2

= - r 3-r - 1 + ••• = = + ••••

3
47re r^ \ r" 47re r
J

The final result contains the characteristic quadrupole polynomial (3z 2 — r

2
), as
in Equations (14-23) and (14-24). We show this succession of three elementary
charge distributions in Figure 14-18, and we note that the quadrupole represents
a system with zero net charge elongated along the z axis.

14-8 A Simple Model of the Deuleron

The properties of the deuteron can be understood with the aid of the Schrodinger
equation. The binding energy is especially interesting because the smallness of this
quantity can be explained from a simple description of the proton-neutron interac-
tion.

Let us argue that the spin-dependent aspects of the interaction are only secondary
considerations and concentrate on the main effect of a two-body central force. We must
adopt a model to describe the unknown central potential energy V(r). The selection of
the model is not a critical matter since the binding of this nucleus is not very sensitive
to the detailed shape of the potential energy function. We find that the deuteron is
706 Properties and Models of the Nucleus

Figure 14-19

Square-well model for the binding of the deuteron. The function rR(r) satisfies Equation
(14-27), and the f— stationary-state eigenf unction \p depends only on r. The dashed curve in
the figure shows the limiting form of rR(r) for zero binding energy.

V(r) rR(r)

adequately treated with the use of a square well, parametrized by a well depth V and
a radius r . The parametrization of this model is illustrated in Figure 14-19. Note that
the energy level of the deuteron is found near the top of the well and that no higher
excited states are supposed to exist.

We ignore the neutron -proton mass difference and assign the same mass M to
each particle. Consequently, the reduced mass in the central-force problem has the
value n = M/2, and the coordinate vectors in Figure 14-17 satisfy the relation

'-2' (14-25)

We let the deuteron be described as a pure £, state with energy eigenvalue — E and
b ,

we take the £= spatial eigenf unction to have the form

t = R(r)Y00 (d,4>). (14-26)

The function R(r) satisfies the general radial differential equation, as formulated in
Equation (6-43), for the special situation
situ; where jn = M/2, /= 0, and E = —E We
b
.

can rearrange this equation to read

— (rR)- jM
d2
1
r
[V(r) + E b
](rR) = 0. (14-27)

Since V(r) is a discontinuous step function, the differential equation holds in piecewise

fashion:

M
i(^) -(Vo -E b
)(rR) = iorr<rQ
d,
 14-8 A Simple Model of the Deuteron 707

and

M
— (rR)-—E
d2
2
(rR)=0 b
for r > r .

Let us define the two wave-number parameters,

ME
*=— M(V -E
— n
b
and K= 1
n
b )
,
(14-28)

so that our equations become

(rR)" + K 2
(rR) = for r < r

and

(rR)" - k 2 (rR) = for r > r .

We can identify the solutions immediately:

a sin Kr
rR(r) = { l _ kr . (14-29)
be

(The function cos Kr cannot be used inside the well because an infinite result would
+ ir
follow for R(0). The function e cannot be used outside the well because a
divergence would occur as r -> oo.) A sketch of ihe final solution is included in Figure
14-19. The figure also shows the stationary-state eigenfunction

R(r)

IAtt

as defined in Equation (14-26).

The two pieces of the solution in Equation (14-29) are supposed to match smoothly
at the well boundary r = r . We use this requirement to draw the following implica-
tions:

continuity of rR => a sin Kr = be~

k '"

and

continuity of (rR)' => Ka cos Kr = —kbe~ T

°.

These results represent two conditions in the determination of the three unknown
constants a, and Eb The normalization of the wave function provides the third
b, .

constraint needed to complete the solution. We are mainly interested in E b so let us ,

take the ratio of our two conditions in order to remove a and b from this part of the
problem. The result is a single equation relating E b
to the parameters of the model:

KcotKr =-k or cot-

yjM(V \E^—
—-E -r =-\-
b )
• (14-30)
- E V, b

The second form of this relation follows from Equations (14-28). The usual methods of
quantum mechanics would treat the energy Eb as an unknown quantity to be
708 Properties and Models of the Nucleus

determined for given parameters V and r Alternatively, we can regard E b as known

.

and use Equation (14-30) to express a necessary condition on the parametrization of

the model. The equation is known as the range-depth relation when this point of view is

adopted.
We can penetrate Equation (14-30) most effectively if we look first at the limiting
situation where Eb —> 0. This limit is not far from the physical case, if indeed E b is as
small compared to V as Figure 14-19 suggests. The range-depth relation has the
limiting form

cot r = 0,

and so a simplified relation between V and

()
r follows at once:

,a/j; 77 m 2h 2
p

>0
- V
K 0'0
r
2
= (£, = 0). (14-31)
h 2 AM
We examine this result numerically in the first example at the end of this section and
learn that the estimated well depth is at least an order of magnitude larger than the
measured binding energy, given a realistic choice for the radius parameter. Equations
(14-28) reduce to the limits

{MV»
k -» and K-+
h
-> —77

2r
as E b
-* 0.

Consequently, the solution in Equation (14-29) becomes

77r
a sin — r < r
R(r) - 2r

in the limiting case. The behavior of this solution is indicated by the dashed graph in
the figure. Note that when Eb is quite small the solution rR( r ) just turns over inside
the well. The corresponding broad shape of the eigenfunction \j/ implies that this state
is not able to probe the details of the two-nucleon force with very much resolution.
Hence, the square well is able to give an adequate picture of the binding interaction.
The deuteron is said to be barely bound because of these properties.
The range-depth relation can be analyzed by graphical means when E b is allowed
to have its actual nonzero value. Let us rewrite Equation (14-30) for this purpose,
setting Kr = u:()

u u
— cot u = -k => tan u =
kr

Figure 14-20 shows graphs of the left and right sides of the final equality, plotted as
functions of u. The deuteron solution is determined by the value of u at the first

intersection of the two graphs. (Intersections at larger u have no interpretation in this

 14-8 A Simple Model of the Deuteron 709

Figure 14-20 Figure 14-21

Solution of the deuteron range-depth relation Square-well potential energy including an
tan u = - u/kr The intersection of the two
.
infinitely repulsive core. Realistic values of the
graphs approaches the asymptote u = w/2 in parameters in a model of the deuteron are:
the indicated zero-binding limit. V = 70 MeV, r = 1.7 fm, and rc = 0.4 fm.

V(r)

rc r

particular model.) The figure indicates the following bounds on the solution:

tt JM{V -E b
< Krn < 77 or — <

Thus, the graphs describe an intersection that moves with E b

and has asymptotic
behavior

Krn — > — as k

in the limit of zero binding energy. This result agrees with the conclusions of the
previous paragraph.
Our model for the nucleon-nucleon interaction has not taken account of the
short-range repulsive core discussed at the end of Section 14-7. We can make way for
this effect if we substitute the modified square well in Figure 14-21 for the original
well in Figure 14-19. The problem is altered by the infinite repulsion near r =
because the modified eigenfunction must vanish everywhere inside the proposed core.
This new property gives the probability distribution a vacant region at its center, in
qualitative agreement with the electron-scattering results mentioned in Section 14-7.
The remainder of the analysis goes through as a straightforward exercise, which we
include as Problem 20 at the end of the chapter. The crude model in Figure 14-21 is

intended only as a squared-off approximation to a more realistic two-nucleon interac-

tion. Figure 14-3 shows a better model for the case of the s = system. The s = 1

interaction is expected to have the same general appearance with a somewhat deeper
attractive well.
710 Properties and Models of the nucleus

Example

The range-depth relation for zero binding results in the following numerical
expression of Equation (14-31):

2
77
2
{hcf m 2 (197 MeV- fm)
IVo
2
= - —7- = = 102 MeV fm •
2
if E.* = 0.
4 Mc 2
4 939 MeV

We can use this calculation to constrain the values of the square -well parame-
ters. Thus, a typical radius r = 1.6 fm implies a well depth

102 MeV fm 2
V =
(1.6 fm)
•

=
2
—= 40 MeV,

a figure more than ten times larger than E b

.

Example

Let us return to Equation (14-29) and carry the solution for rR( r) one step
further. The constants < i and b obey the equality

b = a sin Kr •
e
kr
°,

while Equation (14-30) provides the relation

1 K 2

si
K + • *
2 2
° 1 + cot Kr k
:

The quantity A> is known to lie in the interval ( tt/2, w), and so the positive
root is chosen to give

K K
sin Kr = c k 'n
2 2 2 2
yjK + k Jk + k

The result enables us to rewrite the radial sol ution in terms of a single
multiplicative constant:

/ sin Kr r < r
o
ft 1

R(r) = -< K
> r
1 1

\ U ,

2
+ k
2
i r
o-

This expression is put to use in Problems 18 and 19 at the end of the chapter.

14-9 Magic Numbers

Our treatment of the nucleus takes on a further degree of model dependence as we

pass from the two-nucleon system to nuclides with many protons and neutrons.
 14-9 Magic Numbers 71

Figure 14-22

Populations of stable nuclides according to proton number and neutron number.

lllllll il lilllllllllllill lllllliilillllllli 111

20 40 80 80
Magic
20M28) -(82
numbers

illllllllllllllllll

?0
lllllllllllll III llll

40
llllllllllllll

60
lllllllll llllllll

80
llllllll lllllllill

100
llllllllilllil lllllll

120
III
N

Complex by recourse to some approximate method for

nuclei can be studied only
handling bound particles. We have encountered this same situation in our
all the
experience with complex atoms. The independent-particle theory has been a great
success in the analysis of atoms and offers a productive strategy for nuclei as well,
despite the obvious differences between the two systems. We know that the nucleus has
no central core (except in the context of a model) and that the interaction between
two nucleons produces strong scattering effec'is. We might therefore expect the nuclear
force to be dominated by the noncentral interactions of pairs of nucleons. Neverthe-
less, a domain of validity exists for a central-field theory of the nucleus in which an

independent nucleon experiences the average force of all the other nuclear particles.

We have invoked the exclusion principle in Section 14-6 to argue the merits of this
point of view. The central field and the exclusion principle have been brought
together successfully in the shell theory of atoms. We find the same methods fruitful
again, but to a lesser degree, in the theory of nuclei.
Hints of nuclear shell behavior have already been noted in Figure 14-4. These first

indications of the magic numbers have been observed in the larger-than-average

populations of stable nuclides along certain rows and columns of the nuclear chart,
corresponding to certain numbers of bound protons and neutrons. The magic numbers
include these values of Z and N in the following list:

2 8 20 28 50 82 126...

We present the same observations again in Figure 14-22 in the form of distributions of
the stable nuclides, plotted as functions of Z and N. The figureshows the more
obvious accumulations of nuclei at (tin), and at jV = 20 and
Z= 20 (calcium) and 50
82. We note that Ca is doubly magic with Z N
40 = = 20, and we discover that such
4
other doubly magic examples as He (Z = N 2),
= [6
(Z= N= 8), and 208 Pb
(Z 82 and N
= = 26) are species with unusual stability. The binding energies of
1

magic configurations of nucleons tend to be larger than average, enough to stand out
as marked deviations from the smooth graph of E b /A in Figure 14-12. These
fragments of systematic evidence are taken as suggestions of shell closures in nuclei.
We find more compelling evidence of closed-shell behavior when we look at
nucleon separation energies in the vicinity of the magic numbers. These quantities are
712 Properties and Models of the Nucleus

Figure 14-23

Neutron separation energy versus neutron number for several families of isobars. The data are
from the tables of Wapstra and Bos, the source used to construct Figure 14-12.

A
15

En
A = 40 A = 54

10
A = 17
A = 91
(MeV)
A = 140

A = 209
5

Magic
numbers
20) (28

10 20 30 40 SO 80 90 " 120 130

N

analogous to the ionization energies of atoms. Figure 9-7 has taught us to read the
number as a clear indication of atomic shell
variation of ionization energy with atomic
structure. We present nuclear data of the same sort in Figure 14-23 by plotting the
neutron separation energy E n versus N for several groups of isobars. Only a limited
sample of graphs needs to be shown since the results for the selected values of A are
typical of many different isobar families. We find in every case that E n
varies with N
and drops abruptly when TV changes from N*, a magic number, to N* + 1. The
graphs tell us that the binding of the last neutron is relatively large when the nucleus
contains N* neutrons and becomes unusually small with the addition of one more
neutron. We conclude that a closed shell of neutrons occurs at the neutron number
N*. A parallel study of the proton separation energy leads to a similar conclusion for
protons. We recall again that the ionization energy of atoms demonstrates exactly the
same behavior (somewhat more dramatically) whenever the atomic number corre-
sponds to any of the noble gases. We know from Equation (14-10) that E n
is equal to
a difference of nuclear binding energies:

A -l
E„( X) = Eb ( A X) - E (Ab
X).

Hence, a large variation of E n can be associated with a noticeable departure of E h

from the value predicted in Equation (14-12), the semiempirical formula. We give a
numerical illustration of this effect in one of the examples below.
Another way to spot a neutron shell closure is by examining the cross section for the
absorption of thermal neutrons. The reaction of interest is the neutron-capture process
in which a beam of slow neutrons initiates a nuclear transformation accompanied by
the emission of y rays:

A+
n+ A X l
X + y.

This process is also called an (n, y) reaction, where the transformation of the nucleus
is expressed as
A
X(n,y) A + X. l
 14-9 Magic Numbers 713

We define the cross section a for this type of collision by analogy with the definition
given in Section 3-4 for the elastic scattering of charged particles. In the case of
neutron capture, we interpret the cross section as the effective area presented by a
single target nucleus to a single beam neutron. This quantity can be used to measure
the probability for the nucleus to capture the neutron. The («,y) cross section
becomes quite large when the neutron number of the target nucleus is one unit less
than a magic number N* and becomes quite small when the target neutron number is
equal to jV*. These observations constitute good evidence for a closed shell of neutrons
at the magic neutron number TV*.

Example

We offer these cross sections for thermal neutron capture in xenon as an

illustration:

o
y
= 2.6 X 10
6
barns for
l35
Xe(«, y) 136 Xe

and
136
o
y
= 0.26barn for Xe(«, y ) 137 Xe.

Xenon has Z= 54, and so the two situations involve target neutron numbers
equal to N* — 1 and N*, with N* = 82. We can appreciate the enormous size
of the one cross section relative to the other if we recall the definition

-28 2
1 barn = 10 m 2
= (10 fm) .

In these units we have

2
2.6 X 10
6
barns = (16000 fm) 2 and 0.26 barn = (5.1 fm) .

The figures in parentheses may be compared with the scale set by the nuclear
radius. We recall Equation (14-3) to obtain

R = RoA 1
/3 = (l.07fm)(136)' /3 = 5.50 fm

135
for A = 136, and essentially the same A = 135. Obviously,
result for Xe is

136
very hungry for neutrons while Xe is somewhat satiated.

Example

The nuclide
88
,Sr has a magic number of neutrons, = 50. therefore expect N We
the neutron separation energy for this nucleus to be somewhat larger than the
value predicted by the semiempirical mass formula. The actual value of En can
be determined with the aid of Equation (14-10):

£„(
88
Sr) = £ A(
88
Sr) - £ 6(
87
Sr) = (768.47 - 757.35) MeV =11.12 MeV.

(The binding energies are taken from the tables of Wapstra and Bos, the
reference used to construct Figures 14-12 and 14-23.) The prediction from the
774 Properties and Models of the Nucleus

mass formula for an even -even nuclide is given by the expression

En ( A X) = «, - M 2/3
(l " S
2
)

Z2 / 1 4Z ;

+ ^3/4'
A(A- 1)

where £ = [(^4 — 1)//1]

1/3
(The derivation of this result appears as Problem 10
.

at the end of the chapter.) For A = 88 we have £ = 0.9962, and so we get the
following string of terms using the a coefficients quoted in Section 14-5:

£„(
88
Sr) = (15.76 - 2.67 + 0.88 - 5.82 + 1.36) MeV = 9.51 MeV.

The actual value exceeds the predicted value by 1.61 MeV, a substantial 17%
deviation.

14-10 The Nuclear Shell Model

The last three sections have prepared us for a theory of nuclei based on the
independent-nucleon approach. We follow the example of the theory of atoms, and we
employ the central-field approximation and the exclusion principle as the two main
pillars of this investigation. The states of a single nucleon are found by adopting a
central-field model to describe the interaction between the nucleon and the other
A — 1 The exclusion principle governs the protons and neutrons
nuclear particles.
separately and controls the occupation of the single-nucleon energy levels for all A
nucleons. These two ingredients of the theory are enough to predict a nuclear shell
structure. We find, however, that the nuclear shell model must include other dynami-
cal considerations if the theory is to reproduce the expected magic numbers.
We assume a central potential energy V(r) for each nucleon in the nucleus so that
we can apply the properties of angular momentum quantization to the states of each
particle. This procedure enables us to label the states by the single-particle quantum
numbers (n(m e m s
). Hence, the eigenf unction for a nucleon in a stationary state has
the familiar form

The radial function R n/f (r)and the associated energy eigenvalue Enf depend on the
choice of model for V(r). We have discussed these aspects of the general central-force
problem in Section 6-7, and we have formulated the radial differential equation for
and E n( in Equation
R ni,(r) (6-43). Let us rewrite this equation as

d2 2M
-j~S rR ^ + ~^^- r

Ku(r)](rR n ,) = (14-32)

and recall that the effective potential energy includes the ^dependent centrifugal term
along with V(r):

2
h
V*(r)- V ^ + ^^^ + 0- (14-33)

(Note that the nucleon mass M is substituted for the reduced mass in both formulas.)

The index n is introduced in Equation (14-32) as a radial node quantum number

 1410 The Nuclear Shell Model 715

according to the interpretation given in Section 6-7. Thus, the choice of / fixes the
function Veff (r), and the index n then enumerates the ascending energy levels and
counts the nodes of the corresponding radial solutions. We are reminded of these
properties in the example at the end of the section.
Let us emphasize that the original definition of the quantum number n is in use in
this problem. We should not confuse n with the terminology adopted in the theory of
atoms, where the same symbol is used by convention to denote the principal quantum
number. It is clear that the notion of a principal quantum number has no logical
place in the treatment of nucleons.
The model requires the selection of a function V(r) to describe the nuclear central
field. A possible candidate has already been suggested in Figure 14-14. It is possible to
parametrize this potential energy by the formula

V (r)=
v ' T^ZT,
(r-R)/a '
(14-34)
V /
_|_
J g

where V and a do not vary appreciably from one nucleus to the next, while R varies
1/3
as (Observe the similarity between the shape of the potential energy in Figure
/1 .

14-14 and the shape of the nucleon density in Figure 14-8. We appeal to this analogy,
and to Equation (14-2), when we write V(r).) It is more expedient to assume a
square-well approximation for V(r) because the corresponding differential equation
for R n f(r) and E n( admits an exact analytical solution. A possible strategy might be
to start with a preliminary exact solution for a square-well model of the interaction
and then tune in a more realistic numerical solution based on the rounded model of
Equation (14-34). The first stage of this procedure generates a collection of energy
levels resembling those shown in Figure 14-24. Note that the values of En( are
organized according to columns of different ( , as in the presentation of the analogous
atomic problem in Figure 9-4. The second stage of the procedure shifts these energies
to new levels at positions not very far away. Figure 14-25 shows the square-well and
rounded-well levels columns to represent the results of such a method. It is
in parallel
obvious that these must vary with the choice of mass number A. We describe
results
this implementation of the independent-nucleon model as only one possible strategy,

and we understand that any numerical conclusions depend on the parametrization of

the model.
Our description of the single-nucleon energy levels applies to the case where the
single nucleon is a neutron. We must add the effect of Coulomb repulsion to the model
when we consider the interaction of a proton with the remaining A — 1 nucleons. This
additional feature elevates the potential energy well and introduces a repulsive barrier
for the proton, as in the square-well model of Figure 14-15. The resulting single-pro-
ton levels are qualitatively similar to those in Figure 14-25 except for a general
elevation of all the energies.
The shell-model energy levels emerge from Equation (14-32) with only the two
indices n and £ . A degeneracy exists at every level, as in the atomic problem, because
the energy does not depend on the other two single-particle quantum numbers m e and
m Hence, each
s
. value of Enf corresponds to 2(2/+ 1) degenerate states, distinguished

by the up and down and by the various assignments of

orientations of the nucleon spin
m f for the given value of ( These degeneracies are indicated next to the two columns
.

of energy levels in Figure 14-25. We are able to deduce a shell structure of the nucleus
on the basis of this list of numbers and energies.
Let us consider the process of building up the nuclear ground state by taking Z
protons and N neutrons to populate the lowest unoccupied single-nucleon levels. The
716 Properties and Models of the Nucleus

Figure 14-24

Single-nucleon energy levels Enf in a hypothetical square-well model of the nucleon potential
energy.

,\ e= 1 2 3 4 5 6

2m

3p

2/

1/7

3s

2d

1*

'»

1/

2s

1,7

Lp

Is
 14- 10 The Nuclear Shell Model in

Figure 14-25

Shell-model levels and degeneracies for a square well and a rounded well. The cumulative total
of protons or neutrons is supposed to reach a magic number at each of the larger energy gaps.
Only the first three encircled predictions agree with the known magic numbers.

nt
I

2g 2g
1 56

26 (138)

if

2/ V 6 112
2/
14 106

\h \h
2? (92)
3s
3s
2d
2 70
2,1
10 68

lg
U'
IS! (58)

2p
2p

1/
1/
14 (34)

Is
2s
2 (20)
\d
1,1
10 18

lp
Lp

Is

Is

Square Rounded Degeneracy Cumulative

well well total
718 Properties and Models of the Nucleus

exclusion principle permits no more than 2(2/+ 1) occupants in any shell-model level
E nif
for both species of nucleon. This maximum allowed number is given level-by-level,
for protons and for neutrons, according to the list of degeneracies in Figure 14-25.
Another column on the right side of the figure shows a running total of these maximum
occupancies, accumulating upward from the lowest level. We predict a closed shell of
nucleons of either type wherever we encounter a fully occupied level followed by an
appreciable jump to the next higher energy state. The gap between levels implies a
reduced binding energy for the next added nucleon. This same effect is observed in the
building up of the ground states of atoms, where the analogous gaps are found at the
atomic numbers of the noble-gas elements. The nuclear model in the figure predicts a
shell closure when either Z or N reaches 2, 8, and 20, in agreement with the first three
magic numbers, but fails to continue in the proper sequence thereafter. We are forced
to conclude that the nuclear shell model is either incorrect or incomplete in its present
form.
The difficulty cannot be resolved by choosing a different central field. A new type
of additional ingredient is put forward instead in the form of a nuclear spin-orbit
interaction. We recall from Sections 8-9, 9-4, and 9-7 that the spin-orbit coupling in
atoms causes a splitting of the single-particle energy levels E nf for all /# orbital
states. The splitting occurs because the atomic interaction contributes a different
energy shift for the two allowed values of the total angular momentum quantum
number j, as indicated in Figure 8-28. We have expressed this interaction in terms of
the central potential energy V (r)
c
in Equations (9-36):

dV
VSI (atom) = —-yj - —
1

-S
1
(
• L.
2m e
c r dr

We know that the atomic spin-orbit effect has a secure theoretical basis in relativistic
quantum mechanics, and we also know that the energy splitting in atoms is rather
small especially for small values of the atomic number. In contrast, the nuclear
splitting is assumed a priori to be large and also inverted, in the manner shown in Figure
14-26. We ascribe this behavior to a nuclear interaction of the form

a~SL dV
VSL (nucleus) = S • L, (14-35)
r dr

in which the central-field function V(r) appeals along with the orbital and spin
angular momenta of the nucleon. The minus sign accomplishes the required inversion

Figure 14-26

Nuclear spin-orbit splitting of a single-nucleon

energy level.

; = <?-

n(

i
= e*
 1410 The Nuclear Shell Model 719

Figure 14-27

Shell-model levels including the effect of nuclear spin-orbit splitting. The degeneracy is given
by %j + 1 at each level Enf) The
. accumulated population of nucleons corresponds to a magic
number at every one of the larger energy gaps.

£ nf and£„

2g • • • ...
- liu 148
h 12
-2gy2 10 136

(126)
120
14 1 18
104
LOO
10 92

(82)
12 8(i
68

6 64
8 58

K) (50)
2 40
4 38
6 34

(28)

© 18

14

Is
l«y2 2
© 1
Rounded — with — Spin-orbit n(j Degeneracy Cumulative
well coupling total
720 Properties and Models of the Nucleus

of the split levels, and the phenomenological constant a"SL produces the desired
amount of energy splitting.

Figure 14-27 shows how the large inverted splitting influences the sequence of
shell-model levels. The interaction splits a given single-nucleon energy E nf (with
/=/= 0) into a pair of energy levels E nf The
. figure uses the notation nc* to designate
the states with j = t+ ^ and j = {—
\, and assigns the lower state to the larger value
of j. Note that the splitting is largeenough to produce rearrangements in the final array
of energies. An energy level with quantum numbers (n(*j) is comprised of 1j + 1
degenerate states corresponding to the various assignments of m for the given value
of j. The figure lists these degeneracies at all the levels and includes a running total of
nucleon populations similar to the scheme employed in Figure 14-25. In this case the

accumulated number of nucleons successfully reproduces a known magic number

whenever the population process reaches a filled level just before the occurrence of a
large energy gap. It is clear that both the large magnitude and the inverted splitting
are required of the nuclear spin-orbit effect if the gaps are to fall in place at the
magic numbers.
The nuclear spin-orbit interaction was originally proposed on phenomenological
grounds after many unsuccessful trials of the independent-nucleon approach. The idea
of a large inverted splitting was introduced in 1949 by M. Goeppert-Mayer and
J. H. D. Jensen in their contributions to the development of the shell model.

Example

Figure 14-28 describes a square-well model for the nucleon potential energy
V{r). Unlike the similar model of the deuteron in Figure 14-19, this illustration
admits more than one bound-state energy level. Let us consider only the / =
case so that Vcfr (r) reduces to V(r) in Equation (14-33). Equation (14-32) then
becomes essentially the same as Equation (14-27) in the treatment of the
deuteron. (The reduced mass and the number of levels are the only differences
between the two problems.) Figure 14-28 shows a well large enough to accom-
modate three bound states, with energy levels Eu , E2i , and E 3t (in E nf
notation). The corresponding solutions of Equation (14-32) can be sketched by
following the guidelines established in Section 6-7. An application of the usual
arguments about curvatures and nodes results in the three graphs of rR n/,(r)
shown in the figure. We see that rR u (r) reproduces the shape of our previous
graph for the deuteron in Figure 14-19, and we note that each successive
function has one additional node. In fact, all three of these £= radial solutions
behave as sine functions inside the well and have parametrizations just like
Equation (14-29). We find the two higher energy levels by solving for the values
of the variable u at the second and third intersections of the two graphs in
Figure 14-20. The qualitative results of this example are extended to the /= 1

case in Problem 22 at the end of the chapter. A much larger family of energy
levels E n( can be obtained for each / if the square well is made sufficiently
large. We have assumed such a system of levels in Figure 14-24.

14-11 Spins and Moments in the Shell Model

The nuclear shell model makes many other predictions beyond the explanation of the
magic numbers. The model is based on a procedure for assigning angular momentum
quantum numbers, and so the results are expected to include properties pertaining to
 14-11 Spins and Moments in the Shell Model 721

Figure 14-28

Square-well model of the nucleon potential energy with three ^=0 bound states.

V(r)

the angularmomentum of the assembled nucleons. Predictions of nuclear spins and

magnetic moments are particularly interesting because these tests of the model are
more stringent than the placement of the magic numbers.
Let us visualize the shell model in terms of the levels shown in Figure 14-27 and use
the quantum numbers (ntfjm^ to denote the single-nucleon states. The notation
implies an identification of the total angular momentum of a nucleon by the familiar
formula

J = L + S.

We extend the same addition of angular momenta over all the A nucleons and express
the nuclear spin vector as

i= LJ* = I(l, + sj. (14-36)

k = \

Note that the and spin angular momenta are added according to the jj-coupling
orbital
scheme. We from our discussion of Figure 9-23 that we are supposed to follow
recall
this plan whenever the spin-orbit interaction has a strong effect.
The sum over nucleons in Equation (14-36) behaves like its analogue in atomic
physics and reduces immediately to a smaller number of terms. Each level nc"j in

Figure 14-27 defines a nuclear subshell consisting of 2j + 1 degenerate states. A

completely filled subshell contributes and positive overall parity, for
zero nuclear spin
reasons just like those given in the case of the complex atom. Consequently, the
nuclear spin and parity of the ground state are determined solely by the dynamics of
the nucleons in the last incomplete subshells.
722 Properties and Models of the Nucleus

The pairing effect plays a decisive role in these residual interactions. Two protons
or two neutrons with opposite values of m. in a given subshell have a greater
probability to be found at small separation where the particles can experience a
greater degree of nuclear attraction. The effect produces maximal binding when even
numbers of like nucleons pair off with canceling angular momenta. These paired
+
protons and paired neutrons make a contribution to the total angular momentum
and parity of an unfilled subshell. Thus, the sum over nucleons in Equation (14-36) is
reduced even further in the state of lowest energy, so that only the last unpaired proton
and neutron are left as surviving contributors. This consequence of the pairing effect is

supported by an abundance of empirical evidence.

We are led at once to the following conclusions about the angular momentum in
the nuclear ground state. An even-even nuclide has no unpaired proton or neutron
and is predicted to have nuclear spin and parity i
p = 0^ in every case. This
prediction is borne out without any known exception. An odd-.4 nuclide has either Z
or N equal to an odd number and therefore has one unpaired proton or neutron in an
unfilled subshell with designation nt° These quantum numbers determine i
fi
, the
nuclear spin and parity of the entire nucleus:

i =j (always a half-integer) and p = sign of (

— l) . (14-37)

An odd-odd nuclide has an unpaired proton and an unpaired neutron. In this

situation Equation (14-36) reduces to the addition of two angular momenta:

I=J, + J„

This coupling problem follows the rules given in Section 9-8 and results in an
inequality involving the proton and neutron quantum numbers:

\j ll -j n \<i<j p + Jn (14-38)

as in Equations (9-44) and (9-45). These upper and lower bounds constitute a
prediction for the nuclear spin. An accompanying prediction for the parity is given as
(
— \Y'{ — 1)^", the product of the orbital parities for the proton and neutron. All these
expectations are illustrated by specific tests of the shell model in the first example at
the end of the section.
Our description of the shell model is based on a hypothetical treatment of the
central field. We should therefore be prepared for deviations in the actual ordering of
the shell-model energies relative to the levels in Figure 14-27. The exact sequence of
levels may vary with the mass number A and may also differ between the two species
of nucleon. Table 14-1 provides separate lists of shell-model levels for a proton and for

a neutron, ordered empirically to agree with observations over a large number of

odd-proton and odd-neutron nuclei. Note that the maximum occupancies and running
totals are included, to be read upward from the bottom, as in Figure 14-27. These lists

exhibit the expected shell closures at the magic numbers. We use some of the entries in
example below.
this table in the first

The
shell model also makes predictions about the magnetic moments of nuclei. The
limitations of the model can be grasped by concentrating on the case of an odd-A
nucleus in the ground state. We visualize this system in terms of (A — l)/2 pairs of
nucleons with antiparallel angular momenta, plus a single unpaired proton or
neutron. We know from Equations (14-37) that the overall nuclear spin and parity are
 14- 11 Spins and Moments in the Shell Model 723

Table 14-1 Empirical Level Sequence of Nuclear Subshells

odd-proton odd-neutron

2^7/2 8 162
1*11/2 12 154
3 d 5/2 6 142
2 Sg/ 2 10 136
"13/2 14 126 -^
3 P 1/2 2 112
2/5/2 6 110
^P-S/2 1 104 3^3/2 4 104
2/7/2 8 100 1^9/2 10 100
l"9/2 10 92 2/7/2 8 90
OS l/, 2 2 82 l"ll/2 12 82 -^
2 "3/2 4 80 2^3/2 I 70
\h n/2 12 76 1/2 2 66
2d 5/2 6 64 1^7/2 8 64
1
St/2 8 33 2d 5/2 6 56
U9/2 Ki 50 1^9/2 10 50 -*
2 P\/2 2 40 2 P\/2 2 40
1/5/2 6 38 1/5/2 6 38
32 32
2^3/2 1 2/>.
V 2
1

1/7/2 8 28 1/7/2 8 28 -+
W 3/2 •1 20 Ws/a 1 20 -*
2^1/2 2 16 2^/2 2 16
lrf
5/2 6 1
1^5/2 6 11
l
P\/2 2 8 1/^1/2 2 8 -^
1^3/2 4 6 1^3/2 4 6
\s l/2 2 2 2 2 "m
"1/2
maximum running maximum runnin g
nCj
nt? «/
" 6
occupancy total J occupancy total

determined by the state of the odd nucleon, and we attribute the magnetic dipole
moment of the entire system to this lone unpaired particle. Both orbital and spin parts
of the magneticmoment contribute if the particle is a proton, while only the spin
magnetic moment contributes if the particle is a neutron. The following analysis treats
both possibilities at the same time.
The prediction is immediate when the odd nucleon is in an {= orbital state.
Only the spin contributes in this circumstance and gives

ju, = either \i
p
or \i
n

for thetwo possible cases.

The
general formula for the magnetic moment of an odd-^4 nucleus follows by
analogy with the result for the magnetic moment of a one-electron atom in Section
8-11. Let us return to Equation (8-45) and rewrite this defining relation in terms of the
724 Properties and Models of the nucleus

orbital and spin magnetic moments of a single bound nucleon:

R = V-l + V-s (gi. L + gs s )- (14-39)

The revised expression employs the substitution of magneton units — nB — > fi N and
contains the explicit orbital and spin g-factors for the nucleon. in the proton case we
take

gL = 1 and gs = gp ,

and in the neutron case we take

St = ° and Ss = Sn-

We then let the measured magnetic dipole moment correspond to the expectation
value of ju.. in the nuclear spin state for which m = The evaluation of (fi.)
i
i.

parallels the treatment in Section 8-1 1 and leads to the result

Vn Si. 3 Ss
- -
00 - + + f(S+ + +
,

- i(i 1) 1) H f
i(i 1) /(*?+ 1)
i + 1 1 2 1

(14-40)

for either type of nucleon in a nucleus with quantum numbers i and /. We relegate
the derivation of this formula to a few detailed remarks at the end of the section.
Equation (14-40) can assume two different forms since the nuclear spin can satisfy
either i= { + \ or = (— \. Let us eliminate £ and examine the resulting depen-
i

dence on i for the two possibilities. The case /= i — L

,
gives

Vn Sl 1\ 31
</0 = '" + - )-
i + 1 2 2 4

.Ss l 31

K)
I \
+ i(i+ 1) - i- +
2 4

f*JV
2

i + 1
|(2* + /-1) + |(*+1)
1
\ Ss
= Mw SiJ * ~ I + "
('-'+*), (14-41)

and the case {— i + ^ gives

Vn iL
<iO
(
t(i'+ 1) + I 2
'+ - \[i + -
i + 1

+
gs
i(i+ 1)
'
+
s)('"
+
fK
ft* -
2
(2z + 3z) + |(-0
i'+ 1 |
gL\* + (i=*-\). (14-42)
I + 1
 14- I I Spins and Moments in the Shell Model 725

Figure 14-29

Magnetic moments versus nuclear spin for odd-proton nuclei. The plotted points fall between
the Schmidt lines.

m
*N
odd-even
j =(+ -i-
.^
6 ^^^93 Nb °

5
^^
^ 51 V °
"5|n°

«Sc°
4
^ 141p r o 209 B| °
27 A |o
"7 Li
°
3

w ^^^^
19po 127|° 139
La°
175
Lu°
2
153 o
7
5As° Eu
31 po
1

39
K°-
-^
1
1 1 1

107
Ag 2 3
/2 % % %

Each of these conclusions can now be specialized for application to an odd-Z or an

odd-iV nucleus. We set gL = 1 and g s = gp to find

(;-I + *)
2 2/
oo>«
M/v
I

i/3 >
Z
i

1
*/.
for '±±, (14-43)

i + 1 \ 2 2

and we set gL = and g 5 = g„ to find

A',

Vn-
00. for i = /+ i, (14-44)
1
gn
Mv
i'+12

in the two possible cases where the odd nucleon is either a proton or a neutron.

Our formulas yield four classes of results for the magnetic moments of the odd-,4

nuclei. We present the predicted dependence on the nuclear spin in Figures 14-29 and
14-30 for each of the four different sets of circumstances. The predictions lie on curves
called Schmidt lines (after T. Schmidt, an originator of the idea that the moments
might be associated with the properties of a single odd nucleon). Experimental values
of the moments odd-^ nuclei are also plotted in the figures. We note a
for several
tendency for the experimental points to fall between the Schmidt lines; however, we
observe a general failure of the simple theory to give a very good agreement with
experiment. Some comparisons with experiment are discussed in the second example
below.
726 Properties and Models of the Nucleus

Figure 14-30

Magnetic moments versus nuclear spin for odd-neutron nuclei. Almost all plotted points lie

between the Schmidt lines.

1L
i~\
even-odd

o 33
S

3
l
/2 k
29 Si o 179 Hf o
"Cr° 173 °
Yb 73
49 Ti° Ge°
9
Be° 91
Zr
o 43
Ca°

3 17
He° i =( +

It is clear that the elementary shell model is not entirely satisfactory as a quantum
theory of the nucleus. The model adheres
an independent-particle theory in which
to
a fixed spherically symmetric nuclear core interacts with an independent nucleon. An
improved self-consistent treatment would allow every nucleon to participate collec-
tively in an interdependent determination of the nuclear state. Some aspects of
nucleon interdependence can be included in the independent-particle theory by letting
the interaction with the nucleon deform the spherically symmetric core. The collective
model of the nucleus builds on the shell model and incorporates this added feature of a
deformed spheroidal nuclear core. The improvement injects some of the philosophy of
the liquid-drop model since the spheroidal core has bulk properties like the liquid
droplet. The rotational dynamics of the core enriches the theory with new rotational
degrees of freedom and thereby opens the way for better agreement with experiment,
particularly in the area of magnetic dipole and electric quadrupole moments.

Detail

Equation (8-49) expresses the crucial part of the derivation of (ju.) in the case
of the one-electron atom. Let us transfer the same construction to the magnetic
moment of the odd- A nucleus in Equation (14-39). We introduce the nuclear
spin vector

I = L + S

in place of the total angular momentum J for the atom and write

2
Oi,/ >«<|i •!/,>.

(This relation is analogous to the expression that follows Equation (8-49) in

Section 8-11.) We then continue in parallel with the steps leading to Equation
 14-11 Spins and Moments in the Shell Model 727

(8-47):

li-I-yUiX + feSML + S)

Ma/ 2 2
[gLL + (g L + g s )S-L + g s S ]
h

8L 8s f T 2 -
g j} + ^ (/ - L* - S2 ) + gsS'<
h

— (I 2
+ L -S2 2
) + -(I 2 - L2 + S 2 )
h

2
Our next move is to insert this result into the expression for (jjl,I ) and take the
expectation value in the state defined by the eigenvalues

I
2
= i(i + l)fi
2
, L 2 = t(t+ \)h
2
,
S 2 = \h 2 , and /, = iti.

These maneuvers produce the following equality:

0O»0'+ 0»
!
i(i + 1) + /(/+ 1) /r
h { 2

g.s
+ i(i+ 1) - t(/+ 1) + ^
2
m

We quote this formula as Equation (14-4U) in the text.

Example

Let us compare our shell-model predictions with a very small sample of the
known nuclear and parities. The doubly magic species 16
spins and 40 Ca have
+
completely filled proton and neutron subshells and are observed to be nuclei
as predicted. The odd-,4 nuclides 'gO g ^K 20 and '|F I0 contain an unpaired ,
,

nucleon and furnish a more interesting test of the shell model. Table 14-1 tells us
that the odd neutron in "O is in a \d b/2 subshell and that the odd proton in
39
K
is Equations (14-37) give the corresponding i p assignments
in a \d i/2 subshell.
in terms of the quantum numbers j and ( of the odd nucleon. Thus, we expect
+
17
to have i
p = 'i since j '
= -, and ^=2, and we expect
9
K to have i
p = )
*

since j '
= % and t= 2. These conclusions agree with experiment, according to
the data in Appendix A. On the other hand, the nuclide 19 F has an odd proton
in a 1^5/2 subshell, and so the shell-model quantum numbers J = \ and 2 /=
+ +
would imply | A i
p = .
\ assignment is observed instead, again as recorded in
Appendix A. The odd -odd nuclide 'yN 7 has an odd proton and an odd neutron
and therefore involves a different test. We consult Table 14-1 and find that both
of the odd nucleons are assigned to l/> 1/2 subshells. Since £p = <fn = 1, the model
predicts an even parity from the product of the two odd-parity factors. Since

Jt,
= Jn = 2> tne m °del predicts a nuclear spin given as either i = or i' = 1
+
from Equation (14-38). Appendix A tells us that
14
N is a 1 nucleus, in
agreement with these predictions.
728 Properties and Models of the Hucleus

Example

We can easily convert Equations (14-43)and (14-44) into the graphs of Figures
14-29 and 14-30 if we proton and neutron g-factors from
recall the values of the

Section 14-1. Let us again use the nuclides

17
and 39 K to test the predictions of
l7
the model. The previous example describes as an odd-neutron nucleus whose
quantum numbers /= 2 and = satisfy the relation — c* + \. The upper
i -, i '

version of Equation (14-44) tells us to expect

V-n 2

A table of nuclear data lists the experimental value as — 1.893, a result quite
39
close to our prediction. In the case of K. we have an odd-proton nucleus whose
quantum numbers c° = 2 and i = A
, obey the relation i = t'— ~2 . The lower
version of Equation (14-43) predicts

u it 3 eh \ 3
1
i+ —2 = -(3 - 2.793) = 0.124.
fi N i + 1 \ 2 ) 5

The listed experimental value 0.391 is somewhat further removed from our
prediction in this instance. We can see the positions of these nuclides with respect
to the Schmidt lines by inspecting the relevant portions of the two figures.

14-12 Charge Independence and Isospin Symmetry

Models are the means of describing the complexities of the nuclear force, in the
interaction of two nucleons and in the binding of many nucleons. We know that the
force between two nucleons is not purely central and is not independent of spin.
However, the two-nucleon problem is not as complex as we might expect, since the
nuclear interactions are known from experiment to be the same for pp, pn, and nn
pairs of nucleons. Evidently, the nuclear force does not depend on the charge of the
interacting particles. This property of charge independence represents a new type of
symmetry principle and conservation law in nuclear physics. Our interest in charge
independence is focused particularly on the effects of the symmetry in the primitive
two-nucleon system. We are also concerned with the manifestations of the symmetry
in the structure of complex nuclei. Our main objective is to introduce charge
independence as a simplifying ingredient in nuclear physics.
The pp, pn, and nn interactions are said to be identical only with regard to the
nuclear characteristics of the interacting particles. This assertion presumes that the
obviously charge-dependent electromagnetic interactions have already been taken into
account wherever these effects may arise. Thus, the proposed nuclear symmetry
defines a relationship between the proton and the neutron and allows a substitution of
the one for the other as far as the nuclear force is concerned. Of course, the two species
of nucleon are not identical in every respect. The particles are distinguished by such
electromagnetic properties as charge and magnetic moment so that their electro-
magnetic interactions are rather different. Hence, the symmetry principle and the
conservation law associated with charge independence are supposed to hold in
circumstances where electromagnetic effects can be neglected relative to the strong
 14-12 Charge Independence and Isospin Symmetry 729

nuclear force. This exact symmetry breaks down and becomes a good approximate
symmetry in the presence of electromagnetism. It is reasonable to regard the small
difference in mass between the neutron and the proton as a measure of the deviation
from exact symmetry. It is then a matter of conjecture that the difference in mass
might be due solely to electromagnetic effects.
Charge independence has played a part in the history of nuclear physics since 1932,
the year of the neutron. The concept originated with Heisenberg and E. U. Condon,
who proposed independently that the proton and the neutron should be treated as
differently charged quantum states of a single generic nucleon. They viewed the
charge of the nucleon as a mere label with no meaning as a physical parameter in
the absence of electromagnetic forces. Their idea was inspired by the near equality of
the nucleon masses and was reinforced by the direct observation of charge indepen-
dence in experiments on pp and np scattering. The notion of a nuclear symmetry was
implemented by powerful mathematical techniques in the subsequent work of E. P.
Wigner.
Let us begin to appreciate the symmetry between protons and neutrons by
considering pairs of mirror nuclides related by the interchange of Z and N. We recall
from Section 14-5 that the mass formula predicts the same binding energy for these
isobars if the distinguishing effects of Coulomb repulsion are disregarded. We there-
fore expect the interchange Z «-» N
have no influence on the level of the nuclear
to

ground state whenever the electromagnetic interactions can be ignored. The mirror
nuclides have the remarkable property that the approximate equality of energies
persists level-by-level up two related systems. An excellent
into the excited states of the
example is 4 and
provided by the pair of nuclides]Be 3 in Figure 14-31. The two
,Li

level schemes exhibit parallel patterns of states with the same nuclear spins and
parities, and with much the same excitation energies above the respective ground

states. We
can argue that the Coulomb effect elevates all the levels of the isobar with
the larger of the two values of Z. We recognize, however, that the mirror symmetry of
energy levels tests only the equality of the pp and nn forces. The comparison gives no
information about the relative strength of the pn force because the number of pn
bonds is exactly the same in the two isobars. This finding establishes a property of the
nuclear force known as charge symmetry. Since the equality of forces is tested in only

two of the three possible combinations, the symmetry under the interchange Z <-» N is

less comprehensive than the full symmetry associated with charge independence.
We can compare all three forces if we select a family of nuclides in which the pp,
pn, and nn bonds occur in varying numbers. This opportunity is offered by any
collection of isobars with an even mass number A. We illustrate the arguments in
Figure 14-32 by drawing sketches of the internucleon bonds in two proton-neutron
systems with odd and even values of A. Figure 14-33 presents physical evidence for
the equality of the three interactions in the form of energy levels for the even-A isobars
18
0, 18 F, and 18 Ne. The parallel columns of levels contain states of each isobar for

which the i p quantum numbers are the same and the corresponding excitation

energies are very similar. Nuclear states with this property are known as isobanc

analogue Their existence as a family is

states. a clear manifestation of charge indepen-
18
dence. We
note in passing that there are energy levels in F for which there are no
18 18
isobaric analogues in the level schemes for and Ne. This feature is another
consequence of the full symmetry of charge independence.
The families of isobar levels in Figures 14-31 and 14-33 have certain structural

characteristics in common with the quantum states of a particle in a central field. We

can grasp the meaning of the new symmetry principle by developing the close analogy
730 Properties and Models ol the Nucleus

Figure 14-31
7 7
Energy levels and i* assignments for the mirror nuclides Li and Be. The excitation energies
are given in MeV. The Be ground state is unstable and undergoes a /8 transition to the ground
7
state of Li, accompanied by an energy release of 0.86 MeV.

3
10 _ /2
3
/2
-

10

'Hh

Figure 14-32

Systems of isobars for testing charge symmetry and charge independence. Only the pp and nn
forces can be compared in the odd-/l nuclides. The pn force can be included in the comparison
when A is even because the number of pn bonds does not remain fixed for the different nuclei.

2 JV= 1 Z= 3

PP PP 1
PP PP 1 PP 3
Bonds pn ? pn 2 pn 3 pn 4 pn 3
nn 1 nn nn 3 nn 1 nn
 14-12 Charge Independence and Isospin Symmetry 731

Figure 14-33

Energy levels assignments for isobars with A = 18. The three level schemes contain
and i
p

threefold families of isobaric analogue states. Certain additional levels also occur as indicated in
l8
F. Energies of excitation are quoted in MeV. Two of the three ground states are unstable so

that (1 transitions take place from U! Ne to 18 F to ,h O.

«Nt

18 F

18Q

between these two rather different physical systems. To clarify the analogy let us
assume for the moment that the isobaric analogue states have exactly the same
energies. We might suppose that this coincidence is accomplished by the removal of
electromagnetic effects. The hypothesis implies sets of degenerate states with common i
p

assignments in which the nuclei are distinguished by the different combinations of Z

and N for the given value of A.
This occurrence of different states with the same energy reminds us of the
degeneracy associated with rotational symmetry in the case of the particle in a central
field. We recall that the energy of a spinless particle may depend on the L 2 quantum
number / but cannot vary with the L : quantum number m f In the more general
.

situation where the particle has spin, the energy may vary with j but not with the
z-component quantum number m r A multiplet of 2j + 1 degenerate states results for
each j, corresponding to a set of quantized orientations of the angular momentum
vector J. We know that the energy cannot depend on these orientations because the
rotational symmetry of the central field precludes the existence of a preferred direction
for the choice of z axis. The introduction of a constant magnetic field then fixes such
 .

732 Properties and Models ol the Nucleus

an axis in space and causes an energy splitting among the 2j + 1 states. This lifting of

the degeneracy is due to the breaking of rotational symmetry by the application of the
external field.

These remarks summarize the ideas of angular momentum quantization and

rotational symmetry and recall the meaning of the observed degeneracies in a central
field. We now wish to transfer these familiar spatial properties of a particle to the
internal nucleon composition of an isobar family. A new rotational symmetry and a
new conservation law are introduced for this purpose. We pretend that electromag-
net ism can be "turned off" so that isobaric analogue states can be made to coincide at
the same energies. The nuclear force is supposed to be responsible for the internal
symmetry that underlies this pattern of degeneracies. We then imagine that the actual
observed energies depart from the degenerate pattern as we turn the electromagnetic
effects back on to break the internal symmetry.
Let us set this proposition aside temporarily and return to our earlier comments
about the original interpretation of charge independence. The notion of a generalized
two-state nucleon treats the designations proton and neutron as internal degrees of
freedom, like the spin orientations up and down for a spin-^ particle. Rotational
symmetry in space implies that these spin orientations have the same energy. By
analogy, we associate the two quantum states of the nucleon with the up and down
orientations of another type of vector quantity. This new vector is fashioned after the
familiar spin S and is known as the isospin T. An abstract three-dimensional isospin
space is invented so that the orientations of the vector T can be defined. We express the
charge-independent property of the nuclear force as a rotational isospin symmetry in the
contrived new space and argue that the equality of masses of the proton and neutron
is evidence for the proposed new symmetry. We then claim that the symmetry is a
manifestation of a new conservation law for isospin, just as ordinary rotational
symmetry is a demonstration of the conservation of angular momentum. The proton
and neutron form a degenerate isospin multiplet, called the nucleon doublet, in this
framework. We can pursue the abstraction a step further and regard the actual
neutron -proton mass difference as a lifting of this degeneracy by the breaking of
isospin symmetry. Electromagnetism acts as a symmetry-breaking effect since the

electromagnetic properties of the nucleon doublet are different for isospin up (the
proton) and isospin down (the neutron).
Let us draw the concepts in the last two paragraphs together and formulate isospin
in quantum mechanical language. We ensure the desired properties of the isospin
vector by imposing quantization rules identical to those enjoyed by the angular
momentum J (or L, or S). Thus, the quantum behavior of the isospin T is expressed in
terms of the quantities T2 and T. by the following eigenvalue conditions:

T 2 =t(t+l) where t may be 0,^,1, §,..., (14-45)

and

Tt =-t,-t+l,...,t-l,t for a given value of t (14-46)

Note that the choice of / may be integral or half-integral and that T, has 2t + 1
quantized values for each choice. (No h factors are used in Equations (14-45) and
(14-46) since T is an abstract dimensionless quantity with no classical interpretation as
an angular momentum.)
Each allowed value of the new isospin quantum number t defines a possible isospin
multiplet consisting of 2t + 1 isobaric members. The nucleon doublet has two states
 14-12 Charge Independence and Isospin Symmetry 733

with isospin up and down, so that the relevant isospin quantum number must be / = r,

The two orientations of T correspond to the assignments

Tz = — r, and + ^ for the neutron and proton, respectively.

Exactly the same isospin assignments are adopted level-by-level for the mirror
7 7
nuclides Li and Be in Figure 14-31.
We assign a T, eigenvalue to a particular state of a given nuclide zX N according
to the general formula

Z- N
(14-47)

The formalism then implies that the assigned system has an isospin quantum number
/ and belongs to a multiplet of 2t + 1 isobar states. The power of isospin symmetry
lies in the ability to predict these nuclear systems as isobaric analogue states. An exact
symmetry would imply an exact equality of energy levels for the predicted isobars.
Figure 14-33 shows an array of t = 1 multiplets, or isospin triplets, in which the T,
eigenvalues are

- 1 in '10,0, in
l
|F9 , and + 1 in |«Ne 8 .

We have already noted that 18 F also contains a number of levels without any
+
counterparts in the other two isobars. The figure shows the i p = 1 ground state of
18
F as one example of this special class. These slates occur only for T, = and must
therefore be isospin singlets with isospin quantum number / = 0. The formalism
allows for the existence of singlet energy levels when A is even and predicts that such
levels should stand alone, unrelated in energy to any other isobars.
We have considered the substitution symmetry of protons and neutrons earlier in
this section, and we have associated the interchange of Z and with the charge N
symmetry of mirror nuclides. Equation (14-47) tells us that this lesser symmetry
operation is just a reversal of the sign of Tz . The rotational aspects of charge
independence embody a more powerful use of the isospin degree of freedom. Let us
turn to the abstract isospin space for an interpretation of this property and consider an
isospin multiplet of nuclear states with isospin quantum number t. The multiplet has
2/ + 1 isobaric analogue states, corresponding to 2t + 1 orientations of a vector T
with length \jt{t + 1 ) in the abstract space. Isospin symmetry allows us to rotate the
vector, and thereby pass from one isobar state to another, without affecting the energy
level. This picture has an approximate validity when the symmetry is not exact.
Let us return to the problem of two nucleons and use our knowledge of isospin to
make some detailed observations. The deuteron is one such system, but so are the
nucleonic configurations pp and nn. Let us also keep in mind that all these systems
have eigenfunctions describing the space and spin states of the two particles. If we
concentrate on isospin properties first and refer to Equation (14-47), we observe the
following possibilities for the value of Tz :

pp has Tz = 1 ,
pn has Tz = 0, and nn has T, = - 1

The total isospin vector for any two-nucleon configuration has the form

T= T, + T2 ,
 .

734 Properties and Models o( the Nucleus

where T, and T, are isospin-^ vectors. The analogous addition of spin-^ vectors
results in the quantized vector sums

| + \ = and 1

We apply the same rules to isospin and conclude that all two-nucleon states must have
either / = or / = 1 It is obvious that the pp and nn systems belong to / = 1 triplets.
.

The pn combination appears in two different isospin states, distinguished by the

properties of antisymmetry or symmetry under the exchange of symbols /?<-»«. Let us
4 5
express all possible isospin states for two nucleons in the notation £' and £ to exhibit
these exchange properties. The / = singlet state is antisymmetric:

V = -j=(pn-np). (14-48)

The three / = 1 triplet states are symmetric:

v
f ,
= nn. (14-49)

(The notation pn/ y2 means there is probability for finding nucleons 1 and 2 to be -,

p and n, respectively.) Note that the triplet states are labeled by their Tz eigenvalues.
We recognize these four expressions as exact analogues of the states of total spin s =
and s = 1, obtained for two spin- r; particles in Section 9-6. Recall that the corre-
A
sponding antisymmetric and symmetric spin eigenf unctions have been listed as \
and xi '" Equations (9-25) and (9-26).
s
The exchange properties of £
/!
and £' can be used to formulate a generalized
version of the Pauli principle. Equation (9-22) instructs us to write eigenfunctions for
two identical fermions as

VX A or f'x

We are reminded that the requirement of fermion antisymmetry is met by multiplying

space and spin factors with opposite properties under the interchange of the respective
pairs of variables. We can regard all of our systems of nucleons as compositions of
identical fermions now that we are adopting the generalized two-state concept for the
nucleon. In this language the eigenfunction for a single nucleon becomes a combina-
tion of a spatial factor with a spin orientation ( f or J, ) and an isospin designation ( p
or n). A state of two nucleons is then described by a triple product of the form

fyY or
S
+ X S
A S
or ^Vf' or fW,
in which the space, spin, and isospin factors are combined to satisfy the required
overall antisymmetry under the interchange of the two fermions.
The deuteron provides an interesting application of the generalized Pauli principle.
We know from Section 14-7 that this pn system is a superposition of iS and D l x

states. The orbital assignments £= and C= 2 correspond to symmetric distributions

 14- 12 Charge Independence and Isospin Symmetry 735

with regard to the interchange of the two spatial variables. The triplet spin state is
likewise symmetric with respect to the two spin orientations. Hence, we describe the
space and spin degrees of freedom by the eigenf unctions \p s and x'S and we select the ,

singlet £ for the isospin description in order to meet the requirement of generalized
antisymmetry. We therefore conclude that the deuteron has isospin quantum number
t = 0. This result is as expected since the alternative t = 1 assignment implies the
existence of impossible isobaric analogues in the systems pp and nn. (Recall that pp
and nn cannot be symmetric in space and spin because of the Pauli principle in its
original form.)
Isospin gives us a new symmetry to use in the classification of quantum systems.
Complexities are simplified and regularities are revealed whenever such an ingredient
is introduced in the analysis of complicated phenomena. The theory of nuclear
structure spans a class of problems in which isospin symmetry plays an influential role.
Isospin principles are also employed extensively, along with other new types of
symmetry, in the phenomenology of elementary particles.

Example

Another illustration of a / = nuclide is found in the ground state of

4
He, the a
particle. Equation (14-47) tells us that this Z= N= 2 system has T. = 0. In
principle, the four isospin- \ nucleons can have their combined isospin vectors in
states with quantum numbers t = 0, t = 1, or t = 2. In fact, the assignments
t = 1 and t = 2 are ruled out because the a particle would then be required to
have isobaric analogues. To be specific, there should exist multiplets of A = 4
p = +
states with in which there would be three isobars for t = 1 or five
i

isobars for / = 2. We know of no such partners of the

4
He ground state, and so
we take the a particle to be a singlet with isospin quantum number / = 0.

Example

The conservation of isospin by the nuclear force is not restricted to collections of

protons and neutrons in a single nucleus. We can also apply the principle to

two-body nuclear reactions of the form

X, + X, ^x 3
+ x 4
.

We let the four nuclides have isospin vectors T, to T 4 , and we write the
conservation of the total isospin as

T= T, + T2 = T3 + T4 .

This relation among quantized isospin vectors acts as a constraint on the states

of the particles in the reaction. Consider, for instance, the (a', a) process

'H+ 12 C- 10 B+ He 4

in which the deuteron, the ground-state carbon nucleus, and the a particle
participate as t = isospin singlets. Isospin symmetry allows the reaction to
10 10
produce only the / = states in B. The ground state of B is among these
736 Properties and Models of the Nucleus

allowed possibilities. Excited states with / = 1 also exist (as isobaric analogues
l0 10 10
with Be and C), but all these B states are forbidden in this reaction because
of the conservation of isospin.

Problems

1. Suppose that the original yray interpretation holds for the experiment in Figure 14-1 and
that the Compton scattering of y rays causes protons to be ejected from the paraffin
detector. Obtain a formula relating the incident y energy and the kinetic energy K of the

observed proton for the case where K is maximum. What y energy is predicted if K is as

large as 5 MeV?
2. Calculate the de Broglie wavelength for an electron with kinetic energy 183 MeV. What
electron beam energy corresponds to a 1 fm de Broglie wavelength?

3. Consult Figure 14-8 and prove that the indicated surface thickness t satisfies the relation

— t

= 4 In 3,
z \

where 2, is a parameter in the formula for the nuclear charge density. Use the data in
14-9 to estimate a universal value for the density of nucleons in the interior of the

nucleus.

4 Data from the nuclear chart for the three stable neon isotopes 2 "Ne,
JI
Ne, and "Ne are:

atomic mass (u) 19.992436 20.993843 21.991383

isotopic abundance (%) 90.51 0.27 9.22

Compute the atomic weight of neon from these figures and compare the result with the

value quoted in the chart.

5. Three doublets are seen in the mass spectrum of a sample containing hydrogen, deu-
terium, carbon, oxygen, and methane. The splittings observed in the M/e ratios of the

ions are:

+-2
0.001548 uA for ('H'H) H+
0.042306 u/e for (
2
HH 2 2
H) - 12 C ++
+

0.036385 u/e for

4
('^C'H'H'H'H) - lei
O+
2 16
Use these data to compute the atomic masses of 'H, H, and 0.
6. Use the atomic mass data in Appendix A to compute the binding energy per nucleon for
,0 ,h
the nuclei Ca, Fe, '"'"Sn, and -'""Pb. These particular cases are indicated on the graph
in Figure 14-12.

7. Derive the formula

(Zef
V=
3
—
5 4w £f) /?

for the Coulomb energy stored in a uniform solid sphere of charge Ze and radius R.
(Determine the work done to construct the sphere by moving infinitesimal spherical shells
of charge radially inward from infinity.)
 Problems 737

8. Use the semiempirical mass formula to compute the atomic mass of each of the isotopes
mentioned in Problem 6. Compare the results with the corresponding entries in Appendix
A.

Use the atomic mass data H, 3 He),

7 7
9. for the three pairs of mirror nuclides (
:i

( Li, Be), and

( B, make three separate predictions for the constant a 3 in the semiempirical mass
C) to

formula. Take M("C) to be 11.011433 u and consult Appendix A for the other atomic
masses.

10. Show that the semiempirical mass formula leads to the following prediction for the
neutron separation energy:

4Z-
£„("X) = a, - M V3 (1 - £
2
) + a,j^i - -
l

1 1
-
A(A- 1)
"5

l/i
where ( = [(A — \)/A] . The result takes this form when ^X is an even-even nuclide.
11. Use the semiempirical mass formula to derive the following leading-order relation
involving nuclear binding energies:

-[E h(
t

^X)+E (<>X)} h
- £A ("X) = -^ + ....

Take Z even and A odd as conditions in the derivation, and use binomial expansions such
as

{a-
V i)
_1/3
= —-fi --) = nL( 1 + J_ + ..

A l/i \ A) A'^y 3A

on the way to the final answer.

2" 7 J08
12. Compute the neutron separation energies for Pb and Pb taking data from Appendix
A. Use the results to make a determination of the constant a b in the mass formula.

13. Consider the Fermi gas model of the nucleus and assume that the Coulomb effects are

approximated inside the nuclear volume by the constant potential energy aZ" / x
' . Refer
to Figure 14-15 and let the potential energy well for the proton gas be elevated by this

amount relative to the depth of the neutron well. Deduce the following relation among the

numbers of nucleons,

N 1 3
= Z 2/J + bZ 2A /\ [

and identify the constant b in terms of the given parameters of the model.

14. Consider the np capture reaction n + p —» d + y in which both of the particles in the

initial state are essentially at rest. Obtain a formula for the binding energy of the deuteron
in terms of the energy of the y ray.

15. Points (x, y, z) on the surface of the indicated ellipsoid of revolution satisfy the equation

x
2.2
y -I- z
2

a b

Choose a suitable volume element and show that the volume of the figure is \ma~b. Let
the ellipsoid contain a uniform distribution of total charge Ze, and derive the formula

Q_= jZe(b -
2 2
a )

for the classical quadrupole moment.

738 Properties and Models of We Nucleus

16. The nuclide '

''Lu has a comparatively large quadrupole moment, Q= + 8.0 e barns.
Use this number and the result of Problem 15 to estimate the presumably small axis ratio
b/a for the nuclear ellipsoid.

17. Prove that the electric quadrupole moment (() ) vanishes in a two-nucleon state described
by an ( = wave function.

18. The square-well model of the deuteron produces an eigenfunction of the form

sin Kr r < r

4>
= K k(,
/Air I
r )
r > rn

A" + k
2

Use the normalization of the wave function to obtain the constant

2 k

1 + krn

The parameters r
Q,
k, and K are identified in Section 14-8.

19. Derive a formula for the expectation value of r in the deuteron state using the results of
the model in Problem 18, and calculate the value of (r) for r() = 1.6 fm.

20. The figure defines the parameters of a square-well model for the deuteron in which the
potential energy includes an infinitely repulsive core. Determine the f— solution of the

differential equation for rR(r) with energy — Eb in each of the three intervals (0, r ),

(r , r(1 ), and (ru ,oo). Use the continuity conditions to derive a relation among V Eb rn () , ,

and r() . Obtain a suitably continuous final form for rli(r) containing a single unknown
normalizing constant.

rc ' •

E,
^b

V(r)

-V

90
21. Make a prediction of the neutron separation energy for the magic-number nuclide Zr
based on the semiempirical mass formula. Compare the result with the value determined
 Problems 739

90
from the measured atomic masses. Use M( Rq Zr) = 88.908900 u and take A/( Zr) from
Appendix A.
22. Assume a square-well potential energy as a central-field model in an independent-nucleon
theory of the nucleus. Draw a figure to represent the effective potential energy for the

£= 1 case, and let there be three (= 1 energy levels, designated as E lf/

, E2p , and E 3p .

Sketch graphs of the corresponding radial solutions rR lp (r), rR 2 Ar), and rR ifl
(r), and
compare with the /= results in the example accompanying Figure 14-28.
23. The next magic number for neutrons after N = 126 is supposed to be jV = 184. Show
how the sequence of levels in Figure 14-27 may be continued to generate this prediction.

24. Deduce the predictions of the shell model for the nuclear spins and parities of the odd-A
l:, J
nuclides N, Na, ' Al, and Mo. Are the results in agreement with the listings in

Appendix A?
25. What does the shell model predict regarding the nuclear spins and parities of the odd-odd
h 10 50
nuclides Li, B, and V? Do the predictions agree with the i
1'
assignments listed in

Appendix A?
26. Calculate the values predicted by the shell model for the magnetic moments of the odd-A
nuclides in Problem 24. Compare the results with experiment, using a table of nuclear

data.

27. Consult a table of nuclear data to find evidence for isospin symmetry among the nuclides
with mass number A = 10.

28. Examine the tabulated energy levels of the A = 17 system of isobars and find evidence for

the existence of isospin multiplets with t = -7 and t = \ quantum numbers.

 F 1 F T £ E H

NUCLEAR
PROCESSES
-

/he structure of a nucleus is defined by the

states of the nuclear quantum system. The nucleus reveals its structure through a
variety of interactive processes in which transformations of the quantum states occur as
observable phenomena. One such process is the emission of y radiation in the
deexcitation of an excited nucleus. This phenomenon is like the radiative deexcitation

ofan atom and is known as y decay. (Of course, the radiation from a nucleus is much
more energetic. The nuclear process results in y rays characteristic of the emitting
species, with typical photon energies in the MeV range.) Radiation from nuclei may
also take the form of ejected fragments or particles. These phenomena are called a
decay or (1 decay, depending on the particular form of emission. The processes of a, ft,
and y decay represent the three specific varieties of radioactivity. Each type of emission
is associated with a certain kind of nuclear instability, and each is accompanied by a

particular sort of transition between the energy states of the nuclear system.
Radioactivity involves the spontaneous disintegration of an unstable atomic nucleus.
The spontaneity of the process implies that the transformation of the system of
nucleons takes place in an isolated nucleus, with no stimulus from any external source
of energy. Radioactive behavior is natural if the emissions are observed for a sample of
nuclides occurring in nature and is artificial if the radiation is induced in the sample
by some sort of external bombardment. Natural radionuclides are generally long-lived,
although species with short half-lives are also found in nature as decay products of
commonly occurring decay chains.
The history of nuclear physics begins with the discovery of radioactivity. Much of
our present understanding of nuclear structure comes from this method of viewing the
nucleus. We devote several sections of the chapter to a full discussion of the various
aspects of nuclear radiation. Historical remarks and general definitions are considered
first, and then the three processes of a, /?, and y decay are taken up in turn.

Nuclear transformations are also observed in the collisions of particles with nuclear
targets. The resulting nuclear reactions are additional sources of information about the
states of the nucleus. We examine the principles behind these investigations later in

740
 151 Radioactivity 741

the chapter. Finally, we consider the fission and fusion of nuclei as transformations of
special interest for the generation of nuclear energy.
These phenomena constitute a modern-day realization of the alchemists' goal. The
transmutation of the elements is accomplished as desired, by a change of species
within the nucleus of the atom.

15-1 Radioactivity

The first observations of nuclear disintegration were made by accident in the x-ray
experiments of A. H. Becquerel in 1896. X rays had just been discovered in the
previous year, and Becquerel's laboratory was actively involved in the investigation of
their properties. Incident x rays were known to cause fluorescent radiation in atoms,
and so a reversal of roles fluorescent stimulation was suggested
was proposed whereby
as a means of producing x rays. Becquerel selected a fluorescent compound of
uranium and indeed found that his sample emitted penetrating radiation. However,
he also found that the uranium compound produced the same energetic emissions with
no external stimulation. It was apparent that this new type of spontaneous radiation
was peculiar to the uranium in the sample and was altogether different from the
proposed atomic x rays.
The nature of the radiation was studied by Rutherford and Becquerel, and also by
Curie and his remarkable colleague M. S. Curie. These investigators established the
existence of nuclear radiation in its three forms a, ft, and y. They demonstrated the

deflection of a and /? rays by a magnetic field and concluded that these emissions had
to be charged particles. The a particles turned out to be helium nuclei, and the
negative /? particles proved to be electrons with properties just like Thomson's cathode
rays.

Marie Curie
742 Nuclear Processes

Figure 15-1
8u
Radioactive decay scheme of Br. The nuclear energy levels are connected by /$ and y
+
transitions. The amounts of released energy are given in MeV. The designation y8 actually
represents two distinct processes, as described in Section 15-4.

17.6 m

The Curies devoted much of their collaborative work to the identification of the
radioactive elements polonium and radium. Their achievements were acknowledged
decades later when the element curium was named after them.
The first investigations of radioactivity were conducted with natural sources
bearing uranium, thorium, and other heavy elements. Artificially induced radioactiv-
ity was demonstrated for the first time in 1934 by J.-F. Joliot and I. Joliot-Curie. They
27
used a particles to bombard the nucleus A1 and initiated a nuclear reaction
30
producing the radionuclide P. The observation of positron emission from this
nucleus showed that radioactivity was not restricted just to the heavy elements.
The chronology of interesting events in nuclear physics should be noted. A
four-decade period began when natural radioactivity was first observed, prior to the
discovery of the nucleus. The neutron came later, followed by artificial radioactivity.

Finally, the period of development reached its dramatic climax with the disclosure of
nuclear fission.

Wehave interpreted radioactivity as the disintegration of an unstable nucleus.

Hereafter, we cast our description in the language of quantum physics and treat the
various phenomena in terms of transitions between nuclear states. The a and ft decays
bring about definite changes of the nuclear species, while the y transition causes a
change only among the states of a given nucleus. Figure 15-1 shows how a scheme of
energy levels can be drawn to illustrate the possible decay processes for a particular
radionuclide. We p assignments and
include several pieces of data to indicate the
i

half-lives of the energy levels and the energy released in the transitions. The figure
employs a useful convention whereby the initial and final nuclear levels appear in
separate parallel columns and exhibit transitions to the left or right depending on the
sign of the charge of the emitted particle. Note that y transitions stay within their own
column in this scheme.
The total charge and the total number of nucleons must be conserved in any
radioactive decay. We know that an a particle is a 4 He nucleus, and so we express the
a decay X —» Y + a in detail as

+
noting that the charge and mass numbers balance explicitly. The /? and fi decays
 151 Radioactivity 743

Figure 15-2

a and fi transitions displayed on a chart of

the nuclides.

^
M&

involve electron emission and positron emission, respectively. We learn later on that a
new type of neutral particle must also be emitted in each of these processes. It would
be premature to divulge this information now, so let us temporarily refer to the two
types of ($ decay as

}X-/+IY + jB- and ^X-> z l Y + 4

1
8
/
+
.

The emitted /? systems do not contain any nucleons; consequently, the mass number
A remains unchanged in these transitions. Hence, all /? decays are identified as
transformations between nuclear isobars, a property illustrated by the A = 80 family
of nuclides in Figure 15-1.
Each of these nuclear transformations proceeds from a parent nucleus X to a
daughter nucleus Y. Figure 15-2 shows how we can represent such decays with the aid
of a chart of the nuclides. If the Z versus N system of axes is employed as in Figure
14-4, then the three different nuclear transitions are described by the following
transformations of coordinates on the chart:

(Z,N) -% (Z- 2,/V- 2),

(Z,iV)-^->(Z + 1,7V- 1),

(Z,N) -^> (Z- l,N+ 1).

Parent and daughter are shown executing these transitions in Figure 15-2.
We can use this method of presenting a and /? decays to describe the radioactivity
232 238
of such naturally occurring sources as Th or U. These heavy radionuclides have
the property that their half-lives are of the same order as the age of the Earth.
10 232 9
(Appendix A gives values of the half-life in the range 10 years for Th and 10
238
years for U.) Each unstable species displays its radioactive behavior in a decay series

where the first nuclear transition in the chain is an a decay with a very long half-life.
The series continues through a succession of a and /? processes from one unstable
nucleus to another until the final stable product of the chain is reached. Figure 15-3
744 Nuclear Processes

Figure 15-3
" 38
Decay series for U. Branchings of a and ft decay modes occur at several locations along
JiH 206
the chain between U and Pb.
Z

238

A = 206

shows how 238

U transforms into
20(>
Pb after such a sequence of nuclear decays. We see
from the figure that every nuclide in the series has a mass number given by
A = 4n + 2, where n varies over nine successive integers from 59 down to 51. The
iH
U decay chain is called the An + 2 series for this reason. Other similarly defined
chains are the An series for
2:i2
Th, the An + 1 series for
2
Np (half-life ~ 10 6 years),
2i, a
and the An + series for
'5
U (half-life ~ 10 years). The longer-lived radionuclides
f2
Th and 2i!! U exist with appreciable abundance in certain natural ores. These
sources are primary contributors of background radiation in our environment.
The instability properties of a and /? decay are associated with the differences in
mass between the parent and daughter nuclides. The two types of process are
triggered by two rather different kinds of decay interaction. We see from the half-lives
of the various decaying species that radioactive decay is a very slow nuclear phenome-
non in either case. Even though a decay is the emission of a nuclear fragment, and is
therefore an effect of the strong nuclear force, the rate of decay is substantially
inhibited because of the Coulomb repulsion between the fragment and the residual
+
daughter. The /? and f$ decays are extremely slow as a general rule because the
processes are under the influence of a very weak force.
The decay properties of a known source include its half-life, decay mode, and

energy release. These characteristics constitute an observable signature for the corre-
sponding radionuclide. The half-life is especially useful because this property gives the
radioactive source a timing mechanism to be used for chronological purposes. A
commonly employed application is radiocarbon dating, which establishes the age of a
carbon-bearing material by comparison with the 5730 year half-life of the /^-active
 15-2 The Exponential Decay Law 745

14
isotope C. The technique is based on the fact that all living organisms continually
exchange CO, in the Earth's environment, where a minute fraction of the carbon
14
nuclei are of the C variety. These unstable nuclides are formed when neutrons from
cosmic-ray interactions are absorbed by the nuclei of nitrogen atoms in the atmo-
14
sphere. The processes of C production and decay are supposed to be at equilibrium
14
in the carbon-dating technique. It is known that the amount of radioactive C
relative to ordinary U C in living matter is of order 10" 12
. It is believed that this value
has remained essentially constant for over 30,000 years. Carbon decay in a specimen
of plant life must therefore occur at a corresponding constant rate, which turns out to
be about one disintegration per second 4 g of carbon. The ingestion of carbon
in every
ceases when a plant dies, and so the amount of 14 C in the specimen decays thereafter
at a rate that decreases by half every 5730 years. The time of death (or the age of the
specimen) is then determinable from a measurement of the rate of decay for a known
mass of carbon. The development of this remarkable technique is attributed to W. F.
Libby. A simple numerical illustration of the method is furnished by the following
application.

Example

14
The production of C in the atmosphere proceeds according to the (/?, p)
reaction

n +' 4 N ^ C 14
-r'H.

The carbon isotope then reverts to

l4
N via the decay process

14
C -* 14
N + 0-.

Let us select a 64 g charcoal sample for carbon dating and suppose that /?
radiation is observed at a rate of 2 disintegrations per second. The decay rate for
a living specimen with the same mass of carbon would be

/ 1 disintegration/s \

(64 g) = 16 disintegrations/s,

using the constant rate quoted in the text. (The derivation of this rate is left to

Problem 5 at the end of the chapter.) The dead rate to the

ratio of the live rate

is

3
2 disintegrations/s 1 / 1 \

16 disintegrations/s 8 \ 2/
l4
The elapsed time since death must therefore be equal to three C half-lives:

3(5.73 X 10
3
y) = 1.72 X 10
4
y.

This result determines the age of the charcoal sample.

15-2 The Exponential Decay Law

The decay of an unstable nucleus is a prime example of a process governed by the

probabilistic concepts of quantum mechanics. The instability is a property of the

species, and the half-life is a measure of the lifetime of the nuclide. However,
746 Nuclear Processes

the lifetime is not a statement of the exact time of decay for a single unstable nucleus
since the decay occurs as a random discrete event. Such an act of chance is predictable
only in terms of a probability for the occurrence of a certain decay transition within a
given interval of time. It follows that the transition probability per unit time
determines the radioactive behavior of a sample containing many nuclei. Thus, the
instability of the nucleus describes a statistical phenomenon, and the half-life of the

sample represents an average time for the observation of a random decay.

Let us formulate the quantum principles of radioactive decay by the following
arguments. We introduce a fundamental quantity, called the decay constant y, as the
transition probability per unit time for the one-step decay X -> Y+ r, where r

denotes the emitted radiation. This decay rate refers to the radioactive behavior of a
single nucleus in the probabilistic sense described above. The decay constant is a
fundamental property of the nucleus because, in principle, the quantity is predictable
from a quantum theory of the decay transition.
We can determine y from experiment if we observe the radiation from a source
containing many nuclei of the species X. We proceed by defining N(t) as the number
of radioactive nuclei in the sample at time /. This number is presumed to be large so
that N can be treated as a continuous variable. We then consider the change dN in
that number after an infinitesimal time interval dt, and we identify the positive
quantity — dN as the corresponding number of decays. The ratio — dN/N represents
the probability of decay in terms of the number of decays occurring in the interval dt
and the number of decaying nuclei present at time t. We employ y, the decay
probability per unit time, to express the probability in the interval between t and
/ + dt:

dN
= ydt. (15-1)
N "
V '

This result implies an activity, or rate of decay, proportional to the instantaneous

number of nuclei in the source:

dN
—
dt
= yN, (15-2)

a relation deduced first on empirical grounds by Rutherford and Soddy as the original
nuclear transformation law. Since y does not depend on t, it is straightforward to
integrate Equation (15-1) and thereby determine N(t):

-
rN(t)dN
I
JNo
—n = Jq
n
/ ydt => -In
N(t)
n
= yt,

taking N (t
to be the number of decaying nuclei at t = 0. We then solve for the desired
quantity to get
N(t)=N e- yl
. (15-3)

This exponential decay law for the fundamental one-step transition X —» Y is

described by the decay curve in Figure 15-4.

A given nucleus in the sample may undergo the transformation X —> Y at any time
from / = onward. We define an average lifetime by computing the mean value of t,
averaged with respect to the number of decays in each time interval dt:
/•OO /-00
- / tdN(t) / te~ y
'dt

- ("dNU) he-y'dt
 15-2 The Exponential Decay Law 747

Figure 15-4

Decay curve corresponding to the exponential decay law N(t) = Nn e Y The indicated mean '.

life t and half-life T, 2 are related to the quantum mechanical decay constant y.
,

N(t)

This lifetime is called the mean life t. The integrations in the definition lead to the
simple result

t= -, (15-4)

so that Equation (15-3) takes the alternative form

N{t) = N e~' /T .
'15-51

The half-life t, i
,., is a different lifetime, already defined as the time required for the
sample to decay to half of its initial population. Appendix A includes a list of values of

t 1/2 for a large number of radionuclides. We show the times t and t 1/2 on the graph
in Figure 15-4, and we observe that the two parameters satisfy the equations

X, a;,
N(r) = and jV(t i/2 ) =

We obtain these results directly from the determination of t in Equation (15-5) and
from the definition of t, The second expression leads
,.,. to a simple relation between
the two lifetimes and the decay constant:

In 2
T 1/2 = Tln2 (15-6)
Y

Equations (15-4) and (15-6) are interesting because they connect experimental and
theoretical quantities, the lifetime of a sample of nuclei on the one hand and the
quantum mechanical decay rate for a single nucleus on the other.

We can measure the activity of a source by counting the rate of emitted charged
particles in a detector. Each observed particle, or count, represents a single nuclear

decay. A typical counter might be a gas-filled ionization chamber containing an

748 Nuclear Processes

applied electric field. A particle is counted when the gas atoms in the chamber are
ionized by the passage of the particle and the ions are collected in the applied field.

The rate of observed counts is the same as the rate of decay of the sample —dN/dt,
except for a possible multiplying correction for the known efficiency of the detector.
This detection efficiency may include at least two factors, the fraction of the total solid
angle subtended by the detector at the source of radiation and the probability for the
particle to produce a signal in the counting circuit.

The decay constant is easily determined by such an experiment. We use the fact
that the measured activity depends on the time:

dN ( dN\

where (
— dN/dt ) denotes the activity at / = 0. If we take the logarithm on both sides
of the equality we get

/ dN\ I dN\

Hence, we can deduce the decay constant y if we plot the counting rate versus t on a
semilogarithmic graph and take the slope of the best straight line through the
experimental data.
The rate of decay of a radioactive source is usually quoted in curies (symbol Ci),
defined by the unit

1 Ci = 37 X 9
10 disintegrations/s.

This large unit of activity is approximately equal to the observed disintegration rate
22(
for a 'Ra source with a mass of 1 g.

Many radionuclides display their activities in sequential chains of decays. Figure

15-3 describes one of the longer radioactive series, and Figure 15-5 shows a schematic
illustration of a typical short chain. Let us confine latter case and our attention to the
formulate the rate equations There are three nuclear
for a general two-step cascade.
states linked by two decay transitions, and so there must be three rates involving two
different decay constants. The figure tells us that X, decays and X 3 grows, while X 2
experiences both decay and growth. We express the corresponding rates in terms of
the decay constants in the figure and find the following relations among the popula-

Figure 15-5

Sequential decay processes X, —» X2 + radiation and X_> —* X + radiation. Each transition

3

has its own probability per unit time.

stable
 15-2 The Exponential Decay Law 749

Figure 15-6

Solutions of the rate equations for the populations of the three levels in Figure 15-5. The results

apply to the case of vanishing initial populations for X, and X,.

tions of the three nuclear levels:

dN x

dN2
—^ = Yl2#l - Y23^2>

y23 N 2
. 15-7)
dt

The first rate has the form of Equation (15-2) so that the population N^t) must

behave according to the basic exponential decay law. We note that the rates sum to
zero, and we conclude that the solutions of the three coupled differential equations
must always obey the constraint

jV, + N 2
+ N 3
= N , a constant.

Figure 15-6 shows a set of qualitative graphs for the special class of solutions in which
the initial populations have the values JV,(0) = N N (0)
,
2
= 0, and jV3 (0) = 0. An
even more specialized case is treated analytically in one of the exercises below.

Example

226
The activity of 1 g of Ra is supposed to be approximately 1 Ci. To verify this
we first convert the 1
g sample into ^ mole, and we then find the number of
nuclei from Avogadro's number:

N = (^ mole)(6.02 X 10
23
/mole) = 2.66 X 10
21
.

226
Appendix A tells us that Ra has a half-life of 1600 years. The rate of decay is
750 Huclear Processes

then given by combining Equations (15-2) and (15-6):

dN N
= yN = In 2
dt t 1/2

(ln2)(2.66 X 10-M )
10
,u „-i
3.65 X 10 s
(1600 y)(365 d/y)(24 h/d)(3600 s/h)

in agreement with the definition of the curie unit of activity

Example

We can use the exponential decay law in conjunction with the quoted half-lives
and abundances of
235
U and 238
U in order to estimate the age of the Earth. Let
us denote these two isotopes as X and X, and express their populations
according to Equation (15-5):

N(t) = N e
- ' /f and N{t) = N e~
l/
\

To get an answer we have to make an assumption about the populations of X

and X at = t 0, the time of genesis for the Earth and its elements. Let us assume
equal initial numbers of the two isotopes, taking :V = N , and regard our
estimate as a consequence of this hypothesis. The ratio of populations then
becomes

N(t)
N(t)

Thus, we learn that the time variable satisfies the equation

\n[N(t)/N(t)] \n[N(t)/N(t)]
l/f- 1/f ln2(l/f 1/2 - 1/t 1/2 )'

using Equation (15-6) to get the final result. The value of / refers to the present
time when the two isotopic abundances are known to be

0.72% for X = 235 U and 99.27% for X = 238 U.

We consult Appendix A to find the two half-lives and use all these data to make
our estimate of the age of the Earth:

ln(99.27/0.72)
9
X 10
9
y = 5.9 X 10 y.
(In 2)( 1/0.704 - 1/4.468)

This conclusion is in reasonable agreement with other geochronological results.

 15-3 a Decay 751

Example

The two-step cascade in Figure 15-5 is somewhat easier to analyze for the
behavior of X 2
when X, is very long-lived. We assume y I2 «: y23 and find that
the solution for the X, population becomes

NM = N l0 e-**' -+ l0

for times of order l/y23 Under these conditions the

. X 2
population is governed
by the rate equation

dN2
= R l2 - y23 N2 ,
dt

where R V2 denotes the approximately constant value of y^A^/):

We integrate the rate equation as follows:

JX R V2 -y,,N2 (t)
N,(i)
dt — 1

In
~ ^12 ~ 723^20
./;
N?0 ^12 Y 2 3^2 •'m
Y2 3

taking N 2i)
to be the initial number of X ;
. nuclei. The solution for N 2(
t ) is found
from this result in two steps:

Rv<-yMt) 723

R - y N20 v2 23

and so

N (t)
2
= —
R„
Y23
+ \N20
\
-—e A',

Y23
Y12
^10+
Y23
/

I
Mo" —^10
Yi'

Y23
l«
Y23'

Our conclusion holds in the interval < / «c 1/y 12 Note that M, may either
.

decay or grow during this interval, depending on the relative size of the ratios
V^io and Yi 2 /Y 23 -

15-3 a Decay

Some of the earliest observations in nuclear physics involved the participation of the a
particle. The emission of a radiation gave evidence of the instability of the nucleus in
Becquerel's discovery of radioactivity. The scattering of a particles gave proof of the
existence of the nucleus in Rutherford's experiments. These first insights into the
nucleus were witnessed with the aid of particles emitted in a decay.
The emission of a particles is generally associated with the heavier unstable nuclei.
An inspection of the nuclear chart reveals that a activity is a main mode of instability
for the isotopes of elements beyond lead at Z= 82 and is only rarely observed in the
lighter species. The emitted particle is a nuclear fragment four times as massive as the
proton. The emission process is energetically favorable for a particles, compared to
752 Nuclear Processes

Figure 15-7

Determination of a-particle velocities by

means of a 180° magnetic spectrograph. The
nonrelativistic momentum is given by Mv =
qBR for an emitted particle of known mass M
and charge q. A measurement of the magnetic
rigidity BR yields a result for the velocity v.

a Source Recorder

other possible nuclear fragments, because of the large binding energy and unusual
stability of the A = 4 nuclide. A tendency for a decay to prevail among the heavier
nuclides is not hard to understand. The a fragment and the residual daughter are
bound together inside the unstable parent nucleus by the attractive short-range
nuclear force. At the same time, the Coulomb repulsion between these two charged
bodies acts as a disruptive influence and contributes to the probability for nuclear
disintegration. Figures 14-4 and 14-12 remind us that these long-range effects of
Coulomb repulsion become increasingly significant in nuclei of larger size. The
heaviest nuclides may also undergo spontaneous fission, another type of fragmentation
process.
Nuclear radiation energy is readily absorbed in matter when the radiation is in the
form of a particles. The moving charges lose their kinetic energy in ionizing collisions
with the atoms in the material medium. Familiar kinematical arguments tell us that
these collisional losses of energy are greater for a particles than for the much lighter /3
radiation. A range in the medium is defined as the distance in which the particle loses
all its kinetic energy. An effective absorber for a particles might be an aluminum foil,

a sheet of paper, or even a volume of air. The range decreases with the density of the
absorbing medium and increases with the energy of the particle. To give an example
at a typical energy, a 6 MeV a particle is observed to travel approximately 5 cm in air
and 0.05 mm aluminum.
in

The velocities of a particles can be measured with accuracy by observing the

deflections of the particles in a known magnetic field. An instrument devised for this
purpose is the magnetic spectrograph, shown schematically in Figure 15-7. Data from
such a device and measurements of range in some absorber can be used in conjunction

to obtain a calibration of range versus energy for the particular absorbing medium.
The resulting range-energy curve then gives a determination of the energy of an a
particle directly from an observation of its range.
The typical a decay X -» Y -I- a is initiated in the ground state of the a-active
parent X. The observed ranges in air vary between 2 and 9 cm for the different
emitters, as the corresponding a-particle energies vary between 4 and 9 MeV. It is

also possible in certain nuclei for the transformation to proceed from an excited state

X* to the daughter state Y. The resulting a particles are emitted with excessive
energy, between 9 and 12 MeV, and are characterized by their distinctive long range.
 15-3 a Decay 753

Figure 15-8

Kinetic energy of emitted « particles versus mass number for several radioactive sources. The
data for the selected elements polonium, radium, thorium, uranium, and curium are taken from
Chart of the Nuclides, 13th edition. All quoted energies are associated with nuclear transitions
X -» Y from the ground state of X A
to the ground state of Y. few of the lighter nuclei emit a
particles with energies smaller than the values plotted here; these cases include the very
144 148
long-lived nuclides Nd and Sm.

Cm

190 200 210 220 230 240 250

This type of a decay is quite rare because the emission process X* —> Y + a must

compete favorably with the y-ray deexcitation X* —> X + y.

Radioactive a emission is said to be monoenergetic since every a particle in a given
decay X —> Y + a is emitted with the same kinetic energy K a Figure 15-8 shows a
.

plot of these unique values of Ka versus the mass number A, organized by element,
for a large number of a-emitting isotopes. One of our two main objectives in this
section is to explain the uniqueness of these energies. We see from the figure that
almost all the observed values fall between 4 and 9 MeV, a rather narrow energy
interval. It is remarkable that the corresponding half-lives have an enormous range of
variation, extending over some 24 orders of magnitude. We observe an inverse
correlation between half-life and a-particle energy, where the longer-lived nuclides
have the smaller values of K a and vice versa. We can illustrate this behavior by
754 Nuclear Processes

Figure 15-9

Monoenergetic a decay for a parent nucleus

at rest.

©
-p < ( Y K») > P

Two-body final state

quoting the following extreme values from the nuclear chart:

t 1/2 = 1.40 X 10'° y and Ka = 4.01 MeV for

232
Th,

while

t 1/2 = 0.30 /xs and Kn = 8.78 MeV for

212
Po.

Our other main goal in this section is to understand the correlation between t 1/2 and
A' n , with special concern for the great disparity in orders of magnitude of the one
quantity compared to the other.
It is easy to see why the energies of the a particles are unique. We apply the
familiar conservation laws of momentum and energy to the process

^X-^*Y+*He,
and we note that the decay produces an a particle in a two-body final state. The parent
nucleus is taken to be at rest, as in Figure 15-9, so that conservation of momentum
requires the emitted a particle and the recoiling daughter nucleus to have equal and
opposite momenta. Conservation of the total relativistic energy provides another
relation involving the nuclear masses:

M x c' = M Y c
2
+ KY + M ac
2
+ Ka .

We can add Z electron masses to both sides of the equation and convert the
expression directly to atomic masses:

M{ A X)c 2 = [M( A -*Y) + M(*He)]c 2 + K Y + K a .

A criterion for a instability emerges from these relations. The nucleus X a unstable,
is

so that the decay X -» Y + a may occur, whenever the mass of X exceeds the sum of
the masses of Y and a. We define the a-disintegration energy, or Q-value for the decay, in
terms of the difference in mass:

A -4
Q= [M{ A X) - M( Y) - M( 4 Hc)]c 2 . (15-8)

This quantity represents the total amount of released energy to be shared by the two
 15-3 a Decay 755

final particles:

d=Ka + Ky . (15-9)

We may use the nonrelativistic formula for kinetic energy and write

2 2
p p
0.
2Ma 2 My
,2
MA I M

The final solution for Ka is a unique prediction for the a-particle kinetic energy, given
in terms of the masses of the particles participating in the decay. We note in passing
that relativistic formulas are required for the total energy because the rest energies
change with the identities of the particles, while nonrelativistic formulas are allowed
for the kinetic energy because the kinetic energies are much smaller than the rest
energies.
Other conservation laws also play a part in the determination of the final state. Let
us refer again to Figure 15-9 and introduce the nuclear spins I x and I Y along with
the orbital angular momentum L for the Ya system. The a particle has spin zero since
4
He is an i = nuclide. Conservation of angular momentum therefore results in the
equality

I X = IY + L. (15-11)

This constraint among quantized angular momentum vectors implies a condition on

the associated quantum numbers, We recognize the vector addition problem from our
discussion of Equation (9-44) and immediately establish the following bounds on the
orbital quantum number <f in terms of the initial and final nuclear spin quantum
numbers:

•Yl <<f<z x +z Y
- . (15-12)

The nuclear states X and Y are also endowed with definite parities. The a particle is
known to have even parity and the final orbital parity is given by ( — 1 )*. Conservation
of parity implies a multiplicative constraint among the various odd and even factors:

(parity of X) = (parity of Y)(even parity of a)(orbital parity).

We to give even orbital parity, if X and Y have the

conclude that £ must be even,
same parity, must be odd if X and Y have opposite parity.
and that /
The most remarkable feature of a decay is the extraordinarily large variation in
the half-life from one nuclide to another, while the corresponding a-particle energies
and Q- values vary within only a single order of magnitude. It is apparent that t 1/2
must have a very sensitive dependence on (). The explanation for this behavior is
found among the first applications of quantum mechanics to the nucleus, in the work
of G. Gamow and others in 1928. To present the arguments we turn to Figure 15-10
and adopt a potential energy for the Ya system, the final state of the decay
X —» Y + a. The two bodies attract each other at short range, where the nuclear force
is dominant, and experience like-charge repulsion at longer range. These effects
combine to produce a Coulomb barrier whose height, for heavy nuclei, reaches 20-30
756 Nuclear Processes

Figure 15-10

Model of the Coulomb barrier for the a decay X —* Y + a. The potential energy of the Ya
system consists of a strongly attractive nuclear contribution at short distance and a repulsive
electrostatic contribution for larger separation between Y and a. The a-disintegration energy Q
determines the probability for penetration of the barrier.

V(r)

MeV at a separation r of order 10 fm. (We estimate these numbers in the example at
the end of the section.) The Q-value is shown in the figure as the energy level of the
system, since the total kinetic energy is equal to Q at very large Ya separation,
according to Equation (15-9). A typical Q-value is less than 10 MeV, and so a
"classical" Ya system cannot leave the region of nuclear binding and reach the distant
region of large Ya separation because of the high Coulomb barrier. This trapping of
the system at short range corresponds to the existence of the temporarily bound
configuration X. The instability of X is attributed to the finite probability for the
quantum system to penetrate the Coulomb barrier and enter the decay regime at large
r. This line of reasoning suggests a possible theory of a decay based on a solution to
the related problem of quantum tunneling.
The stationary-state wave function at the energy level Q determines the probability
of finding the Ya system in its two configurations on either side of the barrier. The
quantity of interest is the transmission probability for penetration from small r to

large r. The decay constant for the process X— Y+> a is directly proportional to this
quantity. We have encountered a similar situation in Section 5-9, in our treatment of
quantum tunneling for a rectangular barrier in one dimension. We return to our main
 15-3 a Decay 757

conclusion in Equation (5-83) and recall that the exponential function

la
exp l2m(V -E]

is the primary governing factor in the transmission probability. (This result is only
qualitatively germane
a decay, a three-dimensional problem with a sharply peaked
to
Coulomb barrier. The one-dimensional analogue is best suited for transitions X —> Y
in which both X
and Y are even-even nuclides. These species have nuclear spin i = 0,
and so the final Ya state has zero orbital angular momentum, according to Equation
(15-12).) Let us apply the one-dimensional analogy as an approximate guide to the
behavior of a decay and adapt the exponential factor to the picture in Figure 15-10.
We substitute a rectangular step of height V and length a in place of the sharp
barrier, and we argue that the decay constant for X — Y + a
> is proportional to the
tunneling factor

2a
exp
h
Wo-£.
where jjl is the Ya reduced mass and Q is the energy level. This factor decreases very
rapidly with increasing choices of V — Q, the height of the barrier above the ()-value.
We predict a further reduction in probability if we let the choice of a grow with

increasing V — Q, to reflect the fact that the quantum tunnel becomes longer with
diminishing Q_. These features of barrier penetration explain qualitatively why the
observed half-lives grow so rapidly with decreasing values of the a-particle energy.
Since a decay is monoenergetic and since the unique energy of the a particles can
be measured with high precision, it is feasible to observe the energy and gain precise
information about nuclear energy levels. These spectroscopic applications of a decay

Figure 15-11

Decay scheme and a-particle spectrum for 3- Th. Nuclear levels are labeled by
"'

their i
p

quantum numbers and half-lives. The a and y emissions have energies as shown in MeV.

1.40 x 10 10

3.9
1 4 4.1
Ka (MeV)
758 Nuclear Processes

have been employed extensively to study nuclear structure in the heavy elements. A
typical radioactive sample may exhibit a spectrum of a particles in which several
unique energies are observed for the emissions from a single source. A case in point is
!2
Th decay, where the thorium source emits a particles in two groups, at 4.01 and
3.95 MeV. Figure 15-11 presents these data in a decay scheme along with a schematic
display of the a-particle spectrum. The two a groups arise from decays of the type

232
Th-» 228 Ra+ 4 He,

where the radium daughter occurs in its ground state and in one of its excited states.

The shows that the a decay to the excited level is followed promptly by a y
figure
deexcitation to the ground state. Note that the a spectrum maps out the relevant
228
energy levels of Ra, while the observed y-ray energy confirms the spacing between
the levels. Other varieties of a-active parent nuclei exist with greater numbers of
excited daughter states and produce decay schemes of greater complexity.

Example

Let us use Appendix A again for a computation of (Rvalues and a-particle

kinetic energies. A good illustration is provided by the above-mentioned a decay
of '
"Th at the higher of the two quoted energies. We look up the atomic masses
of "
Th, Ra, and He, and we then apply Equation (15-8) to obtain the
disintegration energy:

Q= (232.038054 - 228.031069 - 4.002603)(931 .5 MeV) = 4.082 MeV.

The ratio of nuclear masses in the final state is also needed in order to learn how
much of Q is carried away by the a particle. We find this quantity from the
atomic masses by including the masses of the electrons (m ec 2 = 0.5110 MeV):

M„ 4.002603-2(0.5110/931.5)
= 0.01755.
M Ra 228.031069-88(0.5110/931.5)

(We might as well ignore the electron-mass correction since the ratio of atomic
masses produces the same answer to five decimal places. In fact, the ratio of

mass numbers 4/228 is just as good to four decimal places.) Equation (15-10)
gives the desired kinetic energy

4.082 MeV
Kn = = 4.012 MeV.
1.01755

This result corresponds to the smallest of the values plotted in Figure 15-8. The
Qj value is small compared to the height of the Coulomb barrier in the Ra-He
system. Let us estimate the latter quantity by calculating the repulsive Coulomb
potential energy at a range equal to the sum of the two nuclear radii (the
center-to-center distance in the Ya system of Figure 15-9). We use Equation
(14-3) to find the range,

1/3
r = (228 + 4 1/3 )(1.2fm) = 9.2 fm,
 15-4 $ Decay 759

and we then compute the Coulomb potential energy for that separation:

7 7 -2

V(r) =
4ire r

2
X 9
N m /C 2 2
x 10" 19
C)
=
(2)(88)(9
;
(9.2
10
77
T7
X 10^ 15 m)(l.60
— •

X 10" 13 J/MeV)
)(l.60
77 r = 28 MeV.

This barrier height is seven times as large as the Q-value for the decay. Let us
interpret our calculations with the aid of Figure 15-10. We choose a low-lying
energy level to represent the small value of Q. an ^ observe that a very thick
Coulomb barrier is obtained. The resulting quantum tunnel is supposed to be
232
long enough to account for the long half-life of Th.

15-4 Decay

Nuclear decay has properties and mechanisms quite unlike those associated with the
(5

emission of a particles. The radiation from a /3 source contains nonnuclear charged

particles characterized by their small mass and appreciable penetration in matter. The
two kinds of (i decay involve the nuclear transitions

jX^ z ^Y + ft- and ^X ->

z *jY + /T,

in which the proton and neutron numbers change by one unit while the mass number
A remains the same, as indicated in Figure 15-2. A more fundamental picture of the
phenomena appears to be in effect, where fi~ decay transforms a neutron into a
+
proton within the nucleus and /? decay reverses this basic transformation. A
+
qualitative definition of the /?" and /2 instabilities emerges from these observations.

The parent nucleus evidently has two much mass, either because of a neutron excess
+
in the case of /?~ decay or because of a neutron deficiency in the case of /? decay.
Each type of /? transition alters the system of bound nucleons so that the nuclide ^X^
transforms into an isobar of lesser mass, one unit removed in both nucleon numbers Z
and N. The transformation proceeds along a line of constant A on the nuclear chart,
in a direction toward the valley of stability.

Wehave mentioned the valley of stability on two occasions in Chapter 14. The Z
versus TV plot in Figure 14-4 shows the tendency for stable nuclides to lie in a central
valley bounded by radioactive isotopes on either side. The semiempirical mass formula
in Equation (14-13) determines a mass surface in the variables A and Z and defines a
stable valley as the locus of points of minimum mass in each cross section of the
surface at constant A. We describe these features by graphs of the atomic mass
M(jX) as a quadratic function of Z in Figure 14-13, and we note that isobars appear
on the graphs for each choice of A. A ^-unstable isobar takes its position along the
parabolic curve at a value of M above the minimum. A /? transition makes its

appearance on the graph as a link between the unstable parent and its less-massive
daughter one unit away. The link runs from Z to Z+ 1 for /? decay or from Z to
+
Z— 1 for /3 decay. Figure 15-12 shows such a display for the case of the ^-active
isobars at A = mass number corresponding to the decay scheme in Figure
80, the
15-1. Note that the graph of M
versus Z has two branches, one for the even-even
760 Huclear Processes

Figure 15-12

Atomic mass versus atomic number for isobars

at A = 80. Even-even and odd-odd nuclides
lie on different mass curves separated by the
effect of the pairing term in the mass formula.
+
The fi and /S transitions are indicated by
right- and left-directed arrows leading in unit
80
steps to the ultimate stable species Se and
H
"Kr.
M(u)

79 93

79 92

Se^—^Kr
A 80

31 33 35 37

nuclides at lower M
and another for the odd -odd nuclides at higher M. We recall
from Section 14-5 that the two mass curves are expected for even A because of the
pairing effect. We have constructed a similar set of graphs in Figure 14-13 for the
isobars with A = 98, 99, and 100. The odd- A family at A = 99 is plotted again in
figure 15-13 as a graph of M
versus Z and also as a partial decay scheme. The
various (i processes are indicated in both parts of the figure. Observe that the
transitions Z —> Z— 1 appear in the decay scheme in two different forms, designated
by the notation EC and fi + . We distinguish these processes in due course as we
continue through the subsequent discussion.
The conservation laws of angular momentum and energy introduce an immediate
new development in the interpretation of fi decay. Let us consider angular momen-
tum first and note that a problem arises when we examine the spins of the participat-
ing particles and nuclides. The emitted charged particle is either a spin-^ electron in
decay or a spin-^ positron in /? decay. The nuclear transition X —» Y involves
+
fi

no change in A, and so both nuclear spins x and Y must be given by integers, if A isi z

even, or half-integers, if A is odd. In either case a half-unit of spin is missing when

conservation of angular momentum is applied to the decays. The orbital angular
momentum also participates in the conservation law; however, this quantity is integer
valued and cannot account for the missing half-unit of angular momentum. Conserva-
tion of energy presents another glaring problem concerning the energies of the
observed electrons or positrons. The emitted fi particles are not monoenergetic as in

the case of a decay but are distributed In a continuous spectrum of energies, Figure 15-14
shows an example of a fi spectrum in which the kinetic energy of the electrons varies
from nearly zero up to a maximum value determined by the energy released in the
 15-4 £ Decay 761

Figure 15-13

Sequential (i decays in the A = 99 system of isobars. The plot of M versus Z reproduces one of
the graphs in Figure 14-13. Data in the decay scheme include the values of i
p and t i/2 along
with the released energies in MeV. The /? decays descend from the left while the electron-
+
capture transitions and /8 decays descend from the right.

M (u)

98.92

\
\ Pd</

\ Rh
c/(/^
(%/ 15s
Tc Ru

Nb
39 41 43 45
k-z
47

3.64

16.1 d

65.9 h

Mo

+
3%//3
1.361 • • •
1209
• • J

2.13 « 10 5 y

"Tc 0.29\V stable

Ru

nuclear transition. This display of events reveals that less than half of the total

available energy is carried off by the detected charged particles. The missing amounts
of angular momentum and energy are explained by arguing that ft decay must
include another unobserved particle in the final state. The argument treats the two
processes

X-* z ^Y + j8- and |X-^,Y + /r

+
as three-body decays and interprets the symbols /? and /S as two-particle systems. The
new third particle in the final state is hypothesized to share the total angular
momentum and energy and carry away an unobservable portion of these conserved
quantities.
+
The unseen companion of the positron in /3 decay is known as the neutrino. Its
antiparticle, the antineutrino, is emitted to accompany the electron in (i~ decay. We
762 Nuclear Processes

Figure 15-14

Electron spectrum in the /? decay of Bi

Endpoint
1.161 MeV

use the designations v and v, and describe the two nuclear processes as

£X ->^,Y + *-+ F (p~ decay)

and
A +
Z X ->^,Y + e + v (/?+ decay).

We invoke anew type of conservation law for nonnuclear particles when we employ
this notation. By convention, e~ and v are called particles, while e + and v are called
antiparticles, so that the total number of nonnuclear particles is conserved, along with
the total number of nucleons, in each of the decays. Conservation of the total charge
requires the neutrino to be a neutral particle. The original problem of the missing
angular momentum is resolved by assuming that v and v are spin-^ fermions. Since
the electron cannot be a constituent of the nucleus, it follows that the two-body yS
+
systems e'v and e v must be created in the nuclear transformation and are not
regarded as "present in the nucleus" prior to the decay.
The problem of the missing energy in /? decay was acknowledged by 1930, before
the coming of the neutron. An explanation for the continuous j3 spectrum was
urgently needed since the observations presented a challenge to the fundamental law
of conservation of energy. Pauli offered a solution in 1931 by proposing the existence
of an unobserved third particle. The neutrino hypothesis was accepted, even though
the particle itself could not be observed, because the violation of the sacred conserva-
tion laws was not a tolerable alternative. The mass of the neutrino was supposed to be
exceedingly small, perhaps to the point of vanishing, to explain the observed /S

spectrum. The interactions of the neutrino were presumed to be practically negligible

to explain why the particle should not be detected. Predictions of the interaction cross
section were small enough to enable the neutrino to penetrate astronomical distances
in matter. Neutrinos were detected for the first time, despite the incredible weakness of
their interactions, in 1956 by F. Reines and C. L. Cowan.
an experiment completed in
These investigators constructed a large scintillating detector in the vicinity of a
high-power reactor and observed evidence of the neutrino-absorption process

+
v + p -* n + e .
 15-4 p Decay 763

Antineutrinos were produced with a very large flux from the /2-active fission fragments
in the reactor, and absorption events were recorded whenever the final-state particles
were observed. Positrons and neutrons were detected, through the processes of positron
annihilation and neutron capture, by the observation of photons in the scintillating
liquid of the detector. This experiment established the existence of the neutrino, and
later experiments confirmed the very small prediction for the neutrino interaction
cross section.
The neutrino concept certainly does not require the mass of the neutrino to be
precisely zero. We must turn to experiment for a determination of the mass, as we
should for any particle. The question of a neutrino mass is of great interest in some of
the current problems in particle physics. We can safely ignore this question when we
study events in the main part of the /3 spectrum, because the mass of the neutrino is

known to be very small, much smaller than the mass of the electron.
Let us begin our kinematical investigations by considering /? decay. We apply
conservation of energy to the three-body decay of a nucleus X at rest by writing

Mx c
2
= MY c ' + KY + m e
c
2
+ K +E
e v
. (15-13)

Note that the relativistic neutrino energy E v

includes a possible nonzero rest energy
m v c 2 We
. use nuclear masses for the nuclides X and Y, and we assume throughout
that both parent and daughter are in the ground state. The addition of Z electron
masses on each side of the equation results in the equality

{M x + Zm e
)c
2
= [M y + (Z + l)w,]<-' + A' v + A',, + £„,

or

M{ Az X)c 2 = M( z ^)c 2 + Ky + K + e
E„

in terms of atomic masses. We therefore define the (Rvalue, or disintegration energy,

for ~ decay by the equations
ft

d= [M(jX) - M( z ^)]c 2
= KY + K +E
e v . (15-14)

This result identifies a specific total amount of energy to be shared among the three

final particles Y, e~, and v. In fact, the recoil energy of the massive nucleus Y is

usually small enough to be neglected except in situations where e

K
and E v are also
+
very small. The kinematics of /S decay also satisfies Equation (15-13). However, we
take a different step when we add Z electron masses to both sides:

(M x + Zm f
)c
2
= [My + (Z - \)m e
]c
2
+ 2m/ 2 + KY + K + e
E„.

Thus, we obtain the equality

M{jX)c 2 = M{ z A ,Y)c 2 + 2m ec 2 + K Y + K + e
E„

+
when we rewrite the result in terms of atomic masses. The Q-value for fi decay is
764 Nuclear Processes

therefore defined as

d= [M( A2 X) - M{ Z ^Y) - 2m e
}c
2

= KY + KE + E ,.
t
(15-15)

Equations (15-14) and (15-15) give the total amounts of energy released in the two
decays. We note that the nuclides X and Y must give a positive expression for () if ft~
or ft
+
decay is to take place. The equations tell us that K e
is strictly less than Q, as
needed problem of the missing energy. The equations also tell us that the
to solve the
maximum K r approaches Q, for zero nuclear recoil, in the limit of vanishing
value of
neutrino energy. This maximum kinetic energy defines the endpoint in the spectrum for
a given ft decay, as in the illustration provided in Figure 15-14.
The neutrino-mass question comes to the surface when the ft spectrum is examined
close to its endpoint. This region of maximum K (
and minimum E v
is sensitive to the
rest energy of the neutrino because the decay probability is a function of the neutrino
momentum
m 2 c*
Pv = •

The fact that Ev and m vc appear together in this expression implies that a test for a
nonzero mv is conceivable if events can be detected at sufficiently small values of £,,.
(We note in passing that pv can only approach zero for mv = 0, because a zero-mass
neutrino cannot be at rest in any Lorentz frame. The ft spectrum distinguishes the
m v = case since the approach to the endpoint varies gradually with K e
only when
pv = E v /c.) This idea is under investigation in a current experiment to study triton ft

decay,
3
H ^ He :i
+ e~+ v,

near the endpoint of the electron spectrum. Indications suggest a lower bound for m vc 2
around 30 eV, a rather small neutrino rest energy. This question remains unsettled,
however, since there are strong arguments for a much smaller neutrino mass from
other investigations.
+
A nucleus may undergo a second kind of ft transformation in the process of
electron capture. This phenomenon is illustrated in Figure 15-15 by the reaction

in which the electron is absorbed from an atomic orbital state to initiate the nuclear
transformation. The process is most favored when capture occurs for a K electron,
because the /= orbital assignment maximizes the probability of finding the electron
in the volume of space occupied by the nucleus. An electron capture is detected when
an atomic x ray is observed; the x ray results from the transition of an outer electron
to fill the inner hole left by the captured electron. We neglect the atomic binding
energy in the initial state and apply conservation of energy to the process by writing

Mx c
2
+ m t
c
2
= MY c
2
+ KY + E„. (15-16)

The addition of Z— 1 electron masses produces the equation

(Af x + Zm r
)c
2
= [M y + (Z - \)m t
]c
2
+ KY + £„,
 15-4 fi Decay 765

Figure 15-15

Initial and final states of the electron-capture

process.

Atomic orbit

^<Y) ©^

or

M{jX)c 2 = M( z ^Y)c 2 + KY + E v
.

The Q-value for electron capture is therefore given in terms of atomic masses by the
formulas

d= [M(jX) - M( z ^)\c 2
= KY + E„. (15-17)

This amount of energy released to the final Yp state must be a positive quantity, so
that the atomic mass of X must exceed tne atomic mass of Y, if electron capture is to
occur.
+
Equations (15-15) and (15-17) refer to /? transitions between the same parent and
daughter. The difference in Q-values implies that electron capture is energetically
+
allowed whenever /3 decay takes place. The two processes compete under these
+
circumstances, as suggested in some of the transitions shown in Figure 15-13. Since fi

decay gives the smaller Q-value, it is possible to have masses of X and Y for which
Equations (15-15) and (15-17) have opposite signs. In this situation the unstable
+
nucleus undergoes electron capture as its only mode of /? transition. We illustrate
some of the possibilities in the examples below.
Our discussion of ft decay presumes that both X and Y are in their ground states.
A /? transition often leaves the daughter nucleus in an excited state Y*, which then
deexcites by the y-emission process Y* — Y +> y. We observe such a transition by
detecting a y ray in delayed coincidence with the observed /8 particle. The Q-value
formulas determine the total released energy, including y-ray energy, in this situation.

Example

The isobars 272 Mg, 2 ]A\, and ^Si engage in /? processes similar to those of the
A = 99 system in Figure 15-13. A glance at the tabulated atomic masses tells us
27
that A1 is the stable isobar:

27 27 27
26.984342 u for Mg, 26.981539 u for A1, and 26.986704 u for Si.
 >

766 Nuclear Processes

The 2 'Mg nuclide undergoes /8~ decay,

»Mg-»£Al + «"+*,

with released energy given by Equation (15-14):

Q_ = (26.984342 - 26.981539)(931.5 MeV) = 2.611 MeV.

2
One mode of instability for Si is the electron-capture (EC) reaction

e~ + f4 Si -»^A1 + v.

The disintegration energy is found from Equation (15-17):

Q_ = (26.986704 - 26.981539)(931.5 MeV) = 4.811 MeV.

We obtain a result larger than twice the rest energy of the electron, and so we
+
also expect fi decay

+
ftSi -*^A1 + e + v.

Equation (15-15) tells us that the Q-value is found by computing

+
Q(£ ) = (£(EC) - 2m„c 2 = 4.811 MeV - 2(0.51 10 MeV) = 3.789 MeV.

Each of these released energies corresponds to a difference of nuclear ground-state

energy levels. Actually, some of the observed /? decays lead to excited daughter
27
states in A1 and continue on to the ground state by y emission. The same state
of affairs prevails in Figure 15-13.

Example

80
Figure 15-1 includes all three /? processes in the decays of the radionuclide Br.
Let us consult the table of atomic masses and calculate the relevant (^-values.
For /T decay,
80
Br ^ 80 Kr + e~+ J>, we find

= (79.918528 - 79.916376)(931.5 MeV) = 2.005 MeV.

For electron capture, e~ + m)

Br — 80
Se + v, we find

Q(EC)=[A/( 8?Br)-M(^Se)] C 2
= (79.918528 - 79.91 6521 )(931 .5 MeV) = 1.870 MeV.

For /T decay, 80
Br ^ 80 Se + e
+
+ v, we find

+
Q.(P ) = Q( EC - 2m S 2 = ) 1-870 MeV - 2(0.5110 MeV) = 0.848 MeV.

The first two of these released energies are entered on the decay scheme in the
figure.
 15-5 The Weak Nuclear Interaction 767

15-5 The Weak Nuclear Interaction

The /? instabilities of nuclei are caused by a fundamental type of force known as the
weak interaction. We call the force fundamental because its influence applies to the most
basic particles in nature. The weak interaction affects the behavior of nuclear particles
and exhibits properties of strength and range on a scale very different from the strong
nuclear force. Despite its feeble strength, the weak nuclear force is able to reveal many
of its characterizing features through the commonplace phenomenon of nuclear /?
decay. In return, much is learned about the structure of the nucleus through the use of
the /?-decay interaction as a nuclear probe.
The weak force shows its strength in the properties of the neutrino, whose processes
are only of the weak variety. We can appreciate the weakness of the force by
inspecting the extraordinarily small cross sections for the interactions of neutrinos in
matter. We realize some of the consequences when we also learn that neutrinos are
produced in certain nuclear reactions that occur typically in the interiors of stars. The
stars are almost transparent to the passage of neutrinos, and so the weakly interacting
particles easily escape the stellar interiors. The result is a continuing inundation of the
universe with a debris of almost-massless neutral particles.
The primitive weak phenomena in all nuclear /? decays are the neutron and proton
/? processes

n — p +
> e~ + v and p —> n + e
+
+ v inside the nucleus.

The /? decay of the neutron also occurs in the free state and accounts for the observed
instability of this basic nuclear particle. Both nuclear and nonnuclear particles are
engaged in these manifestations of the weak interaction. The proton and neutron have
already been classified by the name nucleon. This subclass of particles is part of a
larger family whose members interact s'rongly with each other. The electron and
neutrino do not participate in the strong nuclear interaction and are called leptons to

distinguish their behavior from that of the nucleons. We define a lepton number L
according to the particle and antiparticle assignments

+
L = + 1 for e~ and v and L = — 1 for e and v.

The nuclear yS decays are then supposed to obey a conservation law for the total
number of leptons along with the familiar law conserving the total number of

nucleons. We have learned to identify p and n as two different charged isospin states

of a single generic nucleon in order to implement the symmetry properties of the

strong nuclear force. It also proves fruitful in the context of the weak interaction to let

an analogous generic lepton be comprised of the two differently charged quantum

states e~ and v. We enlarge upon this notion later when we encounter other types of
leptons.
The construction of a weak interaction theory has had a long history. Theoretical

developments began in nuclear physics in 1934 when Fermi proposed his theory of
/?-decay transitions in nuclei. His picture of the nuclear /? interaction had a number of

very serious shortcomings. Nevertheless, the tentative theory was phenomenologically

instructive as a guide to the (i spectra and selection rules for a large body of nuclear

decays. Several crucial discoveries were made in experiment and in theory during the
1950s. These ingredients became additional aspects of the picture as attention then
turned toward the understanding of the weak decays of the elementary particles.
The Fermi theory draws a close analogy between the weak interaction in nuclear /8
decay and the electromagnetic interaction in atomic y emission. Let us represent the
768 Nuclear Processes

Enrico Fermi

deexcitation of the atom A* -» A + y as a radiative transition of a bound electron

with specific subshell quantum numbers:

In similar fashion let us express the nuclear ft decay X Y + e + v in terms of the

bound neutron-to-proton transformation

n(X) -*/>(Y) + *-+ v.

We illustrate these two fundamental processes in Figure 15-16 by space-time diagrams,

which show the passage with time from the respective initial states to the correspond-
ing final states. In each case the emitted radiation is created by virtue of the relevant
interaction and is not regarded as "present in the emitting source" prior to the
transition. We know from Section 7-5 that the oscillation of the electric dipole moment

( — er) in a transition state describes the atomic photon-emission process and that the
dipole transition amplitude determines the intensity of the radiation. Let us express
the formula for the amplitude in terms of the electron states in the figure by writing

ftt^a/T,

where a, and a, represent initial and final sets of subshell quantum numbers
(nc"m^m ) according to Equation (9-9). In the Fermi theory there is an analogous
s
 15-5 The Weak Nuclear Interaction 769

Figure 15-16

Atomic y emission and nuclear /? decay as bound electron and nucleon single-particle
transitions. The electron states a, and <x
f
denote and final subshell quantum numbers,
initial

while the nucleon states X and Y refer to parent and daughter nuclei.

P(Y)
e(otf)

Time

Space

e(a,) n(X)

amplitude of the form

4>%4>*dT
/

to describe the transition of the nucleon in the nuclear transformation X —» Y. We can

use this integral expression to deduce selection rules for nuclear /? decay. The resulting
constraints on the quantum numbers are analogous to the electric dipole conditions for
atomic radiation.
The transforming nucleon in Figure 15-16 is a bound particle with definite initial

and final orbital quantum numbers. These £ values label the angle dependence of the
nucleon eigenfunctions in the Fermi transition amplitude. The amplitude vanishes if

the / values are not equal, because of the orthogonality of the spherical harmonics in
the integral J^y^Px ^ T This observation means
- that the nucleon does not change its

orbital state, so that the overall parity of the nucleus remains unaltered in the
transformation. An allowed transition is further defined as one in which the pair of
leptons is emitted with orbital angular momentum €= 0. This type of decay is

favored because there is no centrifugal potential energy barrier to inhibit the emission
of the created particles. The nuclear /? process is said to be forbidden whenever the
/= condition on the leptons is not met. (In this context forbiddenness implies a high
degree of suppression rather than an outright prohibition of the decay. Forbidden
transitions actually occur for many unstable species on the nuclear chart. The degree
of suppression grows with increasing { , and so the half-lives tend to be longer for these
nuclides.)
Let us consider only allowed transitions and look for constraints on the change in
the nuclear spin as X
transforms into Y. The emitted /? system consists of two spin- L ,

must appear in states with two possible values

particles; therefore, the pair of leptons
for the total spin quantum number. We recall our analysis of the two electrons in the
helium atom and conclude that the electron-neutrino system can emerge with spins in
the s = singlet and the s = 1 triplet states. We isolate the s = case first and use
conservation of the total angular momentum to argue that the nuclear spin cannot
change in the transition X -» Y, since the leptons are emitted with tf= 0. The
conclusion, that i
x =
Y or A;
= 0, is
i known as a Fermi selection rule. We then turn to
the other possibility in which the / = lepton pair is created with total spin s = 1 . In
770 Nuclear Processes

this case we express the conservation of angular momentum for the process X Y+
by writing
i

x = i
Y + 1.

The addition of vectors constrains the quantized angular momenta such that the
nuclear spin quantum numbers must obey either i
x = *
Y or ix = i
v + 1. We also
note that the conservation law does not permit transitions from i
x = to i
Y = 0. The
result, that A? '
= or + 1, is a second type of selection rule due originally to Gamow
and E. Teller. We distinguish the two cases s = and s = 1 by calling the one a
Fermi transition and the other a Gamow-Teller transition.
We observe that the Fermi transition amplitude /^y'/'x ^ T contains no operation
to change the nuclear spin. Another amplitude must therefore be introduced to
accommodate the A* = + 1 transitions included in the Gamow-Teller selection rule.
The required spin modification does not affect the nuclear parity, and so the parity of
the nuclear state remains unchanged in both Gamow-Teller and Fermi transitions.
Let us summarize our conclusions about the allowed decays and the emission of /?

radiation in an /= state. We separate the two lepton spin-state possibilities by the

following rules:

s = 0, Ai '

= 0, no (15-18)

for Fermi transitions, and

s= 1, A/ = Oor +1 (butO -f> 0), mi (15-19)

for Gamow Teller transitions. Both selection rules are designated "no" to indicate no
change in the parity of the nuclear state. We recall that the total spin quantum
numbers s = and s = 1 refer to antiparallel and parallel spins. Let us apply this
familiar picture to the emission of the pair of leptons and represent the selection rules
schematically with the aid of Figure 15-17. Specific examples of allowed Fermi and

Figure 15-17

Selection rules for Fermi and Gamow-Teller transitions in the decay X— > Y+ e~ + v.

Neutron fi decay involves both of these contributions.

Fermi (x) Gamow-Teller (7)

transition transition j

Y i
4

Antiparallel lepton spins Parallel lepton spins

= <y = or *x = »Y ± 1
'x i'x <y

(but ix = -h ;
Y = 0)
 75-5 The Weak Nuclear Interaction 771

Gamow-Teller /? decays are given below. We have already remarked that forbidden
decays also occur. These processes can be associated with changes in the nuclear
parity and with changes by more than one unit in the nuclear spin.
We have learned in Section 7-5 that the overall parity of an interacting system
obeys a multiplicative conservation law in the radiative transitions of atoms. We also
know that these processes are governed by the electromagnetic interaction. It is

natural to ask whether the overall parity is similarly respected by the weak interaction
in the fi decays of nuclei. We discuss the experimental and theoretical responses to this
important question in Chapter 16, when we turn to the more recent discoveries in
weak interaction physics.

Example

+
The )8 decay of Sc is described as

+
_>i
Sc -»gCa + e + v,

+
which both
in initial and final nuclides have for their i
!'
quantum numbers.
This allowed — > transition is a Fermi process, obeying the selection rules
given in Equations (15-18). The Gamow-Teller selection rules in Equations
32
(15-19) are illustrated by the f$ decay of P,

<-'p _»32c , - , -

+ 32 +
The i
p values are 1 for P and for
!
"S, implying A; = - 1 with no change
in parity. Most allowed /? decays proceed via a combination of Fermi and
Gamow-Teller The decay of the neutron is a case in point since the
transitions.
emitted leptons e~ may have parallel or antiparallel spins, and the
and v

nucleon spin may or may not flip in the n -» p transformation. Forbidden

transitions are also much in evidence across the nuclear chart. An interesting
36
example is furnished by the /? decays of C1,

?fCl -»?j|Ar + *~+ P and 3 3

^C1 -> *S + e
+
+ v,

in which the p quantum numbers transform from 2 + to + This two-unit

i .

change in nuclear spin cannot be balanced by the spins of the leptons alone, and
so a nonzero value of / is needed in the orbital state of the leptons. A
36
suppression of C1 decay results, accounting qualitatively for the long half-life

of the nuclide, t 1/2 = 3 X 10

5
y.

Example

A very crude calculation can be made along the following lines to estimate the
strength of neutrino interactions in matter. Let us examine this question in terms
of the antineutrino absorption reaction v + p —> n + e
+
, as studied in the
Reines-Cowan experiment. We construct the absorption cross section ov as an
effective area presented toan incoming antineutrino by a target proton, incorpo-
rating the probability for an interaction to occur. The primitive weak nucleon
transformation is represented by the (i decay of the neutron n ^> p + e~+ v.
772 Nuclear Processes

The average time of decay is found from the 10.5 min half-life:

t 1/2 (10.5 min)(60 s/min)

t = — — = = 909 s.
In 2 In 2

Let us use the reciprocal of this time interval to set a rough measure of the
probability per unit time for the p — » n transition in the v absorption process.

We neglect the mass of the antineutrino and choose a representative v energy of

3 MeV. The antineutrino then has momentum pv = E v /c and de Broglie
wavelength

he 1240 MeV fm
X = —h = —
E„
=
3 MeV
•

= 413 fm.
pv

We take the antineutrino to be localized within a distance of order A while the

particle moves with speed approaching c. The ratio of these parameters de-
termines a "transit time" for the antineutrino:

13
A 4.13 X 10 in
2I
/ -r- = 1.38 X 10 s.
c 3 X 10" m/s

We multiply this quantity by the interaction probability per unit time to

estimate the probability for an antineutrino interaction:

21
1 1.38 X 10 s
P= t- - = - = 1.52 X 10~ 24 .

t 909 s

The antineutrino collides with a target proton if the radius of the target area A
is within the range of localization of the antineutrino. The collision then causes
the absorption of the antineutrino with a probability given by P. We use these
arguments to estimate the target area

2
A = -n A
2
= tt(4.13 X 10" 13 m) = 5.36 X 10~ 25 m 2

and the absorption cross section

o„ = AP = (5.36 X 10
25
m 2
)(l.52 X 10
24
'

)
= 8.15 X 10
49
m 2
.

Let us pursue the arguments a bit farther to estimate the mean free path /„ for
neutrino interactions in matter. This quantity deduced from the cross section is

by identifying ov £v as the volume swept out by antineutrinos between absorptive

interactions with protons in the given medium. It follows that the mean free
path is given by the formula

',= —1

°,«
.

where n denotes the number of protons per unit volume. We take the absorbing
medium to be liquid hydrogen, and we find n from the density and the proton
 15-6 y Decay 773

mass:

70 kg/m 3
= 4.2 X 10
28
rrT
1.67 X l(T 27 kg

Our estimation then gives

1
= =
''
(8.15 x 10-
49
m 2
)(4.2x 10 28 m- 3
2 9 ' X ^^ m "

Thus, the extremely small v cross section translates into an incredibly long mean
free path. This average distance between interactions is large enough to call for
the use of light-year units:

2.9 X 10
19
m
tv = 7i
15
= 3.1 X 10
3
lt-y.
9.46 X 10 m/lt-y

Of course, our estimates are based on an extremely gross calculation. The actual
cross section is somewhat larger, but only by a single order of magnitude. For 3
MeV antineutrinos, a,, is approximately 10
47
m 2
and {v is of order 100
light-years. We offer these figures to demonstrate the extraordinary weakness of
the weak interaction. The observation of antineutrinos begins to become feasible,
as in the Reines-Cowan experiment, when the v flux upon the target is

sufficiently great to achieve an appreciable enhancement of the detection

probability.

15-6 y Decay

The electromagnetic interaction affects the nucleus through the process of y deexcita-
tion. Nuclear y radiation is emitted whenever a transition occurs from an excited level

to a state of the same nuclide at lower energy. The prior state of excitation of the
nucleus is often the result of some nuclear reaction or disintegration, as in the example
shown in Figure 15-18. If the excited level is not so high as to allow the prompt
ejection of a nuclear particle, then the radiative process offers the main available
mode of decay. Photons produced in these electromagnetic transitions have energies of
MeV order, a typical scale of energy for nuclear excitation. A particular nucleus
yields a spectrum of y rays characteristic of a certain system of excited states. The
resulting decay scheme is unique and serves as a signature for the radiating species.
Measurements of y-ray wavelengths may be made using crystal spectrometers like
those employed for atomic x rays, provided the energies of the emitted photons are not
far beyond the usual x-ray regime. These Bragg techniques are used for y rays with
energies up to 1 MeV. Radiation of moderate energy may also be detected by
introducing a thin-foil material (called a radiator) in the path of the photons and by
observing the ejection of electrons produced by the photoelectric effect or the
2
Compton effect. If the y energy exceeds 2m e
c , the detection of photons can be
performed by letting the y rays produce electron-positron pairs in a thin-foil

absorber.
774 Nuclear Processes

Figure 15-18

Sequential /? and y transitions in the decay of

60
Co. The /? process leads to an excited state
60
of Ni, which then decays to the ground state
by the emission of y rays. The released
energies are quoted in MeV for each decay.

5* 5.27 y
0.318
.Co 3.3 ps
0'
4
2 -

1.173

2*
Y 0.7 ps

1.332

0*
Y stable

Ni

We express the y decay of an excited nucleus as

zX* ix + y,

and we note that the final level need not be the ground state. This process is not
fundamentally different from the radiative deexcitation of an atom, although the
energy scale is appreciably larger for nuclear radiation. Other numerical distinctions
come into play when we consider the enormous range of lifetimes found in y decay.
The vastly different probabilities for the various radiative transitions depend on the
y-ray energies and the i p quantum numbers of the initial and final nuclear states. It is
instructive to organize all these decays with the aid of selection rules similar to those
found for the emission of electromagnetic radiation in atoms.
We have taken the electric dipole transition to be the only important mechanism in
the deexcitation of atoms. Sources of radiation other than the oscillations of the
electric dipole moment must also be considered in nuclear y decay. Figure 14-18
shows the electric dipole as one of a sequence of configurations that make up a
complex distribution of charge. Nuclei may also have quadrupole, octupole, or higher
electric moments as nonnegligible contributors to the radiation field. We classify these
rnultipole structures as 2 -poles, taking k= 1,2,3,... for the sequence of dipole,
quadrupole, octupole, . . . configurations. Magnetic multipoles also exist as distinct

physical systems with the same 2

k
designations. We note that no k = radiation exists
because such a monopole would be spherically symmetric and not transverse, as
field

required for the propagation of electromagnetic waves. Classical examples of electric

 156 y Decay 775

Figure 15-19

Oscillating electric and magnetic dipole

moments.

ci^

and magnetic dipole sources of radiation are shown in Figure 15-19. We associate
electric dipole radiation with the linear oscillation of an electric charge and magnetic
dipole radiation with an oscillating current loop. The analogous k = 1 quantum
systems are described by the expectation values of the electric and magnetic dipole
moments, oscillating in a transition state. Similar descriptions apply to the multipoles
beyond k—\.
The multipole index k is equal to the angular momentum (in h units) carried away
by each photon in a 2*-pole radiation field. This interpretation of k as an angular
momentum quantum number generalizes oui remarks in Section 7-5, where we
consider the special case k = 1 and find that the electric dipole photon radiates one h
unit of angular momentum. The probability for radiative nuclear decay depends
sensitively on the quantum number ';, as large assignments of k imply highly
suppressed rates of decay and long radiative lifetimes. We can illustrate this property
with the aid of the following qualitative list of ranges of the mean life t, organized by
multipole for given extremes of the photon energy e:

~ lb
£1
1

electric dipole 10 to 10
14 12
magnetic dipole Ml 10" to 10 s

10" 10" 8 as e ranges from

electric quadrupole E2 to s

10~ 9 6 1 MeV down

magnetic quadrupole M2 to 10 s
to 200 keV.
electric octupole £3 10" 6 to 10" 2 s

magnetic octupole M3 10~ 4 to 10 s

We use the conventional notation Ek and Mk to symbolize the various electric and
magnetic 2 A
-poles. Note that t grows through many orders of magnitude as k

increases, and observe that the electric multipoles have the faster decays for each
value of k.

and magnetic multipoles carry definite parity as well as definite angular

Electric
momentum. We know that electric dipole radiation has odd parity since the behavior
of the E\ transition amplitude is linked to the space-inversion property of the
odd-parity dipole vector er. Magnetic dipole radiation can be attributed to the
776 Huclear Processes

oscillations of a spin magnetic moment in a transition state. We therefore assign even

parity to the Ml mode, since space inversion has no effect on
These observations
spin.
can be generalized systematically for all electric and magnetic multipoles, with the
following conclusions:

Electric 2*-poles have even/odd parity for even/odd k

and
/t
magnetic 2 -poles have even/odd parity for odd/even k.

Thus, we associate opposite parities with the Ek and Mk modes for each value of k.

Selection rules in nuclear y decay follow from the conservation of overall angular
momentum in the nucleus-plus-radiation system. We let the participants in the process
X* — X +> y have nuclear spin and multipole quantum numbers i*, i, and k, and
we then use these assignments to denote quantized angular momentum vectors in the
conservation law

i* = i + k.

This familiar vector constraint implies that the multipole index k must obey the
condition

\i* - i\<k < i* + i. (15-20)

We have already learned that no radiation multipole exists for k = 0. It follows that
the quantum numbers i* = i = cannot satisfy the vector equality for any k, so that
no — * radiative decay is possible.
Radiation may be emitted with or without a change of parity in the nuclear state.
Conservation of the overall parity calls for the emission of an odd-parity multipole
when X* and X have opposite parity, or an even-parity multipole when X* and X
have equal parity. We can be more specific about the multipoles we invoke the if

space-inversion properties of the various electric and magnetic modes. Thus, we find
that parity conservation permits

El, A/2, E3, . . . radiation with a change in nuclear parity,

and
Ml, E2, A/3, . . . radiation with no change in nuclear parity.

Our list of lifetimes correlates each of these multipoles with a range of values of t.
The enormous variations indicate vividly the role of the selection rules in nuclear y
decay.
The list of t values suggests the existence of nuclear states with large radiative
lifetimes. These metastable systems may
live long enough to allow the direct measure-

ment of such state properties as the mean life, the nuclear spin, and the magnetic
moment. An excited configuration of the nucleus is called an isomeric state, or a nuclear
isomer, if its mean life is long enough to be measurable. The radiative decay is then
said to occur in an isomeric transition, and the phenomenon is known as nuclear isomerism.
We expect isomeric transitions to be accompanied by radiation in the higher multi-
 75-6 y Decay 777

poles, where the probabilities for decay are greatly suppressed, and where the changes
in the nuclear spin are given by several units.
The deexcitation of a nuclear state may also occur by a radwtionless mechanism
known as internal conversion. In this alternative process, the nucleus releases energy in a
transition to a lower state, and the energy is absorbed at once in the electronic
configuration of the associated atom. The exchange of energy results in the ejection of
atomic electrons instead of the emission of a nuclear y ray. An analogous nonradiative
type of transition takes place in atoms through the Auger effect, as discussed in
Section 3-7.

Detail

Transition probabilities for nuclear and atomic radiation vary in powers of a

dimensionless radiation scale parameter £. In the nuclear case the parameter is

defined by the ratio of the nuclear radius and the y-ray wavelength:

R
£
=
A/277

We interpret £ as a means of comparing scales of length for the only two lengths
available in the radiation problem. We then
Equation (2-51) and (14-3) so
recall

that we can express £ in terms of the photon energy and nuclear mass number:

e R A l/i e
£ = 2tt/?
he he

Values of this nuclear parameter are less than ^ for most nuclei, while values of
the analogous atomic ratio are two orders of magnitude smaller for all atoms.
(We illustrate this claim in the first example below.) Since £ is raised to a certain
power to determine the probability for a certain type of transition, it follows that
that type of transition is suppressed much less in nuclei than in atoms. This

comparison of scales tells us why more radiation multipoles are considered in the
case of nuclear y decay.

Example

A typical nuclear y energy might be as large as 2 MeV. The corresponding

wavelength is two orders of magnitude larger than a nuclear diameter:

he 1240 MeV •
fm
X = — = = 620 fm.
e 2 MeV

This comparison of lengths is the idea behind the radiation scale parameter £.
Let us look at the upper end of the range of £ by choosing a large mass number.
778 Nuclear Processes

We take A = 6
3
and again set e = 2 MeV to get

R A l/3 e (1.2fm)(6)(2MeV)
£ = = = 0.073.
he 197 MeV •
fm

The probability for y decay depends on £ raised to a power, where the exponent
increases with the multipole index k. The smallness of £ implies small decay
rates and long lifetimes for radiation in the high multipoles. We find an even
smaller scale parameter when we consider the radiative deexcitation of atoms.
Let us estimate £ for atoms by computing a ratio of typical lengths:

£ = —
2tt/?

A
- = 2tt
6
10^

X
10

10~
m
=
7
—m = 1 X 10" 3 .

Electric dipole transitions take the smallest power of £ and give the only
appreciable modes of decay for such a small scale parameter. This argument
justifies the neglect of all but the E\ mode in the radiation from atoms.

Example

l37
The (3 decay of Cs leads predominantly an isomeric state of 137 Ba, as
to
indicated in Figure 15-20. This y level has a measurable half-life of 2.55 min.
+
Its isomeric transition to the \ ground state is labeled as such in the figure. The
transition occurs with a change in nuclear parity, while the nuclear spin
decreases by four units. Equation (15-20) tells us that the multipole quantum
number is in the range 4 < k < 7, and parity conservation then implies that the
allowed multipoles are A/4, E5, A/6, and El. The A/4 multipole has the
smallest value of k and is expected to give the dominant decay mode. Larger
values of Az are not uncommon in other isomeric transitions on the nuclear
chart. The correspondingly longer half-lives are listed in hours, days, and even
years.

Figure 15-20
IJ7
Isomeric transition in Ba following the fi
l!
decay of Cs. Energies for the fi and y
transitions are given in MeV.

;<
3( 3.17 y
I37
v 95% • • •

Cs 51
5%\\P
W"/? 2.55 m
V" +
IT 0.662
1.17\ '/
2

stable
V/2 '

l>
 15-7 Resonance Radiation 779

15-7 Resonance Radiation

The y-active states of nuclei have radiative lifetimes ranging from attoseconds to
years.The variations span 25 orders of magnitude, and so the methods for measuring
such disparate intervals of time must vary accordingly. We can determine mean lives
longer than 1 jus directly from observations of y-ray counting rates. We can measure
lifetimes greater than 10 ps, for excited nuclei resulting from (5 decay, by detecting
delayed coincidences between the emitted and y rays. Very short lifetimes can be
(5

determined by an indirect measurement based on the concept of natural width. This

property of an unstable energy level is an important general consideration in the study
of nuclear excitations.
An unstable state has an average lifetime given by the mean life t. The uncertain
duration of the system implies an uncertainty in the energy of the state, in keeping
with the energy-time uncertainty principle. We identify the natural width of the
energy level with the energy uncertainty T and connect the width to the lifetime by
the inverse relation

h
r = -. (15-21)
T

Hence, a measurement of T amounts to a determination of t, and vice versa. Widths

are of order 10" eV in atoms, as typical values of t are around 10 8 s. Much larger
7

widths are found in nuclear states since some of the lifetimes are extremely short. To
I6
give an example, an El mean life of 10" s implies a natural width around 10 eV.

The natural width of an unstable level can b" obtained, in principle, from the
following idealized experiment. We consider a source particle and a target particle of
the same species and assume that both particles are constrained from moving. The
emission of a photon by the source may then result in an observable resonant

absorption of the photon by the target. Both the distribution of emitted radiation and
the cross section for y-ray absorption have widths that include the natural width of
we can measure the natural width if we eliminate thermal line
the excited state. Thus,
broadening from such an idealized absorption experiment. The main idealization is, of
course, the assumption of no motion for the particles in their interactions with the
photon. A free emitter and a free absorber must undergo recoil and exchange the
photon off resonance.
Let us examine phenomenon of resonance radiation (or resonance fluorescence)
this

more closely. how emission and absorption can operate in tandem

Figure 15-21 shows
between corresponding energy levels in two similar quantum systems. The interplay of
processes couples the systems, emitter and absorber, by an exchange of photon energy.
We achieve a resonance when the emitter deexcites and produces a photon with just
the energy needed to excite the absorber. The energy-level difference A£ is exactly the
same for both systems, as required for the resonant transfer of the photon. However,
the recoil of each system causes the emitted and absorbed photon energies e and e a to e

be different from A£ and from each other. This mismatch influences the resonance
mechanism to an extent determined by the natural width of the excited state.
The figure describes the kinematics involved in the conservation of energy and
momentum. Let us look first at the photon emission process X* — > X + y and observe
that the energies obey the relation

E*=E + ee + —
P
2

(15-22)
780 Nuclear Processes

Figure 15-21

Resonance radiation and the effects of recoil. The emitted and absorbed photons have unequal
energiese, and e a both different from the transition energy A£.
,

E* E*

\K \E

Emitter Absorber

®
><£h -(*>,

while the photon energy determines the recoil momentum of X:

P= -•

This problem has been studied in Section 3-6, and the solution for the energy of the
emitted photon has been given in Equation (3-61). We rewrite our result as

A£ (15-23)
2Mc 2

and we note that the photon energy is less than the transition energy by an amount
equal to the kinetic energy of the recoiling system X. We then turn to the absorption
process y + X —» X* and find that the recoil effect requires the incident photon
energy to be greater than the transition energy by the same amount:

(A£V
e. = A£ + (15-24)
2Mc 2

(The proof is left to Problem 18 at the end of the chapter.) Figure 15-22 summarizes
our conclusions in terms of a schematic spectrum of energies for photons emitted and
absorbed at the transition energy AZs. Note that the energies occur in broadened
distributions instead of sharp peaks, due in part to the natural width of the excited
energy level E*. We see that resonance radiation may occur only when the two peaks
in the figure have sufficient overlap. The criterion is realized if the indicated width T
is large compared to the recoil kinetic energy

(A£T
K (15-25)
2Mc 2

We meet this condition for resonance when we consider the visible radiation from
atoms, and indeed we observe resonance fluorescence as a common atomic phenome-
 15-7 Resonance Radiation 781

Figure 15-22

Energy distribution of photons emitted and

absorbed as in Figure 15-21. The peaks are
spread by the natural width T and are shifted
to either side of AE by the effects of recoil.

Emission Absorption

A£- K AE &E + K

non. The analogousnuclear problem finds K much larger than T, however. It would
therefore seem that resonance radiation is not an observable phenomenon in nuclei.
The mechanism for resonance can be recovered by letting the emitter approach the
absorber, so that the energy of the emitted photon is Doppler shifted to the larger
value required for absorption. We can determine the desired shift by noting the
connection between Equations (15-23) and (15-24):

1 + AE/2Mc 2 I AE
'1 - AE/2Mc 2
\ Mc 2

to first order in the small ratio AE/Mc 2 We

then recall from Equation (1-9) that the
.

Doppler effect produces a blue-shifted light frequency, with transformation factor

]](c + u)/(c — u) when the emitter moves at speed u toward the absorber. This
,

relation between frequencies can be cast immediately in terms of the photon energies
e„ and e„ to obtain

c + u c + u
£„ = e. = e = e.\ 1 +
'{?

to first order in u/c. The two expressions for e a tell us that the Doppler effect offsets

the recoil effect if the emitter approaches the absorber at velocity

AE
(15-26)
Mc

Resonance fluorescence has been observed in nuclei by experimental methods based

on this idea.
The resonance condition may also be achieved through the Mossbauer effect, a
technique discovered in 1958 in the experiments of R. L. Mossbauer. The effect is

based on the recoil-free property of the emission and absorption of y rays for nuclei
bound in solids. Embedding the emitter and absorber in separate crystals forces the
782 Nuclear Processes

crystal lattice to take up the recoil of the nucleus in both parts of the resonance
mechanism. An equivalent kinematical result is obtained by substituting the very large
mass of the crystal in place of the nuclear mass in the formula for K. The mismatch
between e, and e a disappears under these conditions, as in the idealized case of the
emitter and absorber kept at rest. The recoilless behavior of the Mossbauer system
makes it possible to achieve a resonance for an extremely sharp y transition and
enables us to measure the natural width of the resulting absorption line.
The Mossbauer effect exercises the criterion for nuclear resonance radiation with
great sensitivity. The technique can be used to detect and measure minute shifts in the
energies of photons caused, for instance, by an altered nuclear environment or a small
relative motion within the system. These perturbations on the photon energy are easily
seen in an absorption experiment, since the slightest mismatch between emitter and
absorber causes the Mossbauer device to respond off resonance.
Mossbauer's original observations were made in a low-temperature experiment
l9l
using the 129 keV y ray in the spectrum of Ir. The effect has since been observed in
numerous y transitions of many different nuclides. The capability to detect small
y-ray energy shifts was put to immediate use in several types of precision experiments.

A test of the theory of relativity was among the first applications of the effect. Use of
the technique has also spread into biology and metallurgy. To cite one example, the
57
14.4 keV y ray in Fe has been used to probe the environments of iron nuclei in
samples of organic and metallic matter.

Example

Resonance radiation is best discussed with the aid of numerical illustrations. Let
us start with the relation between mean life and natural width:

Tt = h= 1.055 X 10
- M s = 0.6582 X 10' 15 eV s.
J • •

H
In atoms we expect to find t ~ 10 s and T ~ 10 7
eV, as noted above.
Visible light corresponds to a transition energy around 2 eV, while atomic rest
9
energies are at least as large as 10 eV. If we use these numbers in Equation
(15-25) to assess the recoil effect, we get

2
(A£) (2eV)'
K= = = 2 X 10" 9 eV.
2Mc T
,
2 Q
9 ,
2(l0 eV)

Our estimates find K much less than T and imply that recoil has no adverse
consequences for resonance fluorescence in atoms. The rather different situation
191
in nuclei is nicely illustrated by Mossbauer's nucleus Ir. The 129 keV y ray

comes from a state with half-life t 1/2 = 0.13 ns. The corresponding natural
width is quite small:

0.658 X 10-
|5
h eV s
r = - = -
a
9
= 3.5 X 10" 6 eV.
t 0.13 X 10- s/ln2

Hence, the energy distribution of emitted and absorbed photons forms two
narrow peaks, unlike the broad ones shown in Figure 15-22. The recoil effect
 15-8 Introduction to Nuclear Reactions 783

separates these peaks by the comparatively large energy 2K, where

2 6
(0.129 MeV) (l0 eV/MeV)
K" = 4 ' 68 X I0 ~' eV
2(191)(931.5MeV)

for a free Ir nucleus. (The substitution of the y-ray energy for the transition
energy is a very good approximation here.) Resonance fluorescence can be
observed via the Doppler effect if emission and absorption occur at a relative
velocity given by

A£ 0.129 MeV
"°^= (191X931.5 MeV)
C = 7 - 25X1 °"f - 218m/s '

according to Equation (15-26).

15-8 Introduction to Nuclear Reactions

Nuclear structure is studied by observing the excitations and transformations of the

nucleus. The goals of the investigation are to determine the states of the nucleus
and
todeduce the properties of the nuclear interaction. We know that radioactive decays
can furnish this kind of information, but only for the species that actually participate
in the various decay processes. We gain the capability to examine the states of any
nucleus at any energies when we turn to nuclear reactions as the means of exploration.
A nuclear reaction may be any of the possible consequences of a collision at short
range between a nuclear projectile x and a nuclear target X. We describe such a
process as

x+X-*Y+y or X(x, y)Y,

for situations where the reaction yields a two-body final state composed of a residual
nucleus Y and
an outgoing nuclear particle y. The product Y may be either stable or
radioactive. In either event we call the process a two-body reaction whenever X and Y
are different nuclides. Nuclear scattering is then classified as a special case in which X
and Y are of the same species. We divide scattering into its categories, elastic and
inelastic, and we express the two possibilities as

X(x,x)X and X(x,x')X*.

In the inelastic case, X* denotes an excited state and x' refers to a scattered particle
whose energy is reduced by the excitation of the nuclear target.
A typical two-body reaction experiment might entail the detection of y as a
function of the outgoing angle, for a number of choices of the incident energy. Typical
beam particles might be protons, neutrons, deuterons, a particles, or other ions. A
charged projectile must have enough kinetic energy to penetrate the region of
Coulomb repulsion around the nucleus in order to produce a nuclear interaction with
the target. For insufficient energy the outcome of the charged-particle collision is
expected to agree with the predictions of Rutherford scattering. If we consider protons
in collision with light nuclei as an example, and recall our calculation of short-range
Coulomb repulsion at the end of Section 14-1, we find that a beam energy of several
784 Nuclear Processes

MeV is needed to gain access to the nuclear regime. A suitable proton accelerator

must be supplied to meet this requirement. We can probe the nucleus at lower energy-
if we use neutrons instead, since neutrons are not affected by electrostatic repulsion. A

nuclear reactor serves as a suitable source of neutrons for these low-energy experi-
ments.
Nuclear reactions were first observed in 1919 in Rutherford's laboratory, when
energetic particles were found to be produced by a particles passing through air.

These occasional events were interpreted as a-particle collisions with nitrogen nuclei,
yielding protons in the final state:

14
4
He + N -*'£> +[H or
l4
N( a, /?)
17
0.

Radioactive a emitters were the only available sources of energetic charged particles
until the coming of the accelerator. One of the earliest machines was the high-voltage
generator, developed for the acceleration of protons by J. D. Cockcroft and E. T. S.
Walton. Particles from this device were used to initiate nuclear disintegrations for the
first time in 1932. The accelerated protons bombarded a lithium target and produced
pairs of a particles via the reaction

[H + ]U ^ 4
2
He + 4.He.

These observations were of special interest since the reaction gave one of the earliest

quantitative mass-energy relation.

tests of Einstein's

A nuclear reaction may proceed from the given initial state xXto any final state,

as long as all the relevant conservation laws are obeyed. The total charge and total
number of nucleons must be conserved, to balance the values of Z and A as in the two
processes cited in the previous paragraph. Energy and momentum must satisfy the
familiar conservation laws in all collisions. Every process other than elastic scattering
has different total kinetic energies in the initial and final states. Such reactions are
called exoergic if

Z^final > i-i ^initial'

or endoergic if

Z^^final
< i-> -^initial-

A certain minimum, or threshold, energy is needed to initiate the reaction in the latter
circumstance. Conservation of the total angular momentum constrains the orbital and
nuclear spin quantum numbers of the participating nuclides, and conservation of the
overall parity adds further conditions to these constraints. Finally, since charge
independence is a valid symmetry of the strong nuclear interaction, a further
conservation law is also applied to the total isospin.
The conservation laws lead directly to a number of important kinematical rela-
tions. Let us apply these considerations to the general two-body reaction X(x, y)Y,
taking the target nucleus X to be at rest in the lab frame as in Figure 15-23a. The
determining ingredients in the kinematics are the beam kinetic energy K x
and the
energy released in the reaction. This latter quantity is also known as the Q-value. We
express the conservation of the total relativistic energy according to the notation in the
figure by writing

K x
+ M x
c
2
+ Mx c
2
= Ky + M y
c
2
+ KY + My c
2
.
 15-8 Introduction to Nuclear Reactions 785

Figure 15-23

Kinematics of the two-body reaction x + X -> Y + y in the laboratory frame and in the center
ofmass frame.

CM
© *~Px Q © *-p'
K' K .

(a) Lab frame (b) CM frame

We then define the Q-value by the equations

Q=(M x
+ Mx -M -MY y
)c
2

Ky + K Y - A\ (15-27)

Note that the nuclear masses may be replaced by their atomic-mass counterparts in
the formula for (), since the requisite electron masses make no net contribution. Note
also that the Q-value for a reaction may be either positive or negative, unlike the
strictly positive difference of rest energies required for a decay. According to our
remarks in the previous paragraph, we have Q > in an exoergic reaction and Q <
in an endoergic reaction. The remaining Q = possibility applies in the special case
of elastic scattering.
Equations (15-27) suggest a way to determine an unknown nuclear mass, provided
the other three masses in the reaction are known and the final kinetic energies are
measured. We concede that the small recoil of the residual nucleus Y is difficult to

detect, so that KY is usually not measurable. Fortunately, we are able to remove KY

from consideration by applying conservation of momentum. This constraint on the
variables is expressed by the two equations

px — p cos = /> Y cos (f>

and />,,sin 6 = p Y sin a>,

using the quantities defined in Figure 15-23a. We assume that the kinetic energies are
small compared to the rest energies so that we can employ the nonrelativistic formulas

K = Kj ~ and KY
2M '

2m: 2M,

Note that relativistic energy conservation must be applied to obtain Equations (15-27)
and that approximations to the kinetic energies may then be adopted when the
786 Nuclear Processes

momenta are nonrelativistic. It is possible to eliminate all the kinematical variables of

the nucleus Y by straightforward use of the foregoing equations. We quote the
following result and leave the derivation to Problem 20 at the end of the chapter:

My j
- 21
MY -J-K K V x yv
cos6. (15-28)

In application, the mass ratios X Y and M /M

/M Y are often replaced, without loss M
of accuracy,by the corresponding ratios of mass numbers. We can determine Q from
experiment by measuring the final energy K and angle 6, for a given beam energy
A',. We then consult Equations (15-27) and use the three known mass values to find

the unknown fourth mass.

It is instructive to analyze the two-body reaction in the CM coordinate system,
where the total momentum is zero and the center of mass is at rest. Figure 15-236
describes the process in terms of the transformed kinematical variables, denoted as
primed quantities in the new system. We continue to assume nonrelativistic momenta
so hat we can pass between the
l CM
and lab frames by means of the nonrelativistic
rule for velocity addition:

velocity of x in lab = velocity of x in CM + velocity of CM in lab.

The target X is at rest in the lab; therefore, the center of mass must be moving
through the lab with velocity p'/M x since this quantity must have the same
magnitude as the velocity of X in the CM system. Hence, the velocity-addition rule
takes the form

px // // Mx + M x
= P-
M x
M x
Mx M MX X

and gives an immediate formula for the momentum of x in the two frames:

Mx + M
PX = (15-29)
P'
M„ x
The colliding particles in the CM system have total kinetic energy

P'
2
P'
2
P'
2
Mx + M x
K' = K'x + K'x =
2M X
2M X 2M X
Mx
We use Equation (15-29) to connect this energy with Kx ,
the beam kinetic energy in
the lab:

K= — —
tr p'
2
I A/ x
-— + M \
2
Mx + M x
= =.K'— -. (15-30)
2 A/. 2M. \ Mx Mx
The result shows that K exceeds A" and reminds us that a portion of the beam
x

energy is permanently allocated to the motion of the center of mass.

An endoergic reaction has a negative ()-value associated with the mass inequality
M + My > M x
+ Mx . The threshold for an endoergic process is defined such that y
 15-8 Introduction to Nuclear Reactions 787

and Y are produced at rest in the CM frame. This configuration of the final state in
Figure 15-236 exists when K' assumes its minimum value K'lh as determined from the
,

conserved relativistic energy:

K'th + (M x
+ Mx )c
2
= (M y
+ MY )c
2
.

When we compare with Equations (15-27), we find that the threshold energy in the
CM frame is given directly by the excess mass:

K'th =-d (Q<0). (15-31)

We then use Equation (15-30) to obtain the corresponding beam energy:

= *.'»,—t: = ".
*,h -Q-^T4 (15-32)

This formula for the threshold of the endoergic reaction in the lab satisfies the
inequality K lh
> K[ h and again reminds us that part of the beam energy is not
available for conversion into rest energy. Thus, it is possible to convert all the kinetic
energy of the colliding particles into excess mass in the final state only in the CM
frame.
Finally, let us return to Equation (15-28) and show how the expression can be put
to spectroscopic use in reactions of the general type X(.v, y)Y. We may take the
residual nucleus Y to be in its ground state, or any of its excited states. Each higher
level has a well-defined excitation energy above the level of the ground state, and so
each excited state has a definite mass value Y M . We let the incident beam have a
fixed energy Kx We then arrange the spectrometer
. to detect the outgoing particle y at

a fixed angle 6, so that we obtain a unique determination of K for each possible state
of the nuclide Y. Hence, the energy spectrum for the detected particle serves as an
image of the energy levels of Y. An example of this form of nuclear spectroscopy is

provided by the (d, p) reaction

[H+SX-^X+JH,
A+
in which the excited states of the nucleus '
X are mapped out by the distribution of
outgoing proton energies. We demonstrate some of the analysis in the following
illustration.

Example

Figure 15-24 shows a portion of the energy spectrum of protons produced in the
reaction
27
A\(d, p)
28
A1. The experiment employs a beam of 2.10 MeV deuterons
along with a proton detector set at 90°. The figure also includes a portion of the
28
energy level diagram for the nucleus A1. We refer to Equations (15-27) and
(15-28), and we take

K = Kd =
x
2.10 MeV, Ky = Kp , and 6 = 90°

to obtain

Q= [M( 2 H) + M( 27A\) - M('H) - M(Y)\c

2

^l 1 +
tl- A ''
788 Nuclear Processes

Figure 15-24

Schematic energy spectrum of protons from the reaction "H + "7

A1 —»~ KA1 + 'H. The energy
"H
levels of A1 are also shown. Every level is matched to a proton "line" whose intensity is

proportional to the excitation probability for the corresponding state in Al.

p) 28 AI
?7 AI
(d,

K d =2.\ MeV
.'

0„ = 90°

6 7
Al
KD (MeV)

noting that Y may be any

2,!
A1 state. Let us solve for K. so that we can predict
values for the detected proton energy:

K d (\ - MJM S
KP = d+
)

1 + M/My

If we choose Y to be the Al ground state, we find

Q= (2.014102 + 26.981539 - 1.007825 - 27 .98191 3)(931 .5 MeV)

= 5.499 MeV,

using masses from Appendix A. We then predict the energy for protons detected
at 90° to be

5.50 + 2.10(1 - 2/28)

A\ MeV = 7.19 MeV.
1 + 1/28

(It is adequate to compute the ratios M /M y

p
and M /M
d Y from the mass
numbers since Kd is not given very accurately.) Let us also consider an excited
28
state of A1 at 1.0140 MeV on the energy level diagram. The excitation of this
state results in a correspondingly larger value for the rest energy M(Y)c~, and so
the Q- value is reduced accordingly:

Q= 5.499 MeV - 1 .014 MeV = 4.485 MeV.

 15-9 Huclear Reactions and Nuclear Structure 789

Protons are therefore predicted at 90° with energy

4.48 + 2.10(1 - 2/28)

Kp= MeV = 621 MeV -

1 + i/28

The two calculated values of Kp appear in the figure as the first and fourth lines
at the high end of the proton spectrum.

15-9 Nuclear Reactions and Nuclear Structure

A reaction of the general form X(*, y)Y may yield any two-body system allowed by
the conservation laws. Hence, the collision of a beam particle x with a target nucleus
X produces a particular Yy final state as a random event, subject to the probabilistic
principles of quantum mechanics. The probability for the reaction is expressed by
means of a reaction cross section. This quantity is measurable in a suitably designed
experiment and is predictable in a theory of the nuclear reaction. Any theoretical
treatment of the nuclear process necessarily includes a model of the nucleus itself. The
resulting phenomenology brings experiment and theory together for the interpretation
of nuclear structure.
Let us continue to concentrate on two-body final states as we formulate these ideas.
The events in a given reaction x + X —> Y + y are described in principle by a
quantum mechanical amplitude x(X)', *X). (Wc follow the practice adopted in
Section 8-7 and use right-to-left notation to designate the amplitude.) The construc-
tion of the complex function x is such that |x|~ determines the reaction probability.
We cannot be specific about the form of the function without a detailed theory, except
to say that x depends on the beam eneigy K x
and the angle 6 of the detected particle

y. We suppose that the detector subtends an infinitesimal solid angle d£l, as in our
discussion of Rutherford scattering in Section 3-4. The reaction cross section da is then
defined by complete analogy with the Rutherford cross section:

#y particles detected in dQ,/Ume

da =
#x particles incident on X/area •
time

We make an appropriate definition of the amplitude x so that we can write the

differential reaction cross section as

— (Yy,xX)=\ X
da
(Yy,xX)\-.
|2
(15-33)

This quantity a measurable and calculable function of the variables A", and 8. The
is

total reaction cross section a r is obtained by integrating over all directions of the
detected particle:

,. da
ar = a(Yy, xX) = /^(Y?, *X) dSl. (15-34)

The usual interpretation of the cross section for scattering carries over for reactions as
well. The reaction cross section represents the effective target area presented to a beam
particle x by a target nucleus X for a specific reaction leading to the final state Yy.
790 Nuclear Processes

Figure 15-25

Formation and disintegration of the compound nucleus in the reaction x + X —» [W] —> Y + y.

CM
© *- I K) ©— *- • -*—(x)
Collision
energy A7

i\N) *- Lab frame ( .M trrinif

Released energy K'

These equations adapt at once to the special case of elastic scattering, with total cross
section

, do
if = o(Xx,xX) = j— (Xx,xX) dQ, (15-35)

by taking Y and y to be the same as X and x.

Quantum mechanics makes predictions about the process of interest through the
associated amplitude. In principle, we might argue that x(Y)', vX) should be ob-
tained by solving the Schrodinger equation to find the wave functions for the initial
and final states. In practice, we must acknowledge the difficulty of such a multi-
nucleon problem and turn instead approximate models. A prospective
to the use of
model is viable in this phenomenological approach if the ideas have intuitive appeal
and if the results are subject to direct experimental test.

A useful picture of the interacting nuclear system is provided by the compound model,
a nuclear reaction mechanism proposed by Bohr in 1936. The basic entity in the
model is a temporary composite structure called the compound nucleus. This object is

supposed form in the collision of x with X and then decay into the final system
to
consisting of Y and y. We describe the two-stage process of formation and decay by
the notation

x + X -» fW] -» Y + y.

We visualize the two stages in the lab and CM frames by the sequence of events
shown in Figure 15-25. The model makes three assumptions: the total energy of the
colliding system is rapidly distributed throughout the whole compound structure, the
compound is rather long-lived relative to the time required for x to traverse the region
of nuclear interaction, and the disintegration of the compound is completely indepen-
dent of the circumstances of formation. These premises are understood to have limits
of validity that depend on the energy and mass number of the system.
The model refers to a compound state of the nucleus without specification of the
states of the individual nucleons. These constituents are presumed to execute complex
 15-9 Huclear Reactions and Nuclear Structure 791

Figure 15-26
27
Total cross section and absorption cross section of A1 for incident neutrons. Elastic scattering
is the dominant contribution to the total cross section at these energies.

o(n,y)

5 I.

10 mb-

50 keV 50 keV

random motions upon collision and share their energies quickly by virtue of their
strong short-range interactions. This mode of distribution of the total energy permits
the rapid formation of the compound nuclear state and brings about its subsequent
disintegration into any one of several possible final channels. The random selection of
a decay channel is supposed to occur without memory of the formation state and is
assumed to result from the random exchanges of energy among the nucleons. This
collective view of interacting constituents in the compound model is fundamentally
different from the independent-nucleon theory invoked in Section 14-10 as the basis
for the nuclear shell model.
The best evidence for temporary compound nuclear states is the existence of
resonances. We observe these phenomena in a given reaction as well-defined enhance-
ments of the cross section at specific values of the energy. A resonant nuclear state
represents a system of nucleons whose configuration is especially favorable for the
distribution of a definite amount of total energy. We interpret a resonance as a
quantum state of the compound nucleus, and we assign the state a nuclear spin and
parity according to the experimental evidence. The temporary nature of the state

implies a lifetime t and width T satisfying the uncertainty relation

Pr = h.

6
s but must be larger
'

The lifetime may

be smaller than an E\ decay time of 10
:2
than a nuclear traversal time of 10" s. A resonance is seen as a peak in the cross

section, and so the short lifetime of the compound state can be found by measuring
the resonance width. Figure 15-26 shows an illustration of a resonance for low-energy
27 2ii
neutrons incident on A1 nuclei. The compound nucleus [ Al] is clearly in evidence,
as a resonant state occurs at the same value of the neutron energy in both the
28
scattering and the capture processes
27
A1(«, «)
27
A1 and
27
Al(n, y) Al. discuss the We
numerical aspects of these graphs in the first example at the end of the section.
A formalism for nuclear reactions has been developed by Wigner and G. Breit. The
theory includes an expression, known as the Breit-Wigner formula, for the cross
section in the neighborhood of a resonance. Let us examine the construction of this

formula from the point of view of the CM frame in Figure 15-25. The initial collision
 .

792 Nuclear Processes

energy and the final released energy are identified in the figure as A' and A",
respectively.At resonance we relate the two energies to AE, the excitation energy of
the resonance, by using conservation of energy:

A" + M x
c
2
+ Mx c
2
= Mw c
2
+ AE = K' + M y
c
2
+ MY c
2
,
(15-36)

where M
w c denotes the rest energy of the compound nucleus in its ground state.
Note that the Q-value in Equations (15-27) can be equated to the energy difference
A" — A" at resonance. We then define the new energy

W= A" + (M x
+ Mx - Mw )c
2
= K'+ (My + MY - M w )c
2
,
(15-37)

and we observe that W is equal to AE when the collision is on resonance so that W

serves as a variable for the description of the cross section off resonance. The
momentum of the colliding particles determines the de Broglie wavelength

h
x = -.
p'

This kinematical quantity varies with A" and therefore depends on W. We use A to
introduce an energy-dependent area

a (W) = J— ,
(15-38)
J

anticipating the appearance of the area as one of the factors in the cross section. The
Breit Wigner reaction cross section is given in terms of o by the formula

o r
= o(Yy,xX) = on (W)- ~ 1
—z.
2
(15-39)
(W- AE) + (T/2)

We note that the second factor achieves a maximum value when the variable passes
through resonance at W = AE. Thus, the formula describes the W dependence of a
resonance peak whose sharpness is controlled by the value of the parameter Y. A
similar result follows for elastic scattering by letting the final state Yy be replaced by
the elastic state X*:

a = o{Xx, *X) = aJW)- —£— 2

— 2
z (15-40)
(W- AE) + (T/2)

We have identified the parameter V as the width of the resonance. The other
quantities T and
x
I\ are called partial widths for the two states X* and Yy. The sum
of all such parameters over all possible final states is defined to be equal to T, the total

width. Hence, the ratios Tx/T and T y/T express the probabilities for decay of the
resonance into the channels X* and Yy. These properties of Equations (15-39) and
(15-40) give an excellent description of the cross sections near resonance to support the
notion of the compound nucleus as an idealized representation of the interacting
system.
Another useful picture of the system is provided by the direct model, in which the
collision process is described as a direct reaction. This view of the process holds in energy
 15-9 Huclear Reactions and Nuclear Structure 793

regimes away from resonances, where the collision energy cannot be so effectively
distributed over the whole system. We assume instead that the incident projectile x
interacts rapidly within a small region of the target nucleus and detaches the ejected
particle y, leaving the product nucleus behind. Examples of direct processes are the
(d, p) stripping reaction
2
H +-4 X -» /I + l
X+ H 1

Figure 15-27

Energy levels of
l5
N. The excited state at 12.49 MeV is observed as a resonance for the energies
indicated in the reactions
14
C(/>, n)
14
N,
,4
N(n, «) M N, and "B(a, «) 14 N.

12.49- :2.44 1.78 205

12

11
a+ n B
n + 14 N

p+ la
C
in

MeV ^N
 1

794 Nuclear Processes

and the (p,d) pickup reaction

'H + A X A-\
X + 2 H.

Both of these collisions involve the transfer of a single nucleon between the projectile
and the target. Such processes can be analyzed as direct reactions to test the shell
model or some other independent-nucleon theory of the nucleus.
It is apparent that the compound and direct models provide alternative contexts for

the analysis of nuclear structure in a nuclear reaction. Let us take a last look at
resonances and nucleon transfers as the basic alternative mechanisms. We wish to
consider a few of the processes pertaining to the
15
N system for illustration, so let us

display some of the energy levels of this nucleus in Figure 15-27 for reference. We find
15
abundant evidence of excited states in the compound nucleus [
N] by observing
many resonances in the following reactions:

in
a+-'B-^ N l4
+ K or
14
C + />

n
d + C ^ N i4
+ n or
l4
C +p or "B + a
H H
p + C ^ N +
1

/7+ N^ N
14 14
+ k or
14
C+/> or "B + a.

l4 ,4
The thresholds for the states p N, and a + "B are located at the energies
+ C, n +
shown and the resonant states of 15 N are found at excitation energies
in the figure,
above these levels. We examine some of the numerical details of one of these
resonances in the second example below. We also find the transfer of nucleons at work
when we use spectrometers to detect protons and neutrons in such N-producing
reactions as

a + I2
C ^ ,5 N + />,

d + HC -> I5
N + n,

rf + 14
N ^' r>

N+ p.

The low-lying excited levels of the residual

r,
N nucleus can be determined from the
proton and neutron spectra by techniques described at the end of Section 15-8.

Example

The resonance in Figure 15-26 appears in n + 27A1 collisions at neutron

bombarding energy K = n
35 keV and locates a unique excited level of the
28
compound nucleus [
A1]. To inspect the quantitative details, we transform
the process to the CM frame as in the right half of Figure 15-25 and identify the
nuclei X and W to be
27
A1 and
28
A1. Equation (15-30) gives the transformed
collision energy:

M, 11
K' = K. (0.035 MeV) = 0.034 MeV.
M x + M., I'M

The desired quantity is the excitation energy AE of the

28
A1 resonant state. We
find A£ from K' by using conservation of energy in the CM system, as in
 75-9 Huclear Reactions and Nuclear Structure 795

Equation (15-36):

A' + M n
c
2
+ Mx c
2
= Mw c
2
+ A£.

The resulting excitation energy is found with the aid of the mass table in
Appendix A:

AE = M„ + ( M x - Mw )c
2
+ A"
= (1.008665 + 26.981539 - 27.981913)(931 .5 MeV) + 0.034 MeV
= 7.723 MeV + 0.034 MeV = 7.757 MeV.

This excited up among the energy levels of 28A1. Let us refer to

state occurs well
27
the diagram in Figure 15-24 and note that the n + A1 threshold is located at
the energy (M n + x - M M
w )c = 7.723 MeV. The resonance at Kn = 35 keV
2

appears just beyond this energy, above the range of levels shown in the figure.

Example

An elastic-scattering resonance occurs prominently in the cross section for

14
N(«,n )
14
N at K n
= 1.779 MeV. We wish to find the corresponding excitation
energy in
15
N, and so we first compute the CM collision energy from Equation
(15-30), taking X to be
l4
N:

=
M x— =
14
—
A' A„ V 1 .779 MeV) = 1 .660 MeV.
M x + M„ 15
(

We then turn to Equation (15-36), taking W to be

15
N, and again use Appen-
dix A:

A£ = (M„ + M x - Mw )c
2
+ K'
= (1.008665 + 14.003074 - 15.000109)(931.5 MeV) + 1 .660 MeV
= 10.83 MeV + 1.66 MeV = 12.49 MeV.

Note that the n + N threshold lies at a level 10.83

14
MeV above the
15
N ground
state. The same resonance is also observed in the reactions "B(a, »)
14
N and
14
C(/>, n)
14
N. We can determine the beam energies in these processes by
reversing the above procedure. The CM collision energies are found by taking X
to be "B in the first case.

A" = A£- (Ma + M x -M w c-

= 12.49 MeV - (4.002603 + 11.009305 - 15. 000 109) (93 1.5 MeV)
= 12.49 MeV - 10.99 MeV = 1.50 MeV,

and by taking X to be
14
C in the second case,

K! = A£ - (Mp + M x - Mw )c
2

= 12.49 MeV - (1.007825 + 14.003242 - 15.000109)(931 .5 MeV)

= 12.49 MeV - 10.21 MeV = 2.28 MeV.
796 Nuclear Processes

Note that the a + "B and p + 14 C thresholds have excitation levels in the 15 N
system at 10.99 and 10.21 MeV, respectively. The beam energies at resonance in
the two collisions are

/C = K' = —
15

11
(1 .50 MeV) = ;
2.05 MeV

and

M x + ML 15
K, = — K'
h
= -(2.28 MeV) = 2.44 MeV.
'
Mv 14
v '

We indicate the resonance schematically for these values of K n , Ka , and K

alongside the
ir
'N level at 12.49 MeV in Figure 15-27.

15-10 Nuclear Fission

The splitting of was discovered in the 1930s in experiments on the reactions

the nucleus
of neutrons with heavy Neutrons had come into use as nuclear projectiles, with
nuclei.
the capability to probe the structure of the nucleus at low energy. It was found that
neutrons could be slowed down to thermal velocities by letting the particles undergo
elastic collisions with atoms in a moderating medium. It was also learned that thermal
neutrons could initiate nuclear reactions with substantial cross sections. Fermi pioneered
these studies and was the first to see indications of the fission process. His discovery
came in 1934 in the course of investigations of heavy nuclei, especially uranium, under
irradiation with slow neutrons. Fermi's original intention was to synthesize the nuclei
of unknown elements heavier than uranium. He observed that the radioactive
products of these reactions displayed a complex variety of fi activities that could not
be explained simply in terms of the expected (i decays of the heavy nuclides. O. Hahn
and F. Strassmann repeated Fermi's experiment in 1938 and proved by radiochemical
analysis that the reaction products had the properties of elements in the middle of the
periodic table. In 1939, L. Meitner and O. R. Frisch interpreted the basic process as a
binary splitting of the compound nucleus, resulting in a pair of nuclear fragments of
intermediate mass. They predicted a large release of energy and offered an explana-
tion for the mechanism based on the liquid-drop model of the nucleus. In the same
year their ideas were adopted by Bohr and J.
A. Wheeler in the first theory of nuclear
fission.

The fission process was found to yield neutrons along with the final nuclear
products. This circumstance suggested the possibility of a chain reaction, where the
neutrons produced in the fission of one nucleus could induce subsequent fissions in

other nuclei in a sample of fissile The prospects for the generation of energy
material.
in very large quantity were appreciated by many as early as 1939. It was recognized
that a chain reaction might be put to practical use as a controlled mechanism in a
nuclear reactor, or as a catastrophic device in a nuclear bomb. The first example of a
controlled chain reaction was demonstrated under Fermi's direction in 1942, and the

first test of a nuclear weapon was performed in 1945.

Neutrons may initiate the fission of a heavy nucleus at incident energies as small as
0.025 eV, corresponding to thermal motion at 0°C. The amount of energy released in
a single thermal-neutron fission reaction is around 200 MeV. To get a rough
 1510 Nuclear Fission 797

Figure 15-28

Schematic evolution of the fission process including the ejection of prompt photons and
neutrons. The residual nuclei are radioactive and emit secondary /? and y radiation.

understanding of this result, let us consult Figure 14-12 and compare the binding
energies of nuclei at intermediate and large mass numbers. The figure shows that a
nucleus has about 1 MeV medium A than at high
more binding energy per nucleon at
A. Consequently, in a system of approximately 200 nucleons, we find the rest energy
to be approximately 200 MeV greater when the nucleons are found in a single heavy
nucleus than when the system is divided into two medium-mass fragments. This excess
rest energy determines the total energy released for distribution among all the final

products of the fission reaction.

The fissioning heavy nucleus has a neutron-rich composition so that the fission
fragments contain many more neutrons than protons. The fragments are highly
unstable and deexcite by the prompt emission of y rays along with the all-important
neutrons. A typical fission sequence passes through these early stages according to the
scenario shown in Figure 15-28. The instabilities continue after the neutron-ejection
stage because the residual nuclear products are still rich in neutrons and are therefore
radioactive. The fission products decay to their final stable states by the emission of fi

and y radiation, often in chains of sequential transitions. These last phases of

deexcitation are also indicated in the figure.
The fission uranium by thermal neutrons is energetically possible in the
of
naturally occurring isotope
235
U. The more common species U fissions under
neutron bombardment, provided the incident neutrons exceed a threshold energy
around ! MeV. Many of the heavy nuclides have appreciable fission cross sections for
thermal neutrons. However, only
233
U,
235
U, and 239 Pu have the combined properties
of large cross section and long half-life. These nuclei are the main fissile materials
available, either naturally or synthetically, for the generation of energy on a large
scale.

The absorption of thermal neutrons by

235
U results in the (n, y) radiative-capture
reaction as well as the (n, f) fission process. A single n + 235 U collision may lead to
798 Nuclear Processes

Figure 15-29
235
Fission yield in percentage versus mass number for the thermal-neutron fission of U.

4-

K() 100 120 140 160

either of these channels in random quantum fashion, with probabilities favoring fission
over radiation by an approximate 5 : 1 ratio. We can picture this competition of
236
processes in two stages: the formation of the compound nucleus [
U] and the
immediate disintegration of the intermediate state into either the fission or the
radiation channel.
The fission process does not yield a unique pair of fragment nuclides. Instead, we
observe a distribution of mass-number pairs, comprising a "light group" and a "heavy
235
group," as indicated by the fission-yield graph in Figure 15-29. In the fission of U,
there is a probability in excess of 1% for the occurrence of any light fragment with A
between 85 and 107, together with a corresponding heavy fragment with A between
129 and 151. We note that a symmetric yield into equal-mass fragments is extremely
improbable and that the largest probabilities occur for asymmetric pairs in the
vicinity of the mass numbers 96 and 140.
A typical fission event might display the following chain of representative nuclear
products:

n + "S U 5
U ,5
Sr+ 14,
Xe *Sr + l40
Xe + In.

This example illustrates the essential fact that the excess of neutrons in the original
heavy nucleus is passed along as a large unstable surplus of neutrons in each nuclear
fragment. The instability is partially relieved by the ejection of prompt neutrons, and
the remaining neutron excess is eventually stabilized by subsequent /3~ decays. Our
representative example might exhibit the following series of /? transitions:

94 94
Sr -+ Y - 94 Zr(stable) and 140
Xe - ,40
Cs -> ,40 Ba - ,40
La -» 140
Ce(stable).

Radiative transitions also participate in this cascade of deexcitation processes. The

 1510 Nuclear Fission 799

bookkeeping for the total release of energy can be drawn up roughly as follows:

kinetic energy of nuclear products 165 MeV

kinetic energy of fission neutrons 5
energy of prompt y rays 7

/?-decay energy including neutrinos 1

secondary y-decay energy 6

total fission energy 200 MeV
We note at once that the largest share of the energy is apportioned to the residual
nuclei.
A single fission event may yield two or three ejected neutrons. The many different
fission channels may contain different numbers of neutrons, and so an average number
must be used to identify the neutron yield of a particular fissile nucleus. An average
number of neutrons equal to 2.4 is quoted as the yield of 235 U.
The binary fission of a compound nucleus is a quantum process in which the
fragmentation of the compound and the selection of the pair of fragments proceed at
random. The probabilities for the many different pairs are determined by the complex
dynamics of the nuclear interactions. Models must be employed to describe these
phenomena since no completely satisfactory theory of nuclear fission exists. Our
schematic picture in Figure 15-28 suggests a useful model to show how fission might
evolve. Let us choose a particular pair of nuciear fragments X and Y and take r to be
the variable distance between the two centers. The description begins at r = where
the fragments coincide in a single spherical compound nucleus. The variable then
increases during the evolution of fission in the manner shown in the left half of the
figure. Scission occurs over a small interval around the separation point r = R x + R Y>
a distance determined by the radii of the two nuclear fragments. Beyond this interval,

the attractive nuclear force is not operative and the nuclei are under the influence of
Coulomb repulsion alone.
Let us introduce an r-dependent potential energy of the form shown in Figure
15-30 to represent the regions of attraction and repulsion. The configuration of the
compound nucleus is supposed to vary from deformation to fragmentation and
beyond as r varies across these regions. The potential energy V(r) can be inserted in
the Schrodinger equation, so that a stationary-state eigenfunction can be obtained, to
describe the fission of a given compound nucleus into a specific pair of fragments.
Note that V( r ) has a much like the Coulomb barrier in a decay. The
fission barrier

nucleus disintegrates with a certain decay constant, through the process known as
spontaneous fission, if the stationary state has an energy level below the top of the
236
barrier. Many of the heavy nuclides, including U, exhibit this behavior in their
ground state as a less probable alternative to a decay. Thermal neutrons may also
cause induced fission in the same compound nuclear system, as in the process of main
interest

n thermal + 235tj_> [236TJ] _> X + Y.

We identify this state of the system with an excitation energy above the ground state,
and we note that the energy level lies higherthan the fission barrier. Thus, there is a
distinction between spontaneous and induced fission associated with the two energy
levels shown in the figure.
800 Nuclear Processes

Figure 15-30

Fission- barrier model describing the deformation and fragmentation of the compound nucleus
as a function of fragment separation. The potential energy V(r) pertains to a specific pair of
fragment nuclei X and Y.
V(r)

Induced fission
Spontaneous fission

The
old fission theory of Bohr and Wheeler is still useful as a qualitative guide to
the problem of deformation and fragmentation. Their treatment begins with the
liquid-drop model of a spherical nucleus and focuses on the surface energy and the
Coulomb energy as the only radius-dependent considerations. The corresponding
forces of surface tension and electrostatic repulsion are expected to compete with each
other as the excitation of the droplet deforms the original spherical shape. We have
expressed the surface and Coulomb contributions to the semiempirical mass formula
through the terms

Z2
a,
2
y)
A 2/i and a.,—
3^1/3
j-rr

in Equation (14-13). Let us recall the formula for the nuclear radius,

R = R A '\ l

so that we can identify the surface and electrostatic energies by the formulas

V, = AirR
2
s and V = - (15-41)
5 4tte R

In V we
t
introduce a surface energy s per unit area, and in V we
t
use a result quoted in
Equation (14-11). A small deformation of the spherical droplet implies a small growth
in the radius R. We refer to Figures 15-28 and 15-30 and observe that this small
deformation corresponds to a small departure of the separation variable r from an
equilibrium position at r = 0. It is clear from Equations (15-41) that the sum of Vs

and V may r
either increase or decrease with a growth in R, since the one term
increases as the other decreases. Bohr and Wheeler argue that V s
has the larger role, so
that the nucleus resists deformation, if the ratio Z 2/A is less than a certain critical

value. (We compute this number in the first example at the end of this section and
obtain a value approximately equal to 50.) This criterion establishes the existence of
 1510 Nuclear Fission 801

the stable-equilibrium well shown in the neighborhood of r = in Figure 15-30. A

fission barrier must then develop as r increases, because the repulsive Coulomb
potential energy of the separated fragments eventually becomes the only effect for
large r.

This picture accommodates both types of fission, spontaneous and induced, depend-
ing on the energy level of the compound nucleus. We have already associated
spontaneous fission with the problem of barrier penetration for a level below the top
of the barrier. The large masses severely diminish the penetration probability so that
spontaneous fission usually competes very unfavorably with a decay. We have also
associated induced fission with levels above the barrier. We find that thermal-neutron
235 238
fission occurs for U, but not for U, because the thermal-neutron energy level
236
exceeds the barrier for the compound nucleus [
U], but not for the compound
239 238
nucleus [
U]. Thresholds exist in all fission reactions of the type U(«, /) because
of this property.
The Bohr- Wheeler theory does not agree with experiment in several important
The most glaring defect is
respects. its failure to explain the observed asymmetry in
the distribution of fragment masses. This question remains to be solved in a satisfac-
tory theory of nuclear fission.

Let us turn from theory to practice, and discuss the fission process in the context of
nuclear reactors. The design of a reactor takes advantage of the fact that most of the
total fission energy is carried away as kinetic energy by the final nuclear products.
These energetic massive nuclei quickly dissipate their energies in collisions with atoms
in the fuel element of the reactor. The exchanged energy can be drawn off as heat for
the conversion of water into steam, and the steam can be used to turn turbines and
produce electricity.

The essential feature of the fission process in the development of a chain reaction is

the production of neutrons. These secondary particles are able to sustain the sequence
of reactions if each fission, on the average, causes another subsequent fission. The
critical mass defines the minimum amount of fissile material required for a chain
reaction in a given configuration of the material.
The fission sequence may produce an occasional delayed neutron, with about 1%
probability, instead of the usual prompt variety. The delay occurs because the neutron
does not come from a primary fission fragment, as in Figure 15-28, but comes instead
from some other nuclear product in the sequence after one of the intervening /?
decays. The intervening time may amount to a delay of many seconds in the emission
of the neutron. This effect provides a means by which the chain reaction in a reactor
can be controlled. In practice, the shape of a fissile material is designed to allow room
for neutron absorbers (such as boron or cadmium), whose location can be varied to
control the determination of the critical mass. It is clear, however, that no such
mechanical device is fast enough to regulate the prompt neutrons. The design of the
reactor may instead incorporate a configuration of material in which the mass stays
subcritical for prompt neutrons alone and achieves criticality when delayed neutrons
participate in the process.
Fission reactions induced by thermal neutrons tend to have much larger cross
sections than the same reactions initiated by fast neutrons. The reduced cross section
for fast neutrons poses a problem for reactor design because the typical fission neutron

has an energy in the MeV range. A moderator may be introduced in the fission fuel to

solve this problem. The moderating medium contains light atoms (such as deuterium
or carbon), which undergo elastic collisions with the neutrons and thereby degrade the
neutron energies to thermal levels.
802 Huclear Processes

Enrichment of the fissile material presents another problem if naturally occurring

uranium is used as the reactor fuel. The fissioning uranium species for thermal
235
neutrons is the rarer nuclide U. This isotope can be separated from the more
abundant 238 U by gaseous diffusion or mass spectrography, since these techniques are
sensitive to the small difference in mass between the two nuclei. Another solution is to
manufacture the fissile material from an abundant source. The breeder reactor
239
operates on this principle and makes fissionable Pu from nonfissionable 238
U in the
following series of steps:

n+ 23y U 239
U + y
2»U-» 239 Np + «-+*
239
'Np 239
Pu + e '+ v.

The Pu nucleus fissions under bombardment by slow or fast neutrons, and so the
use of a moderator is not essential if plutonium is the reactor fuel.
Figure 15-28 reminds us that the secondary nuclei in the fission sequence are
radioactive. Some of these nuclides are long-lived hazardous sources of radiation. The
disposition of this waste material is a very serious consideration for the nuclear reactor
program.

Example

It is not difficult to show that [

236
U] should have a fission barrier. We consider
the general situation and return to Equations (15-41). These formulas apply to a
spherical droplet of radius R, with surface and electrostatic forces in equi-
librium. Let us perturb this structure and deduce the critical condition for
stability. We consider a small increase in R and find the perturbing forces from
the expressions

dV d_K 3 Z 2e 2
F= = —87rRs and F. = '

2
~d~R dR 5 4ire Q R

The directions of these two forces are, respectively, inward and outward, as
anticipated. Hence, the equilibrium of the droplet is restorable if the expressions
obey the inequality
2
3 Z'-V
8irRs > 5
5 4tt£ /?

or

Z2 8m
3 '
tf

Let us use the formula R = R A l/3 and rearrange this criterion as follows:

2
Z2 8to Z2 477# J

2
< 2
RlA le /4ire A ' *e*/4ire R

We can obtain a value for the combination of constants by recalling the

 15-10 Nuclear Fission 803

connection between Equations (15-41) and the corresponding terms in the mass
formula:

1ttR 2s = AirRlsA 2 ^ = a,A 2/3

and

3 Z 2e 2 3 e
2
Z2 Z2
5 4tte R 5 477e /? A ,/3 V
a..
/3 "

We express the constants as

2
3 e
AttRis = a.,
2
and = a.,,
3
5 4tte R {)

and we thereby deduce the critical maximum value for Z 2/A

Z 2
MeV
—
A
\
= 2—
a2

a3
= 2
17.81

0.7105 MeV
= 50.13,
J c

using the values quoted for a 2 and a 3 in Section 14-5. The Bohr-Wheeler
argument tells us that the compound nucleus [^W] has a stable equilibrium
configuration and, hence, a fission barrier ii Z 2/A is less than the critical value.
The choice of numbers Z= 92 and A = 236 gives

2
Z 2
(92)
= 35.9,
A 236

so that ["'g^U] meets the desired criterion.

Example

Let us associate the two energy levels in Figure 15-30 with the ground state of
236
U and the excitation state of the system « therma + U. i
235
We can compute the
energies of interest with the aid of a table of masses. (We turn again to
Appendix A and appeal to the original sources of Appendix A as well.) First,

consider the neutron separation energy for the ground state of U:

236
[M + M( 235 U) -
n
Af( U)]c 2

= (1.008665 + 235.043928 - 236. 045566) (93 1.5 MeV)

= 6.546 MeV.

We take this result to represent the difference in energy between the levels in the
figure, and we thus neglect the very small kinetic energy of the thermal neutron.
(Note that the curve in the figure plays no role in this exercise. Remember, the
potential energy V(r) refers to the pair of interacting fragments X and Y.) Next,
804 Huclear Processes

let us focus on the particular fission channel

n+ 23 5u ^94 Sr+ 140

Xe+ 2n

and calculate the Q-value for a reaction leaving the residual nuclei in their
ground states:

Q_ = [M n + M( 235 U) - M( 94 Sr) - A/(

,40
Xe) - 2M n
]c
2

= (235.043928 - 93.91523 - 139.92144 - 1.008665)(931 .5 MeV)

= 185.0 MeV.

This calculation determines the total amount of energy released in the form of
energetic residual nuclei, fast neutrons, and prompt y rays. The ground states of
4
Sr and Xe are fi unstable, and so the subsequent decay chains are further
sources of released energy. A final quantity of interest is the following ratio of
released energy and fissile rest energy:

185 MeV
235 2
= 8.45 X 10
M( U)c (235.0)(931.5 MeV)

The result tells us that the prompt release of energy in this particular channel
amounts to a mere 0.08% conversion of mass to energy in the fission of a single
235
U nucleus.

15-11 Fusion and Thermonuclear Energy

Nuclear fusion occurs when light nuclei combine in a reaction to form a more massive
nucleus in the final state. Nuclear binding energies are such that the fusion of a
typical pair of nuclei at low mass number results in the release of a large quantity of
energy. These reactions are of great interest because of their capability to generate
useful energy on a very large scale. The process has fundamental significance in
astrophysics since fusion is the main contributor to the energy produced in stars. The

process also has practical importance as a potential source of controlled nuclear

energy and as a proven mechanism for a nuclear weapon.
We have employed Figure 14-12 in Section 15-10 to explain how fission causes the
release of energy from nuclei at high mass number. It is apparent that a similar
argument can be applied at the other end of the figure to explain why energy is also
liberated by the fusion of low-mass nuclei. In either case the reaction products lie
toward the intermediate range of mass numbers where the nucleons have greater
binding energy. Thus, both fission and fusion take advantage of an excess in rest
energy to produce a large amount of released energy.
An idealized example of a fusion reaction is provided by the (very improbable)
collision of two protons and two neutrons to yield an a particle and a prompt y ray.
Figure 14-12 tells us that each nucleon in
4
He has about 7 MeV of binding energy, so
that the hypothetical process releases four of these units, approximately 28 MeV, to

the final ay system. We note that an exceptionally large amount of energy is

generated when an a particle is produced because of the especially tight binding of

4
the He nucleus.
 75- / / Fusion and Thermonuclear Energy 805

The more realistic fusion reactions occur in binary collisions. A good example is

deuteron-triton fusion

d + t -* a + n,

in which the formation of the a particle again results in a large release of energy. This
fusion reaction proceeds rapidly, via the strong nuclear interaction, and generates an
energy of 17.6 MeV. Let us describe the nuclear process by writing

2
H + 3
H -* 4
He + n + 17.6 MeV,

and let us also consider the other deuteron-induced processes

3
He + n + 3.3 MeV
-'H + 2
H 3
H + 'H + 4.0 MeV
and

'H + 3
He -> 4
He + 'H + 18.3 MeV.

This collection of four reactions can conceivably operate together as a combined reaction,
in which the nuclei
3
H and 3 He serve as catalysts for the basic process of ternary
deuteron fusion

3d -> a + n + p.

A net Q- value of 21.6 MeV is obtained in the overall release of energy. To confirm
this result, let us sum the four reactions, cancel the catalysts 3
H and 3 He, and divide
by 2 as follows:

6(
"HJ +
3
H + 3 He -» 2( 4 He + n + 'H) + 3 He + 3 H + 43.2 MeV
2 -* 4
=> 3( H) He + n + 'H + 21.6 MeV.

The practical implementation of these combined processes is among the goals of the
current research program in controlled fusion energy. The fusion reaction generates
less energy than a typical fission process; however, the yield of energy per unit mass of
nuclear fuel is greater in the fusion reaction by more than a factor of 3. Further
advantages in favor of fusion are the nonoccurrence of direct radioactive by-products
and the relatively low cost of fusible fuel.
Every fusion reaction involves a collision of particles with positive charge. The
collision energies must therefore be large enough to overcome the effects of Coulomb
repulsion. Let us illustrate this fact with the aid of Figure 15-31 by considering dt
fusion, d + /
— a +> n. Since the reaction is exoergic, an appreciable nuclear interac-
tion might be expected even for a dt collision at rest. The figure tells us instead that
the reaction cross section is severely affected by the Coulomb barrier for low deuteron
bombarding energiesand that the maximum cross section is finally reached around
100 keV. We can undertake a fusion experiment in a regime of energy favorable for
the reaction, simply by accelerating a beam of particles onto a target. Unfortunately,
such a method is not suitable for the generation of useful energy because the energy
released in the reaction is largely dissipated in the ionization of the target. In
principle, this problem can be circumvented by the use of an ionized target. In
 >

806 Huclear Processes

Figure 15-31

Cross section for the reaction "H + !

H — 4 He + n versus deuteron beam energy.

Kd (keV)
20 40 60 80 100 120

practice, fusion is rather improbable under these conditions, as elastic dt scattering is

the dominant process at these energies.

We can achieve fusion on a large scale if we can somehow confine the interacting
nuclei to a small region in which many collisions can occur with sufficient energy.
These conditions of confinement are satisfied in a thermal medium, where an average
particle energy around the desired value k B T = 100 keV corresponds to a tempera-
9
ture around 10 K. (Fusion may also occur in the medium if the temperature is below
this range, provided there are enough interacting nuclei available in the high-energy

tail of the thermal distribution.) The process is said to be thermonuclear because of this
association between fusion and thermal motion at high temperature.
The confined system of particles fits the description of a fully ionized gaseous
medium known as a plasma. Matter in the plasma state consists of coexisting gases of
nuclei and electrons, the debris of atoms ionized by collisions at high temperature.
Neutral matter on Earth can be maintained in this phase only under extraordinary-
laboratory conditions. The plasma state exists much more commonly in the high-tem-
perature interiors of stars, because of the containment provided by the force of
gravitational attraction.
The origin of the energy emitted by stars was one of the first great mysteries of
astrophysics. The problem was originally put in terms of the Sun, a modest star of
well-known size, mass, and temperature. In time, other information about the Sun,
such as composition, gas density, interior temperature, age, and radiation rate, also

became rather well known. was apparent that a chemical reaction could not
It

account for all these properties. It was especially obvious that a new mechanism was
needed to explain the generation of a very large quantity of energy. H. A. Bethe
found a solution to the problem, for ali the normal stars, in 1938. He proposed the
existence of cycles of thermonuclear processes in which the basic effect was the fusion
of four protons to make an a particle. The resulting proton chain was supposed to cause
 15- 1 ] Fusion and Thermonuclear Energy 807

Figure 15-32

Reactions in the proton cycle. The three processes execute the basic proton fusion chain
4p -> a + 2e + + 2v + 2y.

(^

®-^

the "burning" of hydrogen in the formation of helium, an example of the synthesis of

nuclei by the processes of thermonuclear fusion in stars. The evaluation of the various
reaction rates predicted two specific cycles whose relative influence was expected to
depend on the interior temperature of a given star.
Hydrogen burning proceeds via the proton cycle in stars of the main sequence, for
7
masses up to one solar mass and for temperatures in the range (0.8-1.5) X 10 K.
The proton cycle consists of the following reactions:

+
'H +'H -+ 2
H + e + p,

'H + 2
H ^ He 3
+ y,

3
He+ He^ He
3 4
+ 2('H).

Figure 15-32 shows sequence of processes takes four protons through three
how this

successive reaction stages to yield one a particle along with liberated energy in the
form of positrons, neutrinos, and y rays. We note that two copies of the first two
processes are needed to carry out the cycle, and we find that an energy of 26.7 MeV is

released as the net result. This amount includes the y rays produced when the
positrons annihilate with electrons in the stellar plasma. A 2% share of the released
energy is carried away by the emitted neutrinos and is not observed in the luminosity
808 Nuclear Processes

of the star. We note that the cycle starts at a very slow rate since the first process is
+
governed by the weak interaction. In effect, the first reaction is equivalent to the /8

transition p —* n in the presence of a spectator proton. Nevertheless, the generation of

energy proceeds apace in stars like the Sun because of the ample abundance of
hydrogen.
Protons are able to penetrate the Coulomb
barrier and interact with larger nuclei
7
when the temperature exceeds 2 XK, a value beyond that found in the interior of
10
the Sun. The carbon cycle is the main mechanism for stellar energy if the interior
temperature of the star is in this regime. The cycle begins with protons incident on

carbon and proceeds through the following steps:

"H + 12
C ^ N + l:i
y
N ^ nC + e + +
,;i
v

'H + ,:i
C ^ N + y 14

r>
>

H + I4
N -+' + y
O ^ N + e+ +
ls lf,
v
r,

'H +' N -+ C + He.

I2 4

We note that once again four protons are fused in stages to make one a particle. The
other essential property of this cycle is the remarkable fact that C is regenerated,
and not consumed, during the reaction sequence. Thus, carbon participates as a
no large abundance of carbon is needed to sustain the hydrogen-burn-
catalyst, so that
ing chain. The overall reaction rate is much greater, while the loss of released energy
to neutrinos is only somewhat larger, in the carbon cycle than in the proton cycle.
Both of these cycles contribute, although the latter one dominates, in the production of
solar energy.
A star may exhaust its supply of hydrogen and contract, to reach temperatures in
8
excess of 10 K. Helium burning begins in this range of greater temperature, as the
helium nuclei become able to penetrate the higher Coulomb barrier and fuse together
in the formation of carbon. We find that the net result of the cycle of reactions is the
ternary fusion process
4
3( He) -*''C,

and we note that nucleosynthesis is well underway at this stage. Newly formed carbon
acts as a catalyst in the carbon cycle for these temperatures, and carbon fusion also
l2
sets in as the C composition of the star increases. Thus, heavier nuclei appear in a
succession of fusions performed by the (a,y) reactions

4
He + 12
C ^ 16
+ y,
4 16 20
He + T* Ne + y,
4
He + 20 Ne ^ Mg 24
+ y.

At 10 9 K and beyond, carbon burning and oxygen burning commence in the reactions

12
C+ C^ Ne+ 12 20 4
He,
l6
+ 16
-» 28 Si 4
+ He.

The synthesis of nuclei continues via the fusion process until the top of the curve in
56
Figure 14-12 is reached with the formation of Fe.
 1511 Fusion and Thermonuclear Energy 809

The building up of nuclei beyond iron takes place through a series of neutron-cap-
ture reactions and occasional /? decays. These stages of nucleosynthesis depend
critically on the availability of neutrons in the stellar plasma. Neutron captures
proceed slowly, allowing time for the decay of unstable nuclei, if the number of
accessible neutrons is small. These slowly progressing syntheses come to an end at the
209
last stable nucleus Bi. Very large numbers of neutrons may also become available
in rarer situations. A rapid succession of neutron captures can then occur, with no
intervening (5 decays, to carry the formation of heavier nuclei to the highest possible
mass numbers. The existence in nature of heavy elements like thorium and uranium is
supposed to be due to such a mechanism.
We have noted that the proton cycle generates energy in stars quite slowly since the
weak interaction controls the first step in the cycle. Laboratory fusion reactions must
rely instead on the strong interactions of the nuclear particles. Candidate processes
include the dt fusion reaction d + t -* a + n, and the deuteron fusion chain 3d — a >

+ n + p. It is clear that the extraordinary conditions of the plasma phase must be

established in the laboratory if fusion is to be useful as a source of controlled
thermonuclear energy. Containment of the plasma for indefinite times is accomplished
in stars by the force of gravity. Terrestrial facilities do not possess this capability and
must depend on magnetic and inertial schemes of confinement in order to maintain
the interacting medium at sufficiently high temperature and density. In magnetic
confinement, the hot ionized medium is insulated from the colder walls of the gas
chamber by The main technologi-
specially designed configurations of magnetic fields.
cal problems scheme are to achieve a combination of fusion conditions and
in this
containment times and to preserve a balance between the energy released for use and
the energy stored for maintenance of the plasma. Inertial confinement is based on the
employment of laser beams to induce fusion. The laser light is arranged to bombard a
small pellet of deuterium and tritium from all directions at once, so that the resulting
implosion can ionize and compress the vaporized material to the temperatures and
densities needed for fusion. These techniques are currently under investigation, and
the prospects for developing controlled thermonuclear fusion are hopeful.

Example

We can appreciate a few of the advantages and problems of nuclear fusion by

calculating some numbers. Let us consider the dt fusion reaction, "H + 3 H -»
4
He + n and begin with the Q- value:

(D= (2.014102 + 3.016049 - 4.002603 - 1.008665) (931 .5 MeV)

= 17.59 MeV.

The Coulomb barrier may be estimated by using the formula R = R A l/i to

find the center-to-center distance for

2
H and 3
H in contact,

r=(l.2fm)(2 1/3 + 3
1/3
) = 3.2 fm,

and by computing the Coulomb potential energy at the distance r:

V{r) = Z2 Z3 -
e
2

47re n r
= (1)(1)~ —MeV
1.44
—
3.2 fm
-fm
= 0.45 MeV.
810 Nuclear Processes

Actually, the collision energy does not need to be as large as this to give an
appreciable fusion cross section, as Figure 15-31 indicates. Let us ignore the
collision energy by taking the initial dt system to be fused at rest, and let us
construct a variant of Equation (15-10), so that we can predict unique energies
for the final a particle and neutron:

M
—
= K+ K= K \l n
/
+

17.6 MeV
=> K n
= - = 14.1 MeV and K = 3.5 MeV.
1 + 1/4

Such energetic neutrons would be able to escape from the plasma. A shroud of
lithium could be provided to recover the energy and regenerate
3
H through the
exoergic capture reaction

n + 6 Li ^ 4
He + 3 H.

Escaping neutrons would also create other problems, since their interactions
outside the plasma would induce radioactivity and cause radiation damage in

the surrounding structures.

Example

The reactions of the proton cycle generate the proton fusion chain

\p -> a + 2e
l

+ 2v + 2y

in the manner illustrated in Figure 15-32. The released energy is given by the
difference of rest energies (4M., — M a
— 2m )c 2 Let
e
. us reexpress the basic
process by introducing four electrons on both sides:

+
4(p + e~) -» (a + 2e~) + 2(e~+ e ) + 2v + 2y.

This maneuver enables us to account for the subsequent annihilation of the

emitted positrons via the familiar reaction

e~+ ^
+
— 2y.

We can now identify a total release of energy Q in the form of neutrinos and y
+
rays (including those from e~e annihilation), and also allow for a-particle
recoil, by introducing atomic masses and writing the simple expression

4M( H)c 2 = M( 4 He)c 2 +

l

Q.

The calculation of this quantity gives

Q= [4Af('H) - M( 4 He)]c 2 = [4(1.007825) - 4.002603] (931 .5 MeV)

= 26.73 MeV
 Problems 811

01

26.7 Me 1

= 6.68 MeV per proton in a single fusion,

t

The proton chain supplies the energy radiated by the Sun, with a rate of
26
radiation known to be 4.0 X 10 W. Let us use this number to compute the rate
of proton consumption by fusion in the Sun:

26
4.0 X 10 J/jf
7—————— —, — r- = 3.7 X 10
38
protons/s.
(6.68 Me V/proton)( 1.60 X 10~ l3
J/MeV)

We can estimate the number of available protons in the Sun by supposing that
30
protons constitute the entire 2.0 X 10 kg solar mass:

30
2.0 X 10 kg
7
1.2 X 10" protons.
1.67 X 10 " kg/proton

The Sun can then be expected to exhaust its supply of protons in a time
estimated as

57
1.2 X 10
18
38
3.2 X 10 s.
3.7 X 10 s~'

11
It is comforting to know that the prediction exceeds 10 years.

Problems

1. Positron-emitting radionuclides are produced artificially in (a, n) reactions with '"B and
~' 7
A1 targets. Identify the radioactive nucleus and the corresponding nuclear decay product
for each of these reaction-and-decay processes.
2. The An series begins with the natural radionuclide 23 "Th and ends with the stable nuclide
208
Pb. The chain of decays proceeds through the following steps:

a, /?", /?", a, a, a, a, /T a and

, /? , /T, and a,

where a branching of a and ji decay modes occurs toward the end of the series. Draw up
a partial chart of the nuclides and make a plot of this decay chain, identifying each of the
nuclides in the series.

3. Derive the formulas

t = — and t, ,
= In 2 • t
Y

relating the mean life t, the decay constant y, and the half-life t, _,
for the exponential

decay of a radioactive nucleus.

y0
4. Calculate the mass of a 100 Ci Sr source.
l4
5. The production and decay of radioactive C are in equilibrium in the Earth's environ-
ment. Let the equilibrium mass ratio for
l4
C relative to ordinary 12 C be 1.5 X 10~ 12 in
812 Nuclear Processes

14
organic matter, and show that the rate of C decay in a live sample is 1 disintegration/s
for every 4 g of carbon.

6. Let the sequential decay scheme in Figure 15-5 have decay constants such that y, 2
s> y,,,
and assume vanishing initial populations for X , and X 3 . Simplify the rate equations in
this situation, and determine the populations N,(0, N.,(<)> and N s
(/) for < / <K I/Y23.
Sketch a graph for each of these solutions.

7. Let the initial populations for the two-step cascade in Figure 15-5 be such that A', = .Y ;

= at 1 = 0. Obtain the corresponding solutions to the rate equations, valid for any
choice of the parameters y, , and y2j Determine the form of the solutions in the special
.

case Y| 2 ^ Y>-(,
for times much less than l/y^. These limiting results should agree with

those from Problem 6.

8. The energies of a particles are determined by means of a magnetic spectrograph, shown

in Figure 15-7, in which an emitted a particle moves in a semicircular orbit of radius R
because of the application of a magnetic field B. The product BR (the so-called magnetic

rigidity) is found to be 0.3316 T m •

and 0.3149 T m •
for the a sources J10
Po and ~~ fa
Ra,
respectively. Use these data to compute the corresponding a-particle energies. Take the
~ 7
mass of the a particle to be 6.645 X 10 kg, and observe that a nonrelativistic

calculation is valid.

9. Use data from Appendix A to compute the kinetic energies of a particles emitted in the

decays of Po and U. The results should agree with information plotted in Figure
15-8.
2,
10. Ra is a known a emitter. Recently, this nucleus has been observed to undergo another
14
more rxotic mode of radioactive decay in which C fragments are emitted instead of a
particles. The two decay modes are
223
Ra -> L''''Rn + 4 He and 223
Ra -+ 209 Pb + M C,
where the a decay dominates by a factor of order 10 . Calculate the kinetic energy of the
emitted fragment in each case, using M( 20<, Pb) = 208.981080 u and M( 2l9 Rn) =
219.009485 u along with other mass data obtainable from Appendix A. Estimate the
height of the Coulomb barrier for each of the decays.
i2
11. The nuclide P is ($ active. Identify the decay process and use masses given in

Appendix A to compute the Q-value.

4l 4l
12. The atomic mass of Ca is 40.962278 u. Show that Ca is unstable with respect to
electron capture and compute the corresponding disintegration energy. Is B+ decay
possible for this nuclide?
3 3 3
13. The isobars |S, f C) and f Ar have atomic masses 35.967079, 35.968307 and 35.967546
u. Identify all the B instabilities in this system and calculate the corresponding Q-values.

14. Isobar masses at A = 64 are:

4
$Co ^Ni ^Cu ^Zn (

;
Ga
63.935812 u 63.927968 u 63.929766 u 63.929146 u 63.936837 u

Identify every possible B transition in this system and compute the Q-value for each
process.
40
15. The nuclide K is B unstable. Identify all possible ft processes and compute the
corresponding disintegration energies. The relevant atomic masses are listed in Appen-
dix A.

16. Refer to Figure 15-18 and classify the three indicated transitions according to the selection
rules for B and y decay.
 Problems 813

17. Predict the radiation multipole for each of the y-ray transitions shown in the figure.

0.81 s
2*

0'
*
1 3;..
0.80 s

n 1.064
'•/,
15.

2.319
%" >' 0.13 ns
IT
0.909
0.570
'/.
' 0* V
)

J -7
,Pb

Refer to the photon absorption process in Figure 15-21, and show that the incident photon
energy ea must exceed the transition energy A£ by the amount (&E)i2 /2Mc~.
A 14.4 keV y ray is emitted in a transition to the ground state in 57
Fe. The half-life of the

excited state is 98 ns. Calculate the natural width of the excited state and the recoil kinetic
energy of the nucleus. Determine the relative velocity required between emitter and
absorber to meet the criterion for resonance radiation.

20. The Q-value for the two-body reaction in Figure 15-23 can be expressed in terms of
measurable kinematical quantities by the equation

M Jmm
= K\ 1 4- —-\ - K,
\
- 2- -JKKcos
~M~) My V '
'

in which mass numbers may be substituted for the various nuclear masses. Derive this

result using nonrelativistic kinetic-energy formulas.

21. Consider a present-day version of Rutherford's («,/>) reaction:

4
He + 14
N ^ l7 +'H.
214
Take the incident a particles (from Po) to have energy 7.69 MeV, and let the outgoing

protons be detected at 9 = 90°. Calculate the Q-value using mass data from Appendix A,

and predict the kinetic energy of the observed protons. Determine the threshold energy
required for accelerator-produced a particles in the same endoergic reaction.

46
22. The energy levels in Sc can be deduced from the energy spectrum of outgoing protons,
detected at fixed angle, in the reaction
45
Sc(y, /?)
46
Sc. Let 6.974 MeV deuterons be
45
incident on a Sc target, and consider proton detection at 37.5°. Predict the energy of the
46 4fa
protons for the case where Sc is left in the ground state and for the case where Sc is

4b
left in an excited state at excitation energy 0.4441 MeV. The atomic mass of Sc is

45.955174 u, and the other relevant masses are listed in Appendix A.

23. Identify the compound nucleus in each of the following reactions:

10
B (a, p) v C, ' Na
25 U
(a,p)
26
Mg, 32
S (a, />)
35
C1,
65
Cu (/>, n)
65
Zn,
27
A1 (d, a) Mg, and P (d, pf2 P. Which
reactions are exoergic, and which are endoergic?

24 The Breit-Wigner cross section near resonance is

2 2
(W- A£) + (r/2)

for the reaction x + X -» Y + y. Take o to be essentially constant across the resonance,

 +

814 Huclear Processes

and show that T gives the full width of the resonance peak at half-maximum, as indicated

in the drawing. Refer to the graphs in Figure 15-26 and estimate the full width T and the
27 28
partial widths T„ and Ty using the, fact that, at the energies given, A1 + n and A1 + y
are the only channels open for reactions initiated by n + 27A1 collisions.

IV
sl<

i0
25. Resonances are observed in the reaction ~'A\(oc, p) Si at a-particle bombarding energies
.'5.95, 4.84, and 6.57 MeV. Compute the excitation energy for each of the corresponding

levels of the compound nucleus.

26. A beam of a particles is incident on a Be target, and a resonance is seen at 1.732 MeV
beam energy. Calculate the excitation energy of the corresponding state of the compound
l2
nucleus. The same resonant state occurs in neutron collisions with a C target. Compute
the value of the neutron beam energy at the position of the resonance.

27. Use the Maxwell-Boltzmann distribution of particle kinetic energies to deduce a velocity
distribution function for thermal neutrons. (The second example in Section 2-3 is a useful
place to start.) Determine the temperature dependence of the most probable velocity, and
show that the corresponding neutron kinetic energy is equal to k H T Calculate the value
.

of the energy and the velocity for neutrons at 0°C

M>
28. Assume that the energy released in the fission of a single
"
U nucleus is 200 MeV, and
compute the total amount of energy obtained from a 1 g sample of U. Convert the
answer to an energy in megawatt-hours.

29. The fission of Pu by thermal neutrons yields

"M
Mo+ m Te + 3* and 94
Sr
143
Ba + 3n,

as well as many other possible sets of nuclear products. Calculate the prompt energy
release in the two instances, given the masses (in u) 93.91523, 103.91358, 132.91097, and
142.92055 for the Sr, Mo, Te, and Ba nuclides.

30. Consider the symmetric fission of the compound nucleus [^Wj into a pair of like nuclei.

Deduce an expression for the height of the Coulomb barrier in the form CZ 2 /A {
'
, and
calculate a value for the constant C.

31. Calculate the energies released in the fusion reactions "H + (,

Li -» 2(
4
He) and 'H +"B
- 4
3( He).

32. Compute the energy released in each of the four stages of the cycle that make up the

ternary deuteron fusion process 3d —* a + n + p, and confirm the result quoted in the

text for the net (Rvalue.

33. Determine the energy released at each stage of the carbon cycle. Relevant masses not
given in Appendix A are A/(
n N) = 13.005739 u and M( ]
''Q) = 15.003065 u.
 SIXTEEN
ELEMENTARY
PARTICLES

/he search for the basic components of matter

has been the most enduring of all scientific endeavors. The investigation of this idea
has always turned on questions of scale, since the operative measure of smallness has
usually been set in advance by the limitations of current experiment. Thus, in Dalton's
time, it was realistic to picture matter as a composition of atoms and to regard these
smallest units as identical constituents for a given element and as distinct constituents
for different elements. The atom was known by 1900 to be divisible and to have a
structure containing elections. Distinguishing properties and unifying features could
be drawn among the atoms on the basis of these different structures. Soon, Rutherford's
experiments confirmed the existence of the atomic nucleus and reduced the examina-
tion to a smaller scale where the fundamental constituents of the nucleus could also be
identified.
The family of elementary particles had a very modest size in the early 1930s, when
all matter was supposed to be made of electrons, protons, and neutrons. Photons were
included in the picture as quanta to account for the radiation emitted by atoms, and
neutrinos were admitted by virtue of their conjectured role in [5 decay. The new
quantum theory was also in place and provided a theoretical framework for the whole
system of known particles. This simple organizational scheme became obsolete,
however, as many new particles were soon discovered. The new developments called
for revisions of theory in particular, since the nature of the fundamental interactions of all
the particles proved to be the central issue.

Our study of the nucleus has already introduced us to the reciprocal domains of
high energy and small scale. We proceed now to higher regimes of energy as we turn
to the examination of matter and the interactions of particles at shorter range.
Relativity must also play an essential part in any investigation involving collisions at
high energy. We find that, i the- collision energy increases, a succession of thresholds
occurs where the energies are sufficient to create the masses of new particles. Our
small family of elementary particles thus becomes a rather large array of species,
whose ranks still continue to grow in number. Nature has furnished some of the

8'b
816 Elementary Particles

evidence for these particles in cosmic-ray processes, while the great body of experi-

mental information about the known particles has come primarily from accelerators
and detectors, the sophisticated machinery of high-energy physics.
Elementary particle theory has its own elaborate apparatus for treating phenomena
at high energy. The theory is concerned with the principles pertaining to the four
main forces of nature — the strong, electromagnetic, weak, and gravitational interac-
tions of particles. We have already been introduced to the first three forces in such
problems as the nuclear binding of protons and neutrons, the emission of photons by
atomic and nuclear systems, and the /? decay of radioactive nuclei. Our goal is to
understand the distinguishing features and, especially, the unifying characteristics of
these very different interactions.
Particle physics is currently enjoying a period of unprecedented fundamental
progress, following decades of previous developments in phenomenology. The theoreti-
cal discoveries include a general formalism for a theory of the interactions of particles,
a basic principle to underlie all theories, and a demonstrable realization of such a
theory in successful agreement with experiment. Achievements in the laboratory have
been just as momentous. The experiments have given timely confirmation of the most
and continue to point the way toward possible new
crucial theoretical predictions
physics.
We examine these more recent discoveries in the latter part of the chapter, after we
present the necessary phenomenological background. The phenomenology is im-
portant in its own right because the observations describe the properties of the
particles, and because and
the interpretations indicate the organization of the large
growing particle family. A
scheme emerges from this investigation,
classification
bearing new conservation laws and quantum numbers. These attributes of the
particles represent new symmetry properties of the fundamental interactions. We learn
that it is possible to implement the concepts of symmetry by introducing a substructure
for the particles themselves. Thus, a collection of uniquely designed constituents takes
its place in the theory on a scale smaller than that of the observed particles. This
substructure reveals its existence in certain kinds of experiments. The notions of
symmetry and substructure finally culminate in a theory of the fundamental interac-
tions, where the basic principles operate among the new particle subentities at the

more primitive level.

16-1 Introduction to High-Energy Physics

Particle phenomena were studied in cosmic-ray processes before the coming of the
high-energy accelerator. Several of the original elementary particles were discovered
in these investigations. The existence of cosmic radiation was proposed in 1911 by
V. F. Hess in order to explain the presence of ionization in the atmosphere. It was
suggested that radioactive elements on Earth might be responsible; however, this
hypothesis was ruled out when it was found that the ionization increased with altitude.
Hess argued on the basis of his experiments that the radiation must be coming from
outer space.
Cosmic rays are classified as primary and secondary forms of radiation. The
primary component refers to the extremely energetic radiation that impinges from
space on the upper atmosphere of the Earth. The secondary component is produced
copiously as the result of collisions of primary radiation with particles in the
atmosphere. The primaries are known to be particles with positive charge because of
their characteristic deflections in the Earth's magnetic field. Most of these particles are
 161 Introduction to High-Energy Physics 817

protons, although surprising abundances of other nuclei are also observed. The flux of
the radiation does not vary with time or direction in space as the particles enter the
magnetic field of the Earth. The most striking aspect of the primary radiation is its

enormous range of energy, spanning 12 orders of magnitude from 10 8 to 10 20 eV.

Solar, galactic, and even extragalactic sources of the radiation are possible. The Sun is
a likely contributor, but only in the lower regimes of energy, and then only during
periods of solar activity. It is believed that the particles are produced with large
amounts of nuclear energy in astrophysical events and are then accelerated to even
greater energies by configurations of varying magnetic fields in space.
Secondary radiation is produced in showers as the primary particles penetrate the
Earth's atmosphere. The secondaries usually include pions and muons, new members
soon to be added to the growing family of elementary particles. The particle-produc-
tion events may occur as reactions or decays according to the following typical
scenario. A primary proton interacts with the nucleus of an atom in the atmosphere,
and a portion of the large collision energy is transformed to create several energetic
unstable pions. The charged pions decay into the lighter muons, and the neutral pions
decay into photons. Muons are also unstable and decay into electrons or positrons as
they descend to the Earth. Many muons actually survive the descent without decay,
since time dilation allows the faster ones to live longer and travel farther in the Earth's
frame from neutral pion decay can make electron-positron pairs
of reference. Photons
in the vicinity of atmospheric nuclei. The positrons may then annihilate with other
more photons. These processes cascade through many stages and
electrons to generate
an extensive shower of electrons and muons at the surface of the Earth.
result in
Cosmic rays remain interesting even in the age of the accelerator, chiefly because
the radiation is still the only source of certain kinds of information about particles.
The observations offer a possible view of super-energetic phenomena and ultramassive
particles, beyond the range of existing accelerators. Special interest is attached to the
primaries since these particles provide unique samples of galactic and extragalactic
matter for inspection on Earth. Finally, the origin of cosmic radiation continues to be
one of the intriguing unsolved puzzles in astrophysics.
Experiments in elementary particle physics have come to rely on accelerators as
controlled sources of particles of increasing energy. The following historical sketch
should give some orientation for these developments. The probing of the nucleus by
accelerated particles began in 1932 with the use of protons from the Cockcroft-
Walton generator, a fact already noted in Chapter 15. The cyclotron was designed for
similar purposes by E. O. Lawrence in 1929, and subsequent versions of the design
evolved in size to meet the demands for higher energy. In effect, the development of
the cyclotron set in motion the transition of laboratories from nuclear to particle
physics. This type of machine reached its limit for the acceleration of protons at

energies around tens of MeV. The cyclotron was superseded in 1945 by the invention
of the synchrocyclotron and its immediate successor the proton synchrotron. The
innovative features of these accelerators were developed independently by V. I.
Veksler and E. M. McMillan. Their contributions to machine design made it possible
to accelerate beams of protons to hundreds of MeV and, eventually, to energies far
beyond.
Detectors also had to be devised so that the subnuclear particles could be seen in
the experiments. Two particular types of apparatus, the cloud chamber and the
bubble chamber, should be mentioned because of their place in history and because of
their instrumental relation to each other. The cloud chamber was constructed in 1911
by C. T. R. Wilson and was put to immediate use in nuclear and cosmic-ray
818 Elementary Particles

Ernest Lawrence

experiments. Electronic counters were added to the instrument so that the operation of
the chamber could be triggered by incoming particles. This modification was built
into the design of the cloud chamber by P. M. S. Blackett in 1931. Most of the early
pictures of elementary particle processes were taken with the aid of these detectors.
The bubble chamber was invented in 1952 by D. A. Glaser and proved to be a more
sensitive device for observing the tracks of particles. High-energy physics enjoyed a
time of remarkable productivity as a result of the introduction of the bubble chamber
in the accelerator laboratory.
Each of the high-energy devices operates on the basis of classical principles. The
Cockcroft Walton generator accelerates protons through a large potential difference,
built up by a high-voltage transformer and voltage-multiplying circuits. Machines
with the same basic design are still employed today as low-energy injectors for the
higher-energy accelerators.
The cyclotron is a circular accelerator, shown schematically in Figure 16-1. in

which protons are guided in semicircular orbits by magnetic fields and are boosted to
successively higher velocities by intervening electric fields. The figure shows how the E
field in the gaps of the cyclotron alternates in direction synchronously with each
semicircular pass of the proton, and how each accelerating boost enlarges the radius of
the orbit. Equation (1-45) governs the relativistic motion of the proton and reduces to
the following nonrelativistic expression for the angular velocity:

v eB
eBR
R

This quantity remains constant as long as the nonrelativistic approximation holds.

Hence, the time for each semicircular orbit does not change with the orbit radius, as
 161 Introduction to High-Energy Physics 819

Figure 16-1

Schematic design of the cyclotron. Protons

from the ion source S follow semicircular
paths in the D-shaped regions of magnetic
field B. Acceleration is produced by an electric
field E that reverses direction in synchronism
with the orbiting time of the particles.

required to ensure synchronism with the reversal of the electric field. Relativity
eventually takes effect with the replacement of the proton mass M by the relativistic
form yv M, an increasing function of the velocity v. The orbiting time must therefore
begin to grow with v, so that the faster protons arrive at the gaps behind schedule and
the synchronous operation of the cyclotron breaks down.
Synchronism can be recovered by varying the frequency of the applied E field.
The synchrocyclotron incorporates this mechanism to achieve the acceleration of
protons at much larger energies. The strength of the B field may also be varied to
gain the same effect. The relation p = eBR holds for a stable circular orbit and
suggests that, if R is kept fixed, a small increase in B can cause a small increase in the
momentum p. The proton synchrotron makes use of this notion, along with a slowly
changing £"-field frequency to achieve synchronization, and along with certain focus-
ing techniques to stabilize an equilibrium orbit of fixed radius. Accelerators of this
type are not limited in their design energy by any theoretical considerations.
Both the cloud chamber and the bubble chamber are optical detectors in which the
paths of charged particles are seen as visible tracks. The tracks are made in the cloud
chamber from droplets of liquid suspended in a gas. In operation, a volume of air and
vapor in the chamber is allowed to expand and undergo a reduction in temperature.
The vapor becomes saturated so that a condensation of droplets can occur along the
ionized path left by a charged particle passing through the chamber. The supplemen-
tal use of electronic counters enables the expansion of the chamber and the photo-
graph by the arrival of the incoming particle. The tracks
of the track to be initiated
are made in the bubble chamber from bubbles of gas suspended in a liquid. In
operation, the liquid is kept below the boiling point and is then allowed to expand.
The reduction in pressure lowers the boiling point so that localized boiling can occur
to form bubbles along the path of a charged particle moving through the chamber.
The visualization of tracks makes it possible to analyze the kinematics of the observed
particles in both devices. These procedures have been used extensively to reconstruct
events in high-energy collisions.
It should not be assumed that every accelerator is designed for the bombardment of

a fixed target. The colliding-beam accelerator is another kind of machine, in which

820 Elementary Particles

two beams circulate in opposite directions in separate storage rings and undergo
collisions where the rings intersect. This design has certain advantages from the
standpoint of usable energy. Since the center of mass of the colliding particles is taken
to be at rest, all the collision energy is available in the system for the initiation of CM
reactions and, especially, for the creation of new particles. A most impressive example
of such an accelerator is the proton-antiproton collider at the- CERN laboratory in
Switzerland. The colliding particles in this machine can have up to 270 GeV kinetic
energy each of the two beams. Of course, many more collisions can occur for a
in
single beam incident on a dense target. The energy advantage is overriding, however,
if high energy is the main goal of the design. A comparison of energies can be drawn

up with the aid of a previous example, discussed at the end of Section 1-10. The
formula of interest is the relation between the total kinetic energies A' and A" in the
two frames where the target particle is at rest and where the center of mass is at rest.
The earlier example gives this relation in terms of the two total relativistic energies. A
simple conversion of energies leads us to the desired result:

A= 2A' 1 + -). (16-1)

Note that the formula applies to collisions of equal-mass particles and that A appears
as a quadratic function of A'. Some of the striking consequences of this result are
demonstrated in the following numerical illustration.

Example

Equation (16-1) can be used to determine how large the single-beam energy A
must be in a fixed-target accelerator to produce the equivalent energy of a CM
given colliding-beam accelerator with collision energy A'. Let the colliding
particles be protons in each instance and, for convenience, let the proton mass be
approximated as 1 GeV/c 2 The formula then becomes
.

1 + —
A'

where both energies are expressed in GeV. The numerical results are listed for

comparison in the following table:

Colliding-Beam Energies K' (GeV) K (GeV)

10 Me Von 10 MeV 0.02 0.0402 (40.2 MeV)
100 Me Von 100 MeV 0.2 0.42 (420 MeV)
1 GeV on GeV 1 2 6
10 GeV on 10 GeV 20 240
100 GeV on 100 GeV 200 20,400 (20.4 TeV)
270 GeV on 270 GeV 540 147,000 (147 TeV)

The quadratic dependence of A on A' begins to be noticeable when A' is

comparable to Mc 2 and
, becomes an enormous effect at the higher values of A'.
 16-2 Particles and Fields 821

The calculation of the last entry deserves closer inspection:

/
540
K= 2(540) 1 + - -
\
= 2(540)(136) = 146,880.

The energies of the colliding beams in this case are the same as those for the
protons and antiprotons in the giant CERN collider.

16-2 Particles and Fields

The main goal of particle physics is to understand the interactions of the fundamental
particles. We know that the strong nuclear interaction accounts for the binding of
protons and neutrons at short range, with energies of the order of several MeV per
nucleon. We
have already speculated that the proton and neutron are not fundamen-
tal and that the force between the particles is a demonstration of a more basic
interaction among more elementary entities. The electromagnetic interaction is sup-
posed to be a fundamental mechanism for the emission and absorption of photons and
the behavior of charged particles. The Coulomb force yields the structure of the atom
as one of its manifestations. We know that this force has infinite range and produces
atomic binding energies of the order of several eV. Nuclear /? decay is attributable to
the weak interaction. We have assessed its extraordinary weakness in Section 15-5 by
estimating the cross section for the absorption of neutrinos in matter. The weak force
is known to have a very short range by the fact that leptons are created in the
immediate vicinity of a nucleon in the n —> p transition. We are able to judge the
relative strengths of the strong, electromagnetic, and weak interactions when we
compare the cross sections in typical reactions or the lifetimes in typical decays. It is

obvious that the interactions differ very substantially as to range, strength, and energy
scale. Consequently, the prospects for unifying the forces of nature according to some
common principle may appear to be quite remote. In fact, the most notable
development in the theory of elementary particles has been the achievement of a
fundamental unification among some of the forces.
The theoretical apparatus of particle physics is provided by the relativistic quan-
tum theory of fields. Our understanding of particle theory depends on this kind of
machinery as much as our progress in experiment relies on the accelerator. The
formalism of field theory is too advanced for the purposes of this text. Fortunately, the

theory produces certain graphic techniques that furnish an intuitive picture of the

essential ideas. We wish to adopt these visual techniques so that we can gain a
qualitative understanding of particle behavior. We find that the Schrodinger equation
must be set aside because the Schrodinger theory is limited to the nonrelativistic
treatment of a fixed number of particles. We turn instead to quantum field theory in
order to incorporate relativity with the principles of quantum mechanics and provide
for the creation and destruction of particles.
Relativistic quantum mechanics has been discussed briefly in Section 8-10 in the
context of Dirac's theory for spin-^ particles. We recall that the prediction of
antiparticles is among the conclusions of this remarkable theory. The Dirac equation
2
for a free particle has solutions for any relativistic energy above the value mc ,
or
2
below the value -mc The . antiparticle concept stems
of from the latter class

solutions. We can illustrate Dirac's interpretation of the negative energy states by

means of the energy level diagram in Figure 16-2. The nonexistence of a lowest state
822 Elementary Particles

Figure 16-2

Energy levels for a free Dirac particle. The vacuum is interpreted as a sea of fully occupied
negative energy states, and a hole in the sea is interpreted as an antiparticle with positive
energy.

'

hv > 2mc 2

seems to imply that a particle can make an unending series of radiative transitions to
lower energy and emit photons indefinitely. To prevent this instability, Dirac's
hypothesis defines the no-particle state (the vacuum) as a system in which every
negative level is fully occupied by a spin-up and a spin-down fermion. A particle at
positive energy is then unable to fall below the level E= mc 2 because the exclusion
principle prohibits transitions to the filled levels at negative energy. The argument
goes on to consider the effect on the vacuum state of an incident photon with energy
greater than 2mc . The figure shows that the absorption of the photon excites a
particle to a positive energy level and leaves a hole in the negative energy sea. The
absence of a negative-energy particle is interpreted as the presence of a positive-
energy antiparticle. We can express this absorption process in terms of electrons and
positrons by writing

y + (Dirac sea) -» e + (Dirac sea with a hole)

di

y + vac —> e + e.

Thus, the phenomenon shown in the figure has the same behavior as the process of
electron-positron pair production. Dirac's argument relies only on the Pauli principle,
and so the prediction of antiparticles applies to fermions of all sorts.
Confirmation of Dirac's prediction came in 1932 with the discovery of the positron
by C. D. Anderson. The new particle was found in a cosmic-ray experiment using a
cloud chamber with an applied magnetic field. The events of interest showed tracks
originating in a thin lead plate and curving in opposite directions in the applied field,
as indicated in Figure 16-3. Since no entry track was visible, Anderson concluded that
the process was initiated by a cosmic-ray photon and that the oppositely charged
tracks were due to electron-positron pair production.
The first principles of quantum field theory were introduced before 1930 by Dirac,
Heisenberg, Pauli, and others. Their work was beset by profound difficulties that

delayed the formulation of a consistent theory for many years. The most urgent
 16-2 Particles and Fields 823

Figure 16-3

Anderson's discovery of the positron. The

pair-production process y —> e~ + e
+
takes
place in the vicinity of a lead nucleus.

Cosmic-ray photon

Lead plate

Cloud chamber

problem was an interacting system could be

to ensure that the observable properties of
expressed as any stage of approximation. A theory was said to be
finite quantities at

renormalizable if the mathematical formalism guaranteed this behavior. The first

fundamental particle theory to be so constructed was quantum electrodynamics the name ,

given to the theory of the electromagnetic interaction. This feat was achieved during
the 1940s through the work of Feynman, J. Schwinger, S.-I. Tomonaga, and F. J.
Dyson. Very precise calculations were performed with the theory, and the results were
compared with measurements of similar precision. The credibility of quantum elec-
trodynamics drew support from the fact that extraordinary agreement was obtained in
every case. Two of the more stringent tests of theory and experiment were the
determinations of the Lamb shift and the g-factor for electron spin, quantities already
mentioned in Section 8-10. Quantum field theory has also been applied to the other
interactions. It would be premature to discuss the consequences until more has been
said about these other forces later in the chapter.
Let us turn our qualitative comments about field theory to better advantage now,
and extract some tangible benefits for later use. The theory assigns a field to each
fundamental particle and casts the interactions of particles in terms of the correspond-

ing interactions of fields. The field varies in space and time and has the quantum
mechanical properties an operator that creates and destroys the associated particle
of
in states of definite momentum and energy. Thus, as an example, the electromagnetic
field (actually, the electromagnetic vector potential) acts as a quantized field and

createsand destroys quanta identified as photons. Interactions can be represented

according to a scheme, introduced by Feynman, in which the procedures of the theory
are summarized by space-time diagrams. These Feynman diagrams are much the same
in appearance as the ones drawn in Figure 15-16. The intuitive content of the
diagrams is immediately apparent and compelling. In fact, the appeal to intuition is
our sole motive in referring to fields at all. We intend to use the diagrams as "pictures
of the theory," and ignore the fact that we know nothing at all about the formalism
behind them. This naive approach serves our interests throughout the chapter.
Figure 16-4 illustrates how these visual aids are applied to two particular processes
in quantum electrodynamics. We diagrams as world-lines in
interpret the lines in such
space-time, where time runs in the vertical direction. The bremsstrahlung diagram
shows the emission of a photon as an electron passes through the electric field of a
824 Elementary Particles

Richard Feynman

nucleus. The is a source of electromagnetic radiation, and the

accelerating electron
emitted photon quantum of electromagnetic energy and momentum belonging to
is a
this radiation held. The scattering diagram shows the world-lines of two electrons in

the act of mutual electromagnetic interaction. Each particle undergoes a change of

energy and momentum, and so a transfer of these quantities must proceed from one
particle to the other in order to satisfy the conservation laws in the overall collision.
The transfer of energy and momentum is evidently accomplished by the exchange of a
photon, because the electromagnetic interaction is the cause of the scattering and
because the photon is the quantum of the electromagnetic field. We may suppose that
the photon originates in the radiation field of the one accelerating electron and is

absorbed into the field of the other. The bremsstrahlung photon and the exchanged
photon are said to be real and virtual, respectively, since the one can be observed in a
detector while the other cannot.
Figure 16-5 summarizes the main points to assume in our heuristic introduction to
quantum field theory. The basic diagrams of quantum electrodynamics are drawn as
vertices describing photon emission and photon absorption by a particle of charge e.

Each vertex contains the world-line of a moving charge, and so the corresponding
element of the theory has the form of a current, as indicated in the figure. The coupling
of the photon to the current represents the interaction between the electromagnetic
field and the charged particle. This interaction is proportional to the charge e, since e

is an explicit factor in the current itself. A coupling constant, given by e, is therefore

included in the figure beside each of the vertices. Powers of e can then be associated
with diagrams in which several vertices are connected together. For instance, there are
two vertices in the scattering diagram in Figure 16-4, and so the corresponding
amplitude for the elastic scattering of electrons must be proportional to e It is .
 16-2 Particles anil Fields 825

Figure 16-4 Figure 16-5

Feynman diagrams for bremsstrahlung Vertices describing the basic photon-current
emission and electron-electron scattering. quantum
interaction in electrodynamics. The
strength of the interaction is proportional to
the charge e.

Current

conventional to introduce the dimensionless fine structure constant

ii7E hc

and rewrite the dependence on the charge so that a power of a is substituted for every
two powers of e. Graphical techniques based on currents, quanta, and coupling
constants are similarly employed for the other fundamental particle interactions.

Example

Let us recall that the interaction of an electron with an applied magnetic field is

expressed in terms of the magnetic moment of the particle. We can represent the
interaction with the aid of Figure 16-6 by showing the behavior of the electron
current under the influence of the applied field. The indicated diagrams describe

Figure 16-6

Feynman diagrams defining the magnetic moment of the electron. The indicated contributions
to gs are of order a a ,
1

, a 2 ,. . . . The number of distinct diagrams increases with each

ascending power of a.

B® -
826 Elementary Particles

the contributions to the magnetic moment in terms of an increasing number of

virtual photons. The leading term in this series corresponds to the Dirac
prediction g s = 2, since the associated diagram contains no exchanged photons
and, hence, no corrections due to quantum electrodynamics. Succeeding di-
agrams must contain an increasing even number of vertices as in the sample
shown in the figure. Consequently, the set of all such contributions to the
magnetic moment gives the deviation from g s = 2 in the form of a power series
in e~ or, equivalently, a power series in a. These terms are expected to diminish
in size as the powers grow because of the smallness of the fine structure constant.

16-3 Mesons and the Nuclear Force

Many of the early ideas about particles were motivated by observations taken from
nuclear physics. The theory of the nuclear force was originally regarded as fertile

ground for particle concepts, since the interactions of nucleons were presumed to be
explainable in a fundamental theory of the strong interaction. Quantum field theory
had been used to express the theory of the electromagnetic interaction, and so the
same methods were expected to be applicable to the force between nucleons. The two
conspicuous aspects of this force, which any proposed nuclear field theory would have
to accommodate, were the properties of short range and charge independence.
A new kind of field, called the meson field, was introduced in 1935 by H. Yukawa to
act as a mediator for the interactions of nuclear particles. The field was assumed to be
composed of quanta, (ailed mesons. The exchange of a meson was supposed to furnish
the basic mechanism for the strong force between a pair of nucleons, as in the
exchange diagram shown in Figure 16-7. These notions were patterned closely after
the properties of photons, the quanta of the electromagnetic field. Yukawa made
allowance for the short range of the force by endowing his hypothesized mesons with
mass. Charge independence could also be incorporated in the theory by letting the
mesons exist with different charges. The analogy with quantum electrodynamics went
further to include a mesonic version of the bremsstrahlung process. The theory
predicted meson emission, also shown in Figure 16-7, in which a quantum of the field
was allowed to materialize as a meson whenever a nucleon passed within range of
real
another nuclear where the collision energy was enough to
particle, in circumstances

create the meson mass. In 1947 the predicted meson was discovered as a cosmic-ray
particle in the execution of this particular process.

Figure 16-7

Exchange of a virtual meson between nucleons and meson emission by a nucleon in the field of

a nucleus.

M .^
 16-3 Mesons and the Nuclear Force 827

The mass meson and the range of the nuclear force can be related to each
of the
other. Let us use theFeynman diagram for virtual meson exchange in Figure 16-7 to
deduce the relation. The meson is emitted by the one nucleon and absorbed by the
other in the indicated time interval A«. Consequently, there is a temporary increase in
the total energy of the two-nucleon system by an amount at least as large as the meson
rest energy mc 2 This momentary violation of energy conservation cannot be detected
.

since the exchange of the virtual meson cannot be observed. Thus, the energy of the
system is uncertain for a time At by an amount AE > mc 2 and so the uncertainty ,

principle can be invoked to determine the time interval:

h h

A£ mc

The range of the meson cannot exceed the distance

h
cAt < —
mc

because the velocity of the exchanged particle must be less than c. This argument

serves to define the spatial extent of the meson field, and hence the range of the
nuclear force, as

r =— h
• (16-2)
mc

The result is such that 2irr is equal to the meson Compton wavelength h/mc. We
note that r and m are inversely related. Hence, if the general formula is also applied

in the case of the electromagnetic field and the mass of the

the range of the field
quantum (the photon) are linked with parameters and m = 0, as expected. r = oo

We reach the same conclusion if we employ a relativistic wave equation to describe

the meson field. Let us recall the relativistic relation between energy and momentum,
given in Equation (1-35), and make the usual operator assignments

d
p
2 — -
> h
2
V 2
and E — ih—> .

dt

In this case the differential operations are assumed to act on a meson wave function
4>(r, t). We obtain the partial differential equation for $ by the familiar substitution:

la
i a 2
m 2c 2
-cY + E 2 = m 2c* => V 2
- - tt^
of-
c
= -TT*-
n
(16 - 3 >

This candidate for a relativistic wave equation is attributed to O. Klein and W.

Gordon and predates the Dirac equation. We wish to interpret the parameter given by
Equation (16-2) as a range from the meson field. Let us insert the expression for r
into Equation (16-3) and make the interpretation in terms of a time-independent wave
function for a static meson state. The equation becomes

V 2 $=— $ (16-4)

when the time-derivative term is deleted. A spherically symmetric solution to the

828 Elementary Particles

equation is given by the function

4>(r)=4> .
(16-5)

We leave the proof of this result to Problem 7 at the end of the chapter. Equation
(16-5) describes a static meson field whose exponential fall-off with r is controlled by
the value of r . This scale parameter therefore plays the role of a range, determined
by the mass of the meson in accord with Equation (16-2).
The meson theory of the nuclear force called for three differently charged species of
meson, with charges +e, 0, and —e, in order to allow for the property of charge
independence. Evidence for this feature of the nucleon-nucleon interaction came

originally from a cyclotron experiment undertaken in 1949 to investigate neutron-

proton elastic scattering. The collision energy was intended to be large enough to
reveal the details of the nuclear force on a scale comparable to the range r The .

cyclotron was used to accelerate deuterons, and these particles were stripped of their
protons to produce a beam of energetic neutrons. Hydrogenous material was placed in
the beam to furnish a dense target of protons, and detectors were supplied to
determine the angle dependence of the scattered neutrons. A regime of energy was
chosen so that neutron diffraction would result, and indeed a large cross section was
observed for scattering in the forward direction. It was especially interesting to
discover that the cross section also showed equally large scattering in the backward
direction.
We show the results of the experiment and interpret the results in the two parts of
Figure 16-8. These illustrations employ the center of mass system as the ideal frame
for picturing the forward -backward symmetry of np scattering. Large backward
scattering is shown in the upper part of the figure as a growth of the differential cross
section toward the 180° direction. The symmetry of this angular distribution is

explained in the lower part of the figure in terms of two kinds of contribution to the
neutron proton interaction. The expected diffraction of neutrons at forward angles is

seen as direct scattering, associated with the effect of a short-range meson field and the
exchange of an uncharged meson. The observation of scattered neutrons at backward
angles is interpreted as charge-exchange scattering, in which the nuclear force transforms
neutrons into protons inside the region of interaction. This feature of the force between
nucleons is evidence for a charge-changing property of the meson field, which necessi-

tates the exchange of charge-bearing quanta between the interacting particles. The
symmetry of the scattering for forward and backward angles implies an equality of
contributions from the exchange of the corresponding neutral and charged mesons.
These observations enable us to express the charge independence of the nucleon-
nucleon interaction as a characteristic ingredient of the meson theory. Evidently,
charge independence is a symmetry property of the interactions of mesons with
nucleons, which constrains the nucleons to emit the differently charged mesons with
equal probabilities. It is interesting that the quanta of the meson field can carry charge
momentum and energy. This notion is
as well as a bold extension of the ideas of
quantum field theory. Quantum electrodynamics has no such behavior, since the
emission of photons does not cause a change in the charge of the emitting particle.
The notion has real substance because charged mesons do exist among the observed
particles and because their properties indeed conform to the symmetrical predictions
implied by charge independence.
 16-3 Mesons and the Huclear Force 829

Figure 16-8

Differential cross section for np elastic scattering. The data are plotted versus neutron-scattering
angle in the CM system, and the results are interpreted in terms of direct and charge-exchange
scattering. A
symmetrical distribution of scattered neutrons implies a symmetry of the nuclear
force resulting from the exchange of neutral and charged mesons.

:(.)

90 MeV neutrons

in

60 120 180

e (deg)
cu

Forward angle

Backward angle

Charged
exchange

Meson theory has not been a great success, primarily because the strong interac-
tions of nucleons are far more complicated than the simple exchange of single mesons
suggests. In fact, meson theory is not fundamental at all, as quantum electrodynamics
is, since the particles of the theory are not fundamental and, hence, not qualified to
serve as basic elements in a field theory. The connection between the range of a field
and mass of an exchanged quantum is still a very useful idea. The property of
the
charge independence is also very important as a symmetry to simplify the phenome-
nology of nucleons and mesons. We give more attention to this property in other
sections of the chapter.

Example

Let us examine the range-mass relation and extract a numerical estimate for the
meson mass. Equation (16-2) can be rearranged to give the rest energy:

he 197.3 MeV •
fm
830 Elementary Particles

Then, if we choose a typical range for the nuclear force to be 1.50 fm, we obtain

197 MeV •
fm
mc 2 = = 131 MeV
1 .50 fm

as the predicted value for the rest energy of the exchanged meson.

16-4 Muons and Pions

New particles began to make their existence known in cosmic-ray events in the 1930s,
starting with Anderson's discovery of the positron in 1932. The muon was the next to
be seen in 1937, in experiments performed by Anderson and S. H. Neddermeyer.
These studies of the secondary cosmic rays found evidence of penetrating charged
particles whose radiative behavior in matter was not understood in terms of properties
of the known particles. The anomaly was at first thought to be due to a failure of
quantum electrodynamics, the theory of the radiative process. The experiments
indicated a more constructive alternative, however, in which the observed penetrabil-
ity of the particles in matter was explained by proposing a new species of particle,
with charge + e and with mass two orders of magnitude larger than the electron mass.
The new was temporarily given the name mesotron, or fx meson, because it
particle
was quantum of Yukawa's field theory. This
originally believed to be the predicted
belief collapsed when it was demonstrated that the particles penetrated matter with
little interaction, so that the candidate could not qualify for identification as a strongly
interacting meson. Instead, the observations established the existence of the two muons
f
ju and ju. as new particles unrelated to the nuclear force. The detailed properties of
tin muons were eventually determined in the course of accelerator experiments during
the 1950s.
The oppositely charged muons are spin- ^ fermions with mass 106 MeV/c". We
can rule out the possibility that these are Yukawa's mesons because the quanta
exchanged in Figures 16-7 and 16-8 must be integer-spin bosons in uncharged as well
as charged varieties. The muons are unstable and decay via the fi process

— T
ju. > e + 2 neutrinos,

with a lifetime of 2.2 X 10

fi
s. These decays tell us that the muon should be classified
as a member of the lepton family along with the electron and neutrino. Lepton
conservation implies that ju and ju '
are to be designated as lepton and antilepton, in
+
keeping with our previous assignments for e~ and e . We can be more specific about
these designations in Section 16-5 when we learn about some of the further properties
of neutrinos. The similarity between the leptons /x and e may tempt us to conclude
that the muon is simply an excited state of the It would then less massive electron.
follow that the radiative transition ju > e y should occur as the —
dominant mode of +
decay. In fact, the radiative mode is not observed, as though the particles are under
the influence of some internal attribute that distinguishes fi from e and requires muon
decay to proceed via the weak interaction.
The charged forms of Yukawa's meson were discovered in cosmic rays in 1947.
Their tracks were detected in photographic exposures taken at high altitudes in
experiments conducted by C. F. Powell. The mesons were found with charge + e and
+
were called m mesons, or pions, it and it~. It was evident from the tracks that the
 16-4 Muons and Pions 831

Successive decays m -* fi
-* e in a cosmic-ray
exposure

v I

.. .

'
.

-i

particles were produced in meson-emission reactions, like the one in Figure 16-7, in
which high-energy nucleons emitted pions in collisions with atomic nuclei in the upper
atmosphere. The photographic plates also showed the decays of the unstable charged
pions into muons. The processes were interpreted as

+ v and /x + v,

representing new forms of lepton-conserving /? decay governed by the fundamental

weak interaction. It make pions in the laboratory in
soon became possible to
accelerator experiments. The neutral meson tt° was seen for the first time in these
pion-production reactions. The observable signature for this unstable particle was its
832 Elementary Particles

distinctive and rapid decay into y rays

77° —> y + y,

an electromagnetic decay process. Pion production was studied with the aid of
accelerated beams of protons and neutrons in such reactions as -

+
+ n + n + 77
( p + n + 77

p + p
-»
o
and " + P '
a + /' + 77°

\p+P+ 77

P + P + 77

These interactions of nucleons were observed to obey the principle of nucleon-number

conservation and to occur with substantial cross sections. Thus, it was established that
the new mesons were indeed strongly interacting particles of the kind predicted by
Yukawa's nuclear field theory.
The pion masses are 140 MeV/c 2 for 77 * and 135 MeV/c 2 for 77°. These values
are quite consistent with expectations based on the range of the nuclear force. The
decays of the charged and uncharged pions are very different, however. This fact is
emphasized by the large disparity between the two lifetimes, 2.6 X 10~ 8 s for 77 * and
s for 77°. We know that the weak and electromagnetic interactions are
7
8.3 X 10
responsible for the two modes of decay, and we can argue that the observed lifetimes
are indicative of the distinctions between the two interactions. The pion is the first in a
succession of new unstable elementary particles whose production is controlled by the
strong interaction and whose decay is governed by an interaction of lesser strength.
The charged pions have been used extensively as beam particles to probe the strong
interactions between mesons and nucleons. Scattering processes such as

,ir~ + p
77 + p —* 77 + p and 77 + p

have given indications of several resonant states in the pion-nucleon system. The cross
sectionshave a scale typical of the strong interactions, and the resonances stand out as
unique excitations of the interacting particles. Pion-nucleon collisions also lead to
other kinds of final states, revealing the existence of new types of particles. We return
to this development in another section.
Pions have spin and parity quantum numbers that represent intrinsic qualities of
the particles. We must turn to experiment to learn such properties, in the same spirit
as for the nuclear spin and parity p in the case of nuclei. Experiments sensitive to
i

these characteristics tell us that the pion is a spin-0 meson with odd parity. Such
particles are designated by 0~ quantum numbers and are called pseudoscalar mesons.
The arguments for this assignment are discussed in two of the following exercises.

Example

We can get a very rough estimate of the scale expected for a strong interaction
cross section by computing the area of a disk of radius r j, the range of the
nuclear force A typical choice for r gives the result

2
77r
2
= 77(1.5 X 10" I5 m) = 7.1 X 10- 30 m = 2
71mb.
 164 Muons and Pions 833

In fact, the cross sections for the elastic scattering of protons by protons and
pions by protons vary with the collision energy and have values of order tens of
millibarns.

Example

The spin of the pion is known from a comparison of the cross sections for the two
inversely related processes

+ +
p + p -» 77 + d and 77 + d -> p + p.

The rate of each reaction is determined by the probability for producing the
respective final particles and is proportional to the number of final states
available at the given energy. In particular, the cross section for the first of the
two reactions contains a spin-multiplicity factor for the deuteron, given by

2i d + 1 =3 for i . = 1,

along with a similar factor (2sv + 1) pertaining to the unknown pion spin s„.

The cross sections are also proportional to the squared moduli of the complex
reaction amplitudes

+ 2 + 2
\x(ir d, pp)\ and \x(pp,* d)\ -

These quantities are identical if the processes are compared at the same values
of the CM energy. The ratio of cross sections therefore contains the factor
{2s n + 1 ) as the only unknown ingredient. This sort of analysis can be applied to
the two reactions to give the result s„ = 0.

Example

The parity of the pion is known from an observation of the reaction

tt~+ d —» n + n

and from the fact that the overall parity cannot change in a process governed by
the strong interaction. The reaction of interest proceeds from an initial bound
state corresponding to a 77-mesic atom, in which the ir~ meson replaces the
electron in its atomic orbit around the deuteron. A strong ir~d interaction occurs
in the initial {= orbital state, so that all the initial angular momentum
quantum numbers are known quantities:

K= °> i
d
= !> and ^
= °-

The total angular momentum quantum number must therefore have the value
j = 1 in the initial state, and conservation of angular momentum implies j = 1

in the final state as well. The spins of the two final neutrons are constrained by
the Pauli principle, so that the only allowed spin state is the triplet with total
spin quantum number 5=1. (The s = alternative is ruled out because s =
834 Elementary Particles

and j = would imply /= 1 for the nn orbital state. The combination s =

1

and c* = would then give a spin-antisymmetric and space-antisymmetric wave

1

function for the two identical fermions.) These arguments result in a unique set
of final angular momentum quantum numbers,
s = 1 , c" = 1 , and 7=1,
since no other value of ( satisfies the constraints. The corresponding parity is
odd, and so the overall parity of the ( = m~ d system must also be odd because
of parity conservation. We assemble the initial parity multiplicatively from the
three separate factors

(unknown pion parity)(even deuteron parity )(even orbital parity).

Thus, we find the overall parity to be odd if we assign the pion an odd intrinsic
parity.

16-5 Neutrinos

The weak decays of the muon and pion call attention again to the neutrino and the
idea of lepton conservation. We have identified the neutrino v to be the neutral,
almost massless, spin- !
, fermion that occurs undetected along with the emitted
positron in nuclear (i
y
decay. We recall that the particle v is designated as a lepton.
The antilepton v is then distinguished from v according to the Dirac interpretation of
an antiparticle. We must now refine these bookkeeping procedures to make allowance
for other kinds of leptons and, especially, other kinds of neutrinos.
The lepton concept must be enlarged in order to accommodate the results of the
two-neutrino experiment of 1962. Let us divulge the conclusion before we describe the
experiment itself. We consider neutrino processes, which may be either reactions or
decays, and we observe the neutrino that appears in association with a muon to be
intrinsically different from the neutrino that accompanies an electron. The two varieties

are discriminated accordingly by the names muon-neutrino (symbol v ) in the one

case, and electron-neutrino (symbol vf ) in the other. This distinction means that
neutrinos from the muonic decays of charged pions are not the same as neutrinos from
the fl decays of nuclei. Hence, tt ± decay must be written as

7r^ix + + v
fi
md M + "«>

while neutron ($ decay takes the form

n — p +> e + ve .

Neutrinos have served as beam particles through the use of reactors since the 1950s
and through the use of accelerators since the 1960s. The neutrino-induced production
of leptons may yield either muons or electrons in accordance with the particular type
+
of incident neutrino. Thus, there are reactions that lead either to ju~ and ju ,

v^ + n p + fi and v^ + p -> n + /x ,

+
or to e~ and e ,

— p + +
vr + n > e~ and ve -\-
p —* n + e ,

depending on the choice of neutrinos and antineutrinos in the incident beams.

 16-5 Heutrinos 835

The two-neutrino experiment was among the first to use an accelerator as a source
of high-energy neutrinos. A proton beam from the accelerator was directed onto a
nuclear target to produce fast forward pions, and the decays of the charged pions
provided the desired neutrinos. Meters of steel were placed in the beamline to absorb
muons and The resulting neutrino beam was then allowed
other unwanted particles.
to pass through an array of aluminum plates so that observations could be made of
the occasional interactions between the beam particles and the nuclear material in the
plates. These neutrino collisions were found to yield muons in every case. Equal
numbers of electrons and muons would have been seen if there had been no difference
between v„ and v. The observation of muons alone showed instead that the incident
neutrinos, originating in m decay, were identifiable as distinct muon-neutrinos.
The interpretation of this experiment suggests a classification of leptons into
subgroups, or leptomc generations, in which a distinction is introduced on the basis of an
enlarged set of conserved lepton quantum numbers. These new lepton numbers are
regarded as internal attributes that express the electron-lepton and muon-lepton
content of the various particles. Thus, the conserved lepton number L, introduced in
Section 15-5, turns into the pair of separately conserved lepton numbers L and
e
L^.
These quantum numbers are assigned to the different generations as follows:

and have (L e = + 1 and - 1 , L = 0)

while

M
v
and
V
v.,
have(L = f 0, L = +1 and -l).
M M

We see that the separate conservation laws for L and L^ are obeyed
e
in the /? decays
of the neutron and pion, as described above. The charged pions also exhibit the rare
electronic decay modes

+ '+
e + v, and w~ v.

as a further illustration. We note that the new scheme of conserved quantum numbers
+ -> +
immediately accounts for the nonoccurrence of the radiative decay ju. e + y. The
observed /? instability of the muon involves the emission of two neutrinos, whose
identities must be specified to conform to these ideas. If we write ju." decay as

H~^> e~+ ve + Vp,

we see that lepton conservation is satisfied by the assignment (L e = 0, L^ = + 1 ) on

both sides of the process.
A third leptonic generation has recently been identified, following the discovery in
+
1975 of the new massive charged leptons t" and t . If we grant these particles their

own distinct neutrinos vT and vT , and if we introduce a third conserved lepton

quantum number L T we ,
obtain

+
T T
and nth (L, = 0, LM = 0, LT = + 1 and - l)
VT i>T
T

as the third generation of leptons. The extended principles of lepton conservation are
836 Elementary Particles

supposed to hold in the r-decay processes

to cite only a few examples. All these remarks presume the existence of a distinct
tauon-neutrino. This conjecture has not been confirmed directly by experiment.
Several unanswered questions about neutrinos still stand out. The topics of greatest
concern are the mass of the neutrino, solar neutrinos, and neutrino oscillations. These
problems have important bearing on the theory of weak phenomena and on the
theory of astrophysical processes.
Until recent times the mass of the neutrino has not been accessible to decisive
measurement, so that values of the mass have been found only in terms of upper
bounds. We have mentioned a Dossible approach to this question in Section 15-4 in
the context of a current study of the endpoint in the /? spectrum of triton decay. The
quoted lower bound of 30 eV refers to the rest energy mv c2 for the electron-antineu-
trino emitted in the process

3
H -> 3
He + e~+ vt .

This bound is disputed to be much too large, on grounds related to an entirely

different experiment discussed below. The neutrino-mass issue has great cosmological
significance, even if the mass happens to be extremely small. Neutrinos inundate the
universe and can make an enormous contribution to the force of gravity if the mass is

nonvanishing. Masses can be assigned to vr , v and vT , and gravitational effects can

be estimated, in order to evaluate the critical conditions required to make the universe
close. Closure would imply a slowing down and, eventually, a reversal in the expansion
of the universe, so that the evolution following the Big Bang would terminate
inexorably in a Big Crunch at some time in the distant future.

Neutrinos from stars like the Sun have their origin in the various reactions that take
place deep within the stellar interiors. Consequently, the detection of these neutrinos
on Earth offers a unique view of the processes of stellar energy generation. The flux of
solar neutrinos is currently being studied for this purpose with the aid of large
underground detectors. The mechanism used for the detection of neutrinos is the
t^-capture reaction

37 37
vt + C1 -^ Ar + e~.

Neutrinos are produced in the Sun by several different processes, including certain
branches of the proton fusion chain, and a small number are captured by the chlorine
nuclei in a large sample of the liquid C 2C1 4 , a dry-cleaning fluid. (Unfortunately, the
capture reaction has a high neutrino threshold energy, so that neutrinos from the main
proton cycle fall below the level of sensitivity of the detector.) The rate of neutrinos
37
captured per nucleus is found from the quantity of radioactive Ar present after an
exposure of the sample. A useful measure of this quantity is the solar neutrino unit
(symbol SNU), defined as

1 SNU = 10~ 36 neutrino captures per second per 3

CI nucleus.
 16-6 Honconservation of Parity 837

Theory and experiment are in disagreement over the value of the solar neutrino rate.
Models of solar energy generation predict a rate of approximately 6 SNU, while the
measured result is closer to 2 SNU. This factor-of-3 shortfall in the number of
detected neutrinos is an indication of something unusual in the behavior of the Sun, or
in the behavior of the neutrinos.
Oscillation in a beam of neutrinos is a phenomenon in which the lepton-number
composition of the particles varies with the length of the beam. This effect may occur
when a source emits electron-neutrinos, and some p/s transform into v 's as the beam
propagates along. The resulting neutrino beam may then be observed to have a
variable vt content along its path. A similar kind of behavior definitely takes place in
certain other neutral systems to be discussed later on. Neutrino oscillation provides a
plausible explanation for the solar neutrino problem. It is possible that the Sun
produces v t \ at the predicted rate and that an oscillation from vf to v occurs on the
way to the detector on Earth. (This transformation is most likely to occur inside
the volume of the Sun.) A shortage of detected neutrinos is then observed because the
37
arriving v^s cannot participate in the C1 capture reaction. A recent analysis of the
problem of neutrino conversion inside the Sun indicates values of the mass for ve and
v^ far below the lower bound for v found in the triton /?-decay experiment.
t

Neutrinos provide many means of access to information about the weak interaction.
Phenomena such as fi decays and reactor processes are able to probe the interaction at
low energy, and neutrino beams from accelerators are able to explore the properties of
the interaction at high energy. Experiments in the latter category have contributed to
many recent developments in the theory of the fundamental particles.

16-6 Nonconservation of Parity

Conservation laws are related to the basic dynamical principles that govern a physical
system. We may identify a conserved quantity from principle if the dynamical theory
is known, or we may recognize the conserved nature of such a quantity from empirical
evidence if the theory is not fully established. In either case, the conservation law
supplies a scheme of organization, known as a symmetry, that reduces the complexity of
the given system. We use conserved quantities for this purpose in classical mechanics
when we let constants of the motion act as parameters to designate the orbits of
particles. We also use such quantities in quantum mechanics when we let quantum
numbers serve as labels to specify the states of the system. Many of our more familiar
conserved quantities are associated with spatial behavior. Conservation of angular
momentum is a case in point. The conservation law stems from rotational symmetry,
and the angular momentum quantum numbers identify the various quantum states.
Parity is another independent spatial property of a quantum system. Our aim is to
examine its meaning as a symmetry so that we can understand the circumstances in
which the associated conservation law is violated.
Let us first recall the problem of particle motion in one dimension with potential
energy V(x), where V behaves as an even function satisfying V( — x) = V(x). This
property implies the existence of energy eigenfunctions having symmetric and anti-
symmetric behavior under the reflection x -* —x. Thus, states of definite energy exist

with definite even and odd parity as a result of the reflection symmetry of V.
We then recall that the parity property in three dimensions pertains to space
inversion (
— x, —y, —z). This operation differs
in all three coordinates (x, y, z) -*
from where only one coordinate changes sign. Figure 16-9 illustrates
mirror reflection,
the distinction and shows how space inversion is represented as a mirror reflection
838 Elementary Particles

Figure 1 6-9

Transformation of the coordinate axes by space inversion and by mirror reflection. A reflection
in one axis, followed by a 180° rotation about the same axis, is equivalent to the space-inversion
operation in which all three axes are reflected.
y

G-

-y
Mirror

accompanied by a 180° rotation about the reflected axis. The central-force problem is
governed by a potential energy V(r), where V remains unchanged under the inversion
r —» — r. Consequently, stationary states exist in the form of angular momentum
eigenfunctions with orbital quantum number ( and with definite parity given by
f
{— \) . Again, the parity of the states originates in the inversion symmetry of V. Since
inversion is thesame as reflection accompanied by rotation, as in Figure 16-9, and
since rotational symmetry is already a property of V, it follows that the parity of the
states is associated directly with the mirror symmetry of the interaction expressed
by V.

We have introduced parity as a mathematical aspect of wave functions, and we

have learned that parity is an intrinsic observable of particles as in the case of the
nucleus and, more recently, the pion. Parity can also be used to classify the inversion
properties of certain observables. The position vector r is the basic odd-parity quantity
inasmuch as inversion is defined by the operation r —* — r. The momentum vector p
also has odd parity because of its connection to r through the operator assignment
p —* ( h/i )V- Both r and p belong to a class of polar vector quantities whose members
change sign under space inversion. The angular momentum vector L = r X p is a
product of two odd factors and therefore has even parity. The spin vector S is also
even since spin has the quantum mechanical properties of angular momentum. Both L
and S belong to a class of axial vector quantities whose members do not change sign
under space inversion. We can use these considerations of parity to advantage
whenever inversion-symmetric interactions determine the states of the system.
Our investigation of parity is concerned with the issue of symmetry under the
operation r —* — r. We know from our remarks on Figure 16-9 that an examination of
mirror behavior is sufficient if rotational symmetry is already known to hold. It is

advantageous to recognize this property since mirror reflection is easier to visualize.

The question of interest then asks whether a given physical process has a mirror image
 16-6 Nonconservation of Parity 839

that also occurs in nature as an equally operative physical process. To illustrate, let us
imagine taking a device made of several moving parts and using the image in a mirror
to assemble a reflected version of the original machinery. We could then compare the
two machines and argue that the original and the duplicate should function in
mirror-symmetric states of motion. In a similar spirit, let us consider two optically
active materials whose respective molecules rotate the plane of polarization of light in
opposite directions. It would be surprising if the two species of molecules could exist as
exact mirror images of each other and yet could rotate the light in opposite directions
by different amounts. These mirror-related phenomena have no distinguishable physi-
cal effects and therefore offer no operational way to tell right- and left-handed systems
apart. We note that any existing asymmetric physical behavior could be used as a
means of differentiating between right- and left-handedness. These models of familiar
macroscopic symmetry do not prepare us for the mirror asymmetry that exists among
subnuclear particles.

The nucleon and the pion exist, and by virtue of the

possess internal structure,
strong interaction. Both the strong and electromagnetic interactions are known from
experiment to offer no evidence for any violation of reflection symmetry. Since these
two strongest interactions respect the parity property, it makes sense to assign an
intrinsic parity to the particles and treat this quantum number as a conserved
quantity. We have already applied the concept of parity conservation in the context of
these particular interactions to deduce the parity of the pion and to establish the
parity selection rule for radiative decay. The weak interaction has yet to be examined
for its behavior under the parity operation. It is in this domain that we find decisive

evidence for a breakdown of reflection symmetry.

A puzzle developed early in the 1950s out of experiments on the properties of
known at the time as tau and theta mesons. The two species
certain unstable particles,
were distinguished by their different modes of weak decay. It was observed that tau
decayed into three pions while theta decayed into two pions, and it was shown that
these final states had odd and even overall parities, respectively. This observation
suggested that odd and even parities should be assigned to the parent tau and theta
particles themselves. The puzzling aspect of the situation was the fact that the two
unstable mesons were identical in every other respect. In particular, the masses of tau
and theta were equal, and the circumstances of their production in strong interaction
processes were the same. This so-called tau-theta puzzle was resolved in 1956 by T. D.
Lee and C. N. Yang. They argued that tau and theta were one and the same decaying
particle (now known as the K meson, or kaon) and that the unique-parity particle was
able to decay into pion states with different parities because the weak decay processes
did not conserve parity. This hypothesis of Lee and Yang expressed the proposition of
parity nonconservation by the weak interaction. Specific experiments were recommended to
look for other violations of parity. One of the proposed tests was to investigate the
nuclear /? decays of unstable nuclei whose magnetic moments could be aligned in an
applied magnetic field.

Confirmation of the Lee-Yang idea came promptly in an experiment directed by

60
C. S. Wu on the ft decay of Co,

60
Co ^ 60 Ni + e~ + ve .

The cobalt source was placed in a magnetic field to orient the nuclear moments, and
the sample was kept at low temperature to inhibit the thermal disordering of the
60
aligned spins. The nuclide Co was an excellent choice because of its large nuclear
840 Elementary Particles

Figure 16-10
60
Co decay and its mirror image. Electrons
are emitted to the south in correlation with a
west-to-east spinning motion of the sample of
nuclear spins. The image reverses the spinning
motion, but not the electron direction, to give
an unrealized decay configuration.

oO oa

<2> <U-P

Mirror

+
spin (i p = 5 ) and long half-life (t 1/2 = 5.3 y). Particular advantage was taken of
60
the Co decay sequence (shown in Figure 15-18), in which /? decay occurred from the
60 60 60
Co ground state to an excited state of Ni, and y decay followed to the Ni ground
state. The fi and y radiation could be detected together in the experiment, and the
observed distribution of y rays from the oriented nuclei could be used to monitor the
polarization of the sample. It was found that when the spins were aligned predomi-
nantly in one direction, the electrons in the /?-decay process were emitted prefer-
entially in the opposite direction. This observation was interpreted as a violation of
reflection symmetry. Conservation of parity would have called for equal numbers of
electrons emitted parallel and antiparallel to the spin orientation (as was observed for
the y rays emitted by the same aligned sample).
We can understand the asymmetric emission of electrons by the polarized source as
a violation of mirror symmetry by examining the argument sketched in Figure 16-10.
The sample is shown with its spins pointing north, representing a spinning motion
from west to east, while the electrons are shown radiating to the south. In the mirror,
the image of the experiment shows the electrons emitted again to the south, but in
correlation with a spinning motion from east to west. The mirror image does not
correspond to an observed process of electron emission. Since the image process does
not occur in nature, it follows that the decay of the nucleus is not reflection symmetric.
Parity violation may be used to define right- and left-handedness, since the
symmetry between the two is broken in (i decay. Let us suppose that we are in
communication with an experimenter in another galaxy, and we wish to tell the
60
person how to make a left-hand screw. The instructions would be to align a Co
sample and observe the direction of the emitted electrons. The threads should then be
cut so that the screw advances in the electron direction as it turns in the sense of the
spinning nuclei. The violation of reflection symmetry is needed to convey this

distinction between right and left. It is also essential that the distant experimenter uses
60 60
Co and not anti- Co in order that parity nonconservation alone serves to distinguish
right from left.

Mirror-symmetry violation is a built-in property of the neutrino. We see the

evidence for this parity-nonconserving feature of the particle when we examine (5
decay and find that the neutrino possesses a unique handedness. Figure 16-11 demon-
 16-6 Honconsemtion of Parity 841

Figure 16-11

Experiment determine the neutrino spin orientation. Electron capture occurs in an { =

to
and so
initial state, the z component of the total angular momentum can have either
of the
quantum numbers m = + \ or m = - £. The y ray in the final state is observed to be
left-handed, with m = - 1. Therefore, the collinear neutrino must have m =
y + and v \, the
initial-state quantum number must have been m = - \. The bookkeeping depends on the fact
that the initial and final nuclei have i = and on the fact that there are no orbital
contributions to the angular momentum. Since the neutrino is in a spin-up state with respect to
a z axis opposite to its momentum, it follows that the neutrino is a left-handed particle.

s state capture

strates this property in a schematic rendition of a classic experiment,

performed by M.
Goldhaber and others in 1958. A two-step process is shown all at once, beginning with
an electron-capture transition from a metastable state of l52 Eu to an excited state of
l52
Sm, and ending with a y-ray transition to the ground state of l52 Sm. The nuclear
spins in the two interaction stages are given as follows:

I52
+ Eu(*' = 0} -+
152
Sm*(; = \) + ve
15 2
Sm(; = +
I

0) y.

Hence, the net effect is the indicated final state consisting of ve and y along with
Sm(i = 0). A detection scheme for y rays is contrived to guarantee that this final
system has collinear momenta, as shown in the figure. The y rays are observed to have
unique left-handed polarization, and it is inferred that the neutrinos can exist in only
one of the two possible spin states normally allowed for a spin-^ particle. The
experiment draws the conclusion that the neutrino vt is a left-handed particle, having
its spin orientation opposite to its momentum. Such a configuration of spin and
momentum is intrinsically asymmetric under mirror reflection.
This experiment is construed as an observation of the left-handed nature of the
neutrino and, by inference, the right-handed nature of the antineutrino. We note in
passing that the properties of unique handedness and absolute masslessness are
intimately connected. To see the connection, we consider a massive particle whose spin
and momentum are parallel in some Lorentz frame. It is possible to transform to a
frame moving faster than the particle and to find that the momentum is reversed but
the spin is not. The original right-handed configuration of spin and momentum is thus
observed as left-handedness in the new frame. A zero-mass particle always has speed c
and cannot be transformed in this manner. Therefore, its spin and momentum
directions must maintain their parallel or antiparallel relationship in all Lorentz
frames. These remarks are not meant to imply that the neutrino must be massless. We
842 Elementary Particles

Figure 16-12

Spin orientation of the muon-neutrino in the decay tt

+ —> n + + v .

Spin
"*~"
fj — ~~ft
— *" *" 2 axis

Left-handed Left-handed.

argue instead that the neutrino mass may be very small and that a very fast frame is

then required to outrun the neutrino and reverse its observed handedness.
is a basic principle of weak interaction theory. The viola-
Parity nonconservation
tion of mirror symmetry occurs in distinct patterns, as evidenced by the handedness
properties of the neutrinos. These patterns of asymmetry are built into the current
theory of the fundamental particles. Thus, the asymmetry has the same respected
status in particle physics as any of the equally well-established symmetries and
conservation laws.

Example

A simpler observation of neutrino spin orientation is described in Figure 16-12.

In this case we consider the muon-neutrino emitted in pion decay, it
+ — > ju
+
+ v .

The experiment in the figure shows that the muons are observed with their z
component of angular momentum given by m = — \. Angular momentum
conservation then implies mv = + - l

for the neutrinos, since the pion is a spin-0

meson. This observation tells us that v is an intrinsically left-handed particle.

16-7 The Weak Interaction

Let us recall the beginnings of weak interaction theory so that we can start to assemble
a picture of the fundamental weak interaction. The weak theory is rooted in an
analogy with quantum electrodynamics. Since the electromagnetic interaction can be
formulated in terms of the emission and absorption of photons, it is natural to suppose
that a similar idea also holds for the /3-decay interaction.
The original /3-decay theory for elementary particles was an outgrowth of the
formalism for nuclear /? decay. The first ideas were put forward in the Fermi theory of
1934, as discussed in Section 15-5. Fermi's picture drew a parallel between /? decay
and radiative decay by taking the emission of a pair of leptons in a weak nuclear
transition to be similar to the emission of a photon in an electromagnetic transition.

Parity nonconservation was a subsequent development that had to be built into this
primitive theory.
We can rely on Feynman diagrams to visualize the weak theory, as we have done
in the case of quantum electrodynamics in Section 16-2. In fact, such a representation
of nuclear /J decay has already been offered in Figure 15-16. This diagram from the
previous chapter is reproduced for our present purposes in Figure 16-13. We see that
 16-7 The Weak Interaction 843

Figure 16-13 Figure 16-14

Neutron-decay diagram composed of weak Muon decay given by the coupling of weak
nucleon and lepton currents. The weak ^.-lepton and ^-lepton currents. The strength
current-current interaction occurs at very of the coupling is determined by the same Gh
short range, and the strength of the coupling as in neutron decay.
is given by the Fermi constant GF .

the interaction involves the coupling at very short range between a nucleon world-line
and an emitted lepton pair. These coupled elements of the theory are identified as

weak currents, by analogy with the electromagnetic current shown in Figure 16-5. The
neutron-to-proton world-line constitutes a weak nucleon current in which the interacting
particle undergoes a change of identity as the weak transition takes place. This feature
of the weak theory is in contrast with the identity-preserving and charge-preserving
properties of the electromagnetic current. The pair of emitted leptons ve e is repre-
sented in similar fashion by a weak lepton current, whose orientation is contrived to fit

the given diagram. We display these weak currents in Figure 16-13 as separate
elements of the interacting system.
The weak nucleon current of the original Fermi theory is a polar-vector quantity.
Its structure is the same as the electromagnetic current except for the operation that
changes the identity of the nucleon. An analogous weak nucleon current of axial-vec-
tor form is also needed to allow for parity nonconservation. To interpret the
interaction in Figure 16-13, it is understood that both polar-vector and axial-vector
contributions of opposite parity appear in the nucleon current and that the lepton
current incorporates the unique handedness of the neutrino. The resulting construction
is known as the universal Fermi interaction. This version of the weak theory is due to

Feynman and M. Gell-Mann and also to R. E. Marshak and E. C. G. Sudarshan. The

current -current form of the weak interaction has been in use since 1958 and has been
found to give a satisfactory description of all low-energy /?-decay processes.
The universal character of the Fermi theory refers to the adaptability of the
interaction to the substitution of other weak currents. Figure 16-14 shows an example
involving the coupling of two weak lepton currents, one for /i-leptons and one for

^-leptons. We note that the nucleon current of Figure 16-13 is replaced by the ju-lepton
current so that the universal interaction describes the (3 decay of the muon. In all

applications of weak current-current coupling, the strength of the interaction is

expressed in terms of a universal coefficient called the Fermi constant GF . Its value is

given by

GF = 8.95 X KT^MeV m •
844 Elementary Particles

Figure 16-15

Exchange of weak quanta in the f$ decay of

the neutron and in the neutrino reaction
+
\ + P -» M + "•

and is often written in terms of the proton mass as

GF = 1.03 X 1(T 5 he.

\
M
P
C
)

We introduce this quantity as a coupling constant at the vertices of the Feynman

diagrams in Figures 16-13 and 16-14.
We have represented the weak theory by means of an interaction between currents,
as in quantum electrodynamics. We now wish to indicate how the
the case of
interaction may be formalized in a quantum field theory, where a mediating field is
introduced and virtual field quanta are exchanged. The theory is supposed to employ
a weak vector field, by analogy with the electromagnetic field, for use as a mediator
between any pair of weak currents. The quanta exchanged in this field are then
supposed to be analogous to the photon, except that the charge-changing property of
the weak currents requires the new quanta to carry units of charge ±e a.& well as
momentum and energy. Figure 16-15 shows the exchange of these weak quanta,
denoted by W± , between certain weak currents of the universal Fermi theory.
The weak interaction is distinguished by features other than the charged nature of

the quanta and the corresponding charge-changing behavior of the interacting

particles.The weak and electromagnetic theories also differ markedly as to the range
of the respective fields and the mass of the exchanged quanta. We recall that these
properties of a quantum field theory are connected by the range-mass relation in
Equation (16-2). We know that the electromagnetic interaction has infinite range and
that the photon has zero mass. We also know that the weak interaction has very short
range, and so we expect the weak field to have very massive quanta. These considera-
tions imply that weak decays like the one in Figure 16-15 occur at energies too low to
be useful for probing the very short-range details of the weak field. A weakly
interacting probe of very high energy is required if the weak interaction is to be
sampled at distances short enough to reveal the mass of the weak quantum. Reactions
induced by high-energy neutrinos are suitable for this purpose. An example of such a
 16-7 The Weak Interaction 845

neutrino reaction is included in Figure 16-15 to illustrate the exchange of a weak

quantum between a scattered pair of weak currents.
The interaction of a weak current with the massive quanta of a weak vector field
can be formulated in a legitimate quantum field theory. This accomplishment entails
the introduction of other principles beyond the ideas suggested here. A renormalizable
theory results, in which the principles are artfully devised to generate the desired
interaction. The achievement of this goal is one of the recent triumphs in the theory of
the fundamental interactions.

Example

The scale of the weak interaction is set by the Fermi constant G F a very small ,

quantity. We wish to make a comparison with the fine structure constant a of

quantum electrodynamics, but we cannot do
so directly since a is dimensionless
while GF is an approach based on the exchange of
not. Figure 16-15 suggests
weak quanta. Let us assign a coupling constant g to each vertex where a weak
quantum is coupled to a weak current. If we compare the diagrams for neutron
decay between Figures 16-13 and 16-15, we see that G F must be proportional to
2
g The dimensions of G F can then be assembled from the mass of the
.

exchanged quantum and from fundamental constants. A reasonable expression

with these properties may be written in the form

GF =— I

he \ mwc

where g 2 /he is treated as a dimensionless factor and where the range h/m w c is

included to secure the proper dimensions. The mass of the weak quantum W i

2
is now known to be around 81 GeV/c . Let us use this result to compute the
range of the weak field:

he 197 MeV • fm
= 2.4 X 10~ 3 fm.
mw e
2
81 X 10
3
MeV

We can obtain a numerical evaluation of g

2
/hc from the quoted value of GF :

g
2
GF 8.95 X 10" 50 MeV m •
3
1

2
he rfirhc (2.4 X l(T 18 w) (l97 X 1(T 15 MeV m) • 13

2
We note that rw
'it
is very small, and we see that g /hc is analogous to the fine
structure constant

2
e 1

4:7Te hc 137

Thus, the two comparable quantities in the weak and electromagnetic theories
are found to differ by only a factor of 10. We must therefore explain the
846 Elementary Particles

enormous difference in strength between the two interactions by turning to some

other distinguishing property of the two theories. We conclude that the very
weak strength of the weak interaction must be attributed to the extremely short
range of the weak field.

16-8 Strangeness

We are about to describe a proliferation of particles, and we wish to prepare for this
outburst by introducing a preliminary classification scheme. The elementary particles
are conveniently organized into two mutually exclusive families called the Uptons and
the hadrons. Leptons have already been defined in Section 15-5 as particles that do not
engage in any strong interaction processes. The first part of Table 16-1 contains a
complete list of the known leptons, including the new members recently encountered
in this chapter. The strongly interacting particles comprise the much more numerous

family of hadrons. A partial list of some of the existing hadrons is given in the other
two parts of the table. These particles have properties that are more complicated than
the leptons since they participate in all the fundamental interactions. The table
indicates some of their characteristics in the form of several new quantum numbers. Our
goal is to interpret these quantities by uncovering the corresponding symmetries and
conservation laws.
We make a further subdivision of the hadrons according to fermion and boson
properties. The strongly interacting particles with half-integral and integral spins are
called baryons and mesons, respectively. Table 16-1 lists one particular group of
hadrons in each of these two categories. A conserved baryon number B is defined
accordingly:

B = for mesons, B = + 1 for baryons, B = — 1 for antibaryons.

We note that the baryon is a generalization of the nucleon. This interpretation is

borne out by the presence of the proton and neutron in the list of spin- \ baryons. A
conservation law for the total baryon number is adopted by extension of the law from
nuclear physics in which the total nucleon number, or mass number, is conserved.
Baryon number conservation is ultimately an assertion of the stability of the lightest
baryon, the proton, against any known form of decay. We return to this interesting
notion in another context later on.
Our first new quantum number is the strangeness S appearing in the hadronic
parts of Table 16-1. We introduce S coincidentally with the arrival of the new
+
baryons A, 2
+
, . . . and the new mesons K K°,
(called hyperons) (called kaons). , . . .

Let us suppose that we have a beam of 77 mesons of increasing energy incident on

protons in a liquid-hydrogen bubble chamber. Figure 16-16 shows the thresholds for
particle production as the collision energy grows through values large enough to create
the masses of the various new particles. The plotted quantity is the total relativistic
energy of the colliding system in the CM frame, and so the thresholds are given by the
total rest energies for the indicated production channels. The figure includes the
familiar 77
p processes

77 +p -*
\
and 77 + p -» ( ,7° + m +p
+
77~ + p \77 + 77'+ n
 16-8 Strangeness 847

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848 Elementary Particles

Figure 16-16

Thresholds for particle production in reactions initiated by m~ p and K~ p collisions. The

production channels for the two interacting hadron systems have strangeness S = and
S = — 1, respectively.

ir°n w°n-p K°l° -K*Kn

n-p w*n'n vn K°.\ K*l K°7r 1 K°K°n
- 022Z ,
ZTITf, . Y/tr. r cy/V \?///. rs/ss tr/m . ,.

1.0 1.2 1.4 1.6 1.8 2.0 ECM (GeV)

A P r~ * m» « — «» ' nm * '
iimu '

w'l K'p- K°Z°

at the lower energies. The new particles make their first appearance at the thresholds
for the associated production reactions

Our attention is drawn especially to the fact that the observed hyperons and kaons are
+
not seen singly in final states such as K° + n, or tt° + A, or tt + 2~, even though
these systems have thresholds at lower energies. Apparently, the new strange particles

are produced with some intrinsic property that prevents their occurrence until there is

enough energy to create these particles in association with each other. A new kind of
conservation law is in evidence here. The conserved quantity is the strangeness
quantum number S, and the assignment of a value of S to each hadron is such that
the total strangeness is conserved in S =
every hadronic reaction. Thus, if we take
for pions and nucleons, S = + 1 for K+
and S = — 1 for A, 2 and 2~, we and K , ,

see that conservation of strangeness holds in the observed ir~ p reactions. We also note
that the conservation law would be violated by the production of unassociated
hyperons or kaons. Other strange particles observed at the higher m~ p thresholds in
+
Figure 16-16 are the hyperon 2 and the kaons K~ and K°. It is clear that we must
assign S= — 1 to each of these particles if strangeness is to be conserved in the
indicated final states.
Our search for more strange particles can be continued along lines suggested in the
second portion of Figure 16-16. beam of K mesons be incident on protons
If we let a
in our liquid-hydrogen bubble chamber, we find thresholds as shown for the various
final states 7T° + A, 7r° + 2°,. ... All these systems have total strangeness S = — 1.
-
The new baryons Z° and E also appear, with strangeness S = — 2, in the reactions
 16-8 Strangeness 849

at the higher energy thresholds in the figure. It is noteworthy that the new strange
+
baryons are \ particles like the nucleons and that the new kaons are mesons like
the pions. The
organization of the hadrons in Table 16-1 incorporates this observa-
tion. Wefind that the strangeness-conserving m~p and ~ p reactions, indicated by K
the thresholds in the figure, have cross sections in the millibarn range. We therefore
regard the reactions as strong interaction processes.
All strange particles are unstable. Their various modes of decay contain further
information about the validity of strangeness as a conserved quantity. Let us list the
dominant modes for the strange baryons and charged kaons as follows:

p + 77
A
K + 77°

£ + 77°

+
2°^A + y 2-->« + 77"

n + 77

H°- A + 77° E"-> A + 77~

and

+
77 +77° 77"+ 77°
+ +
77 + 77 + 77~ 77~ + 77~ + 77
h
77+77 +77
+
77° + e + V U
t
77 + e~+ V,

JT° + H +
+VU K+ M" + v..

(Neutral kaons decay in a special way to be discussed in Section 16-9.) The lifetimes
for all but the 2° decay are in the range 10"
10
to 10~ 8 s, long enough for the various
charged particles to form measurable tracks in a bubble chamber. Figure 16-17 shows
an example and decay, as recorded by a photograph taken in
of particle production
such a detector. The orders of magnitude of the lifetimes are characteristic of decays
that proceed via the weak interaction. The main observation to associate with this
remark is the fact that strangeness is not conserved in these decays. If we examine each
of the listed strange-particle decays (except the one for 2°), we find that strangeness
conservation is violated by exactly one unit in every case. The exceptional 2 decay
occurs with a much shorter lifetime and yields a photon in the final state. These
circumstances, taken together with the strangeness-conserving nature of the process,
tell us that 2° decay governed by the electromagnetic interaction.
is

Strangeness is assigned as an internal attribute of every hadron, so that the

assignment is completely independent of the other kinematical properties of the
particle. We
handle strangeness as an additive quantum number in the same way that
we treat charge and baryon number. It should be emphasized, however, that charge is
a special type of particle property. Every particle has a charge assignment, where the
charge is directly measurable in terms of the response of an electromagnetic current to
the application of an electromagnetic field. On the other hand, strangeness and
baryon number are defined as useful concepts only for hadrons. A more fundamental
interpretation of thesequantum numbers remains for us to uncover.
Conservation of strangeness is a new property of the strong interaction and also of

the electromagnetic interaction. The weak interaction acknowledges the property of

850 Elementary Particles

Figure 16-17

Associated production and decay of strange particles in a liquid-hydrogen bubble chamber. The
production-decay sequence consists of the processes

w-+p->K° +A
'—> b + 77
P
+
77 + 77
 16-8 Strangeness 851

strangeness but does not observe the conservation law. Instead, the strangeness
quantum number changes in a definite way, by a single unit, in every instance of
strange-particle weak decay. We have already seen the breakdown of a conservation
law due to the weak interaction in our discussion of parity. Here, another conserved
quantity of an internal nature is found to be violated in the same class of physical
processes. It is interesting to note that the strong interaction determines the existence
of thehadrons and obeys the conservation law, while the weak interaction causes their
decay and exhibits a breaking of the law.
Strange particles were first seen in cosmic-ray events by G. D. Rochester and C. C.
Butler in 1947, the year of the pion. Hyperons and kaons began to be produced in
accelerator reactions in the next decade, and associated production was interpreted
during this period. The idea that strange particles were produced in pairs was
originally proposed by A. Pais. Subsequently, the concept of strangeness was fully
developed in terms of a symmetry principle by Gell-Mann. The identification of this
new internal quantum number was the first step in the organization of a body of
symmetries governing all the hadrons.

Example

We can apply the methods of relativistic kinematics from Section 1-11 to study
the associated production of strange particles. mesons Let us consider ir~
incident on protons at rest and determine the threshold beam energy for the
K° + A final state. In the reaction tt~+ p -^> K° + A, we have the two
momentum four-vectors

and &>' =
7!
p i{m K + MA )c

for the initial tt p system in the lab frame and the final K°A system at rest in

the CM frame. Lorentz invariance relates & and &' by the equality

Pi-
K
/ }
=-{m K + Mh fc\

where pm and Em satisfy the relation

2
El =
7T
c
2
pl
l 7T
+ rn 77 c\

We are led to the threshold result for Ev in a few algebraic steps:

(m K + Mjc* = El + 2E„Mp c 2 + M,V - c

2
p;

= 2EvM +(ml + M y p
c
2 2

(m, + MA -(ml + M
2 2
) )
E„ =
2M„
852 Elementary Particles

The beam kinetic energy at threshold is given by the formula

v = E„-
K„ P mx = L
2
(™a + ^a) ~K + M p )
c
TT ft
2Mp
mK + MA + mn + M
=
2Mp
p
{m AK +
v
MA — m
K m
'
— Mp} h )c
2
.

If we consult Table 16-1 to find the various particle masses, we obtain

498 + 1116 + 140 + 938

Kw = -
(498 + 1 1 16 - 140 - 938)MeV = 769 MeV.

Other illustrations of this four-vector technique are offered as problems at the

end of the chapter.

16-9 Neutral K Decay and CP Symmetry

The mesons K and K are produced as distinct particles in strangeness-conserving

strong reactions. Their characteristics are distinguished by the assignment of different
strangeness quantum numbers S = + 1 and S = — 1. We have postponed our discus-
sion of the decays of the neutral kaons because we have not yet described the
symmetry principles that pertain to these remarkable phenomena. The analysis of this
problem is an elegant application of basic quantum mechanics, which leads us directly
to a major experimental discovery.
We are concerned with the properties of the states of particles under the three
symmetry operations of charge conjugation, space inversion, and time reversal (sym-
bols C, P, and T). Charge conjugation C changes particle to antiparticle by the
transformation X— * X. Space inversion P reflects the spatial coordinates according to
the familiar parity operation r — — r. Time reversal T runs the time variable in the
reversed sense through the substitution t-* —t. Our problem is to ascertain the
behavior of the fundamental interactions in a given system as each operation is

allowed to act on the wave function and produce a transformed state. Thus, a
particular physical process is turned into three other processes under the action of the
different symmetry operations, and each of the three is compared in turn to the one
given. The comparison asks specifically whether the transformed copy process is

physical, and whether the transition probability is the same as for the original process.
We recall that we have already pursued this line of inquiry with regard to the P
operation in Section 16-6. If the copy and the original are found to have equal
probability, then the interaction governing the process is said to be C-, P-, or
TT-invariant, depending on the transformation in question. We can also subject the
interacting system to any combination of the three operations. In this way we may
learn, for instance, that CP-invariance holds where C and P symmetries are violated,
and we may then argue that the two violations exactly compensate each other.
An important theorem applies to these considerations. It can be proved from very
general properties of relativistic quantum field theory that every interaction is

invariant under the composite transformation CPT. This invariance means that the
combined symmetry with respect to the three operations together is always respected,
 16-9 Heulral K Decay and CP Symmetry 853

even in situations where any of the three factors exhibit violations. One of the main
consequences of CPT-invariance is the requirement that particle and antiparticle have
the same mass and the same lifetime. It is clear that any observed breakdown of this
symmetry would be cause for alarm, calling for a reevaluation of the principles of
quantum field theory.

Our principal concern is the behavior of the weak interaction with regard to C, P,
and T. We already know that P-invariance /3 decay: the mirror image
is violated in
of a certain decaying sample of aligned nuclei does not exist as an observed physical
system. We can see immediately that C-invariance is also violated by the inherent
left-handedness of the neutrino: the application of C to the neutrino yields a
left-handed antineutrino, a nonexistent particle. Note, however, that when CP is

applied to the left-handed neutrino, a legitimate right-handed antineutrino results, so

that C and P appear to have compensating violations in the weak interaction. No

direct and decisive experimental evidence for time-reversal asymmetry is known,
although tests of this property continue to be explored. We may therefore expect
CP-invariance to hold as a consequence of T'-invariance and the CPT theorem. These
notions furnish the background for our analysis of the neutral kaon system.
+
Neutral kaons decay predominantly into and 77°77° final states. The mesons
ir 7r'
^° and K° have the same mass, charge, and baryon number, and so it is natural to
ask what distinguishes the two particles. We know that the strangeness quantum
numbers are different, since K° has S = + 1 and K° has S = — 1. We also know,
however, that strangeness is not conserved in the decays of strange particles. Conse-
quently, the strangeness distinction between K° and K° becomes inoperative when
the weak decay interaction takes effect. Let is apply quantum mechanics djrectly to

this problem and consider the superposition of the mass-degenerate K° and K states.

We are especially interested in the mixed-strangeness combinations

1 1 _
K,= -^(K° - K°) and K = -^{K° +
2
K°), (16-6)
V2 V2

because these states have definite properties under the CP operation. If we accept this

assertion for the moment, we can perceive a subtle distinction between K and K .

Let us solve Equation (16-6) for the states of definite strangeness:

K°= -i^{K + l
K2 ) and K° = - -^(K, - K2 ). (16-7)

These wave functions correspond to different superpositions of definite-CP states. This

interplay between strangeness and CP properties has very interesting experimental
implications.
Let us examine the behavior of the states under C and P before we turn to the

experimental situation. Charge conjugation changes particle to antiparticle according

to the transformations

CK° = K° and CK° = K°. (16-8)

Space inversion then introduces a minus sign for the 0" particles:

CPK°=-K° and CPK°=-K°. (16-9)

 ~

854 Elementary Particles

The CP properties of the states in Equations (16-6) follow from these operations:

CPK X
=K X
and CPK2 =-K 2
. (16-10)

Thus, we find that the K x

superposition is CP-even, while the K superposition is

CP-odd.
+
Next, we consider the 7r 7r final state that results from neutral kaon decay. This
system must have angular momentum zero and orbital quantum number { = 0. The
overall even parity of the state is determined from the orbital parity, which is even,
and the intrinsic parities of the two pions, which are odd. Thus, when we apply C and
+ +
P to the 77 77 state, we find that C interchanges 77 and it ~, and then P
interchanges them back, such that the sign of the wave function remains unaltered.
+
Consequently, the tt tt~ final state in neutral K decay is CP-even, and the same is
q
true for the tt 7t final state. If CP-invariance is a valid symmetry of the weak
interaction, then the K x
portion of Equations (16-7) must be responsible for the
observed 277 decays since the K 2
state is forbidden to have the CP-even 2tt mode.
Decay into three pions is allowed for K 2 ; however, the ()-value is much smaller for 377
than for 277, so that the probability should be correspondingly smaller for K 2
decay
than for K x
decay. A substantially longer lifetime should therefore be observed for K 2

relative to K
These arguments lead us to the conclusion that, although K° and K°
x
.

are the particles produced with definite strangeness in strong reactions, they are not
the particles observed in weak decays. Instead, K° and K mix to form two distinct
decay states K and K 2 whose lifetimes are quite different because of CP invariance.
x
,

The principles of K - K mixing were developed in 1955 by Gell-Mann and

Pais. (Their analysis actually predated the overthrow of parity and assumed C-invari-
ance instead of CP-invariance to reach the same general conclusions.) The mixing
theory claimed that the familiar neutral K decays into two pions were due to the
CP-even component K and that other decay modes should also exist corresponding
x
,

to a longer-lived state with the CP-odd property of the component K 2 These .

predicted decays were detected in 1956, in apparent fulfillment of CP-invariance. The

two definite-C/5 states were found to have the following principal modes of decay:

+
/t7 + e~+ vf

~+ +
77 e + vt
+
77+77 77 + /A~ + ^
K. -» {
and K 2
-»
{
>77° + 77° 77 + [I + V

77 +77 +77
+
77 + 77~+ 77°

10 8
with lifetimes around 10 and 10 s, respectively. This interpretation of the
neutral kaon system remained intact until 1964.
The logic of K° — K° mixing
quantum mechanical principle of follows from the
superposition. We can pursue the arguments further and show how neutral kaons
participate in the process of regeneration, an extraordinary phenomenon in which a
member of a system is severed away and later grows back. The following discussion of
the process is illustrated in Figure 16-18. We suppose that 77" mesons are incident on
a slab of material and that the collisions in matter produce #°'s via the familiar
 16-9 Heutral K Decay and CP Symmetry 855

Figure 16-18

Regeneration of short-lived neutral kaons. Reactions in slab A produce K°'s whose A',
component decays away, leaving a pure K 2 beam incident onjlab B. The K° and K n parts of
the 2
K
state have different strong reactions in the slab. The K° portions are removed in these
processes so that a beam of K° 's emerges. A regenerated K x
component is contained in the
emergent beam.

©-—
K 2= M1±M tf° = ^
associated-production reaction

+ p -» K° + A.

Equations (16-7) tell us that half of the emerging K s are in the K {

state, which
decays rapidly into two pions. The surviving half consists of kaons in the longer-lived

K2 state. These particles are directed at a second slab of material, located along the
beam-line at a distance such that the transit time between slabs is greater than the K x

lifetime and less than the K 2

lifetime. We can therefore assume that we have a pure
K 2
beam incident on the second slab. These kaons interact strongly with matter
through their K° and K° components, so that strangeness conservation becomes
operative at this stage of the regeneration mechanism. The K° portion of the K 2
state

can make strange baryons in the reactions

K° + p

while the K° portion engages primarily in the scattering process

K° + p -> K° + p.

Thus, the strong reactions in the second slab remove most of the K° half from the
incident K2 state and leave mostly #°'s in the transmitted beam. Equations (16-7)
again tell us that this K° beam is an equal-parts mixture of K and K2 The x
.

remarkable conclusion is summarized by the observation that the K state dies out at x

one end of the beam-line and then grows back at the other through the intervention of
the strong interaction. The rebirth of K is seen by detecting again the rapid decay
x

into two pions, as shown in the figure. This process of regeneration of short-lived
neutral kaons has been observed in the laboratory. The steps in the analysis are
reminiscent of those followed in the Stern-Gerlach thought experiments of Section
8-7. Recall that we have applied superposition to spin states in the case of the
856 Elementary Particles

Stern -Gerlach problem. Here, we superpose states of definite strangeness to describe

A', regeneration. Fundamental quantum principles are at work in both of these
situations, as the particles exhibit wave behavior similar to the polarization states of
light.

The mixing theory of Gell-Mann and Pais predicted that the CP-odd A 2
state
could not decay into two pions. An experiment to place improved bounds on this

forbidden mode was undertaken by J. W. Cronin, V. L. Fitch, and others in 1964.

They discovered that a small fraction of all the observed decays of the long-lived
+
neutral kaon led to the unexpected •7t tt~ final state. A main task of the experiment
was to demonstrate that the detected 277 mode was not the result of regeneration. The
similarly forbidden ir°ir° state was also seen in another investigation in 1967. These
findings constituted proof of the violation of Cf-invariance in the weak interaction.
The results, in conjunction with the CPT theorem, implied a breakdown of time-
reversal symmetry in the neutral kaon system.
The
experiments associate definite lifetimes with the two distinct physical decay
states.These decaying systems do not correspond exactly to the definite-CP states K x

and A 2 The decaying particles are therefore renamed Ks and KL (A-short and
.

A-long) and are called by those names in Table 16-1. The experimental results may
be interpreted by attributing the violation of CTMnvariance to the fact that the
physical decay states A v and K L are not CP-pure. The departure of Ks and K L from
A, and A is expressed in this view by altering the superposition of states to read
'.,

+ eK2 K +
A,=
A,
= 2
and KL = ,
2 eK.
2
. (16-11)
/i + M /T+l El

We learn from experiment that the quantity |c| is of order 10 '

ifwe adopt this
interpretation. The equations describe the short-lived state as mostly CP-even and the
long-lived state as mostly CP-odd. The observed C'P-violation in the decays

Kl „<>
{«<> +

is then presumed to be due to the small CP-even A, contribution in the expression for

K, . Equations (16-6) can be employed to writeKs and K, in terms of the

mass-degenerate states of definite strangeness A and A .This remark is developed
more fully in the example below.
C/Mnvariance implies equal probabilities for the two long-lived modes

+
7r~+ e + v
A ' 77' + e~+ vt

CP-violation is seen in these decays, as positrons are observed in slightly greater

+
number than electrons. The asymmetry between
and e "is interesting because the e

asymmetric behavior provides an absolute means of distinguishing particles and

antiparticles. We could use this effect to communicate the difference between left and
right to an experimenter in a distant galaxy, a thought experiment begun in Section
+
16-6. The first instruction would be to establish the distinction between e and e ~ by
observing the charge asymmetry in K L decay. This step would furnish the standard
60
for differentiating matter from antimatter. The /? decay of aligned Co (or anti-
60
Co) could then be used to distinguish left from right.
 16-9 Heulral K Decay and CP Symmetry 857

Example

Our discussion of neutral kaon mixing and CP-violation can be neatly cast in the
language of the Schrodinger equation. First, let the weak interaction be turned
off and consider the simple time-dependent wave functions for stable kaons at
rest:

K° = Ae-'
m ° c2,/h
and K° = Ae-'
m ^ i/h .

Note that each state is parametrized by the same mass m . The I dependence
satisfies the equations

d
ih ih d _ _
— -K°£
= m K° and — -K° = m
z ()
K .

c dt c dt

These equations can be consolidated in matrix form as

'

ih d K m "
K°]
c
2
dt K° m K°

Next, let the weak interaction be turned on, and introduce the mixing mecha-
nism by altering the form of the "mass matrix:"

m u

:l m

The diagonal elements remain equal because of CPT'-invariance, but CP-viola-

tion requires the off-diagonal elements to be different. This step produces a
matrix equation for K° and K° that couples and mixes the t dependences of the
two-states:
'

d K°~ ni a K
~ ih

2
~dt lK°, . V m [K°\
-

The physical decay states Ks

have unique and distinct lifetimes, by
and KL
definition. Consequently, their t dependences must be unmixed, and so the
Schrodinger equation for these states must have the form

ih d K ms "
\Ks]
2
\ A
K L_ mL Kl\
c dt

We can relate the mass-degenerate states K° and ^° to the physical decay

states Ks and KL with the aid of equations in the text. First, we note that
Equations (16-6) and (16-11) are expressible in terms of matrices:

1 -1
1

and
"l K x

e A',
v'l + l«
858 Elementary Particles

Matrix multiplication then produces the desired result:

A',

K,

The observed and the observed mass parameters m s

CP-violation parameter e

and m L are ultimately connectedto the quantities m, u, and v given in the mass
matrix. We leave the derivation of these relations to Problem 17 at the end of
the chapter. The given quantities are complex-valued, and so the derived
parameters must have the same property. We interpret the meaning of the
complex masses m s and m L by defining the following real and imaginary parts:

h
m s c = m so c l
L0 L
2t, 2^
The solutions for A^ s - and KL are then written as

/h c2 ' /k
A^ = A s e~ imsc2 '
= A s e~ ims <>
e~' /2Ts

and

KL = A L e-' m ch/h = A L e-"n '" c2,/he-' /2r

'- '-.

These states have decaying probabilities:

2 /r° 2
l*s|
2
= \A s e-'
\
and \KL \
= \A L \
2
e~'^.

Thus, we see that m so and m L{) are the masses of the decaying particles Ks and
KL , and ts and tl are the corresponding lifetimes.

16-10 Isospin

The list of baryons and mesons in Table 16-1 includes the assignment of several
internal quantum numbers. These properties are associated with the symmetries and
conservation laws that govern the behavior of every hadron. have just examined We
how the strangeness S is treated as one such conserved quantity. Another internal
attribute with its own unique symmetry and conservation law is the isospin, denoted
for each hadron in the table by the pair of quantum numbers / and T,. We have
already introduced the isospin properties of the strongly interacting particles in
Section 14-12 in our discussion of the charge independence of the nuclear force. The
binding of protons and neutrons in the nucleus is only one of many manifestations of
the strong interaction. Our purpose now is to extend the domain of isospin symmetry
beyond the nucleons so that the concept embraces the whole family of hadrons.
Let us begin by organizing the tabulated baryons and mesons according to two
charts, as in Figure 16-19. The members of each group have spatial properties in
+
common, since the baryons are \ particles and the mesons are ~ particles. (These
 16-10 Isospin 859

Figure 16-19
+
Mass levels of the eight \ baryons and the eight (T mesons listed in Table 16-1.

H
Y v
I
A
S = -1

n P i.o-
.<? = n

S =
5
-0 + S = ±l
A'" a: a A"

7T ^° TT
s = o

Mass -1
2
(Gev/C )

spin and parity assignments are deduced by observing the spatial distributions of
outgoing particles and decays of the various species.) The figure is a
in the reactions
+
mass-level diagram, in which the eight ~2 baryons and eight ~ mesons exhibit their
masses at four different levels and three different levels, respectively. The striking
feature of these displays is the fact that approximate mass degeneracies exist among
certain subsets of the particles. This pattern of degenerate multiplets subdivides the two
hadron systems into singlets, doublets, and triplets, each with a strangeness assignment
and a value for the mass. The charge and the slight deviation in mass appear to be the
only distinguishing characteristics among the members of each of the multiplets.
We have seen multiplets of states of different charge and nearly equal energy
before in the isobaric analogue levels of nuclei. Recall that these degenerate energy
states refer to nuclear isobars with the same i
p assignment and with different values of
Z and N for a given value of the mass number A. The existence of such related
nuclear states reflects the charge independence of the nuclear force and, more
generally, the charge independence of the strong interaction. We know that this
property of the nuclear force is expressed in terms of a symmetry with respect to
rotations in isospin space. Recall that the conserved isospin vector T behaves as a
quantized angular momentum, whereby T2 has eigenvalues given by t(t + 1), and Tz
has 2t + 1 discrete values for each integral or half-integral choice of the isospin
quantum number t. Rotational isospin symmetry then implies that the 2t + 1

quantized orientations of the vector T correspond to different states of equal energy.

We establish a correspondence between these degenerate isospin states and the nearly
equal analogue levels of isobaric nuclei. In the process, we argue that nuclear isospin
multiplets result from charge independence and rotational symmetry in isospin space,
just as degeneracies of angular momentum states arise in the central -force problem
from rotational symmetry in ordinary space. This analogy is implemented by transfer-

ring the properties of angular momentum quantization directly to the isospin vector
 ,

860 Elementary Particles

T. We may also argue that slight deviations from degeneracy within an isospin
multiplet are attributable to the influence of the electromagnetic interaction. These
effects break isospin symmetry, just as the imposition of a magnetic field acts to
separate degenerate states in the central-force problem. Thus, the strong interaction is

indifferent to the isospin direction, while the electromagnetic interaction selects the z
direction in isospin space and breaks the symmetry by distinguishing states of different
T. and different charge.
We assign isospin quantum numbers to nuclei in accordance with the basic / = \
doublet identification of the nucleon, where the proton has T, = + L
,
(isospin up) and
the neutron has Tt = - ',
( isospin down). The z component of isospin for a nuclear
state is then determined by the proton and neutron numbers as in Equation (14-47):

Z- N
T. = .

Let us reconstruct this relation into the form

A A
T=Z- - = - ,

2 e 2

01

Q. A
— = T + z
— (16-12)
e 2

by introducing the mass number A = Z+ N and by using

to define the charge in units of e.

We now proceed to assign the isospin quantum numbers of hadrons simply by

observing the charge independence of the masses in multiplets of the sort shown in
+
Figure 16-19. To illustrate, we note the near degeneracy of the pions 7T~, m and , tt

and take t = 1 to denote a triplet of states with Tz = — 1, 0, and +1. All the
tabulated \ baryons and mesons are similarly organized according to the
following assignments of internal quantum numbers:

Tt - -1 1 •• 2
T, = (1
/'
= +2" T = +1
:

B = 1 5 = N doublet I = 2
i

n P
S = - 1 A singlet I
= A
S 1 2 triplet t
= 1
2" 2° 2+
S= -2 Z doublet I
= 1 "=" •=•0
2

T. = -1 T = -l
1
z 2
T. = Tz -+i Tz = +1
' +
B = S = m triplet I = 1 77 7T° 77

+
S= +1 K doublet t
= 1 K° K
S= -1 K doublet t
= 1
2
K~ K°
S= T) singlet t
= (1
1

These properties are entered in Table 16-1.

 1610 Isospin 861

The values of the charge Q/*, the baryon number B, the strangeness S, and the z
component of isospin Tz obey the relation

£> B+ S
- = Tz + (16-13)
e 2

foreach of the tabulated baryons and mesons. This relation among quantum numbers
is due
to Gell-Mann and K. Nishijima and is meant to be a general formula for all the
hadrons. Since B and S appear together in the equation, it is convenient to define a
new quantity called the hypercharge,

Y = B + S, (16-14)

and write the Gell-Mann-Nishijima relation in the form

- =T+ z
-. (16-15)
e 2

A listing of hypercharge quantum numbers is also included in Table 16-1. We note

that the assigned values of Y range symmetrically between - 1 and + 1 for all listed
baryons and mesons. We also note the close similarity between Equation (16-15) for
hadrons and Equation (16-12) for nuclei.
It is instructive to display the hadrons by plotting their quantum-number assign-
ments on a graph of hypercharge versus z component of isospin. Figure 16-20 shows
+
such a presentation for the \ baryons and " mesons. The two particle patterns are
known as octets, since there are eight members in each group. Note that the designs are
symmetrical in the variables Y and T, and are identical in form. The use of the
hypercharge Y, instead of the strangeness S, accounts for the similar appearance of
the baryon and meson octets. These graphs give a complete picture of the quantum-
number content of the various hadrons. We observe that the isospin t is not directly
The value of this quantum number is evident nevertheless, since each
indicated.
isospin multiplet appears on the graph as a horizontal subset of particles with
862 Elementary Particles

multiplicity 2t+ 1. The symmetry of these patterns suggests an organization of the

hadron families on a higher level beyond the scheme put forward so far.
Let us turn now to the use of isospin as a conserved quantity in elementary particle
phenomenology. We can test the conservation law, and the isospin assignment of the
pion, by comparing the two reactions

+
n +p -> 77° + d and p + p -> 77 + d.

The deuteron is a / = nucleus, and the pion is taken to be a / = 1 triplet of mesons.

Both final states should then have t =
and the same should be true of the initial
1,

states if isospin is conserved. We therefore expect the cross sections to have the ratio

o(n/> ->w°(rf) 1

o(pp -» ir
+
d) " 2'

because we see from Equations (14-48) and (14-49) that the np state has / = 1 in half
of composition, while the pp state has / = 1 exclusively. This prediction for the
its

cross sections in the two reactions is confirmed by experiment.

Charge independence can be put to good use in the study of the interactions of
pions with nucleons. The scattering processes

+ + 77 + p
7r +p ~* 7r + p and 77 +p
77° + n

are especially useful as sources of information about the 77 N system. It is also possible
to examine many other combinations and nucleons. of initial and final states of pions

We learn from charge independence that only two independent complex amplitudes
are required to express all possible combinations. We can understand this property of
pions and nucleons by adding isospins and invoking isospin symmetry. The itN system
has isospins Tw and TN and so the total isospin is expressed as the vector sum
,

T = TW + T„. (16-16)

This prescription instructs us to add quantized vectors corresponding to isospin- 1 and

isospin- ',
. The vector addition produces two values for the total isospin quantum
number according to the rule

= and
1 +
22
I I -
2

(just like the addition of angular momenta J = L + S, where (= and s = ^ 1

combine to form j '

= 7; and j = f).
The main thrust of charge independence can now
be recognized. Rotational isospin symmetry tells us that the strong interaction is

indifferent about the orientation of the vector T in isospin space. Only the magnitude
of T matters, so that a separate independent amplitude need not be introduced for
every possible value of Tz We
. have just found T to have two allowed values of the

magnitude \jt(t + l) , one for t = \ and one for t = f . Consequently, only two
independent quantum mechanical amplitudes are needed to describe all 77./V —» 77N
processes. If we designate these quantities as X1/2 anc^ X3/2J we ^ nc^ mat tne
amplitudes for the elastic and charge-exchange scattering processes cited above are
 16-10 Isospin 863

given by the formulas

+
X(77 />,77>) =X 3 /2,

xi^P^'p) = (x 3/2 + 2Xi/2 )/3,

x(^%, 77-/,) = /2(x 3/2 -X 1/2 )/3. (16-17)

It is clear that isospin symmetry is a rather powerful idea since the number of different

reactions of interest is reduced to a fundamental set labeled only by the isospin

quantum number t.

We
do not need a derivation of the numerical coefficients in Equations (16-17) to
comprehend the basic meaning of the formulas. The first equation says that the m +
p
system can only be in a t = § state, an obvious fact since the z components of isospin
add up to give
7z =
1
-
1 + 1
2
= 1
2

+
for 77 and p. (The same argument applies to the 77 « system where

Tz = -1 - \ = -§.

Charge symmetry tells us that the sign of T. is immaterial and that the elastic
scattering amplitudes for m + p and 77 ~n satisfy ihe identity

+ +
x(v p,7r p) = x(tt 72,77 n) = x 3/2-

This predictionis verifiable and agrees with experiment.) We cannot draw such an

immediate conclusion about the ir~p and m°n states. Both of these systems have
T i:

Tt = - + 1 \ for TT~p and Tz = - \ for ttV

Since 7^ = — ^ occurs in one of the four substates for / = | and also in one of the two
-
substates for t = ^, it is apparent that both tt /) and 77 °« correspond to superpositions
of the < = ^7 and / = \ states. The actual mixtures needed to form the two 777V
systems are well-defined and lead directly to the results quoted in Equations (16-17).
We pursue these remarks somewhat further in Section 16-11.

Example

Our discussions of the internal quantum numbers have been aimed primarily at
the conservation laws pertaining to the strong interaction. Let us consider some
weak decays now so that we can demonstrate a few violations of the laws. In A
decay, A — p + > 77", we have a transition of overall quantum numbers of the

form

S = - 1 and T. = and T =

The changes of strangeness and isospin are AS = 1 and AT, = — ^. In charged

+
K decay, K + -* 77 + 77 , we have another transition of the form

S = 1 and T, S = and T = 1
864 Elementary Particles

and so the changes are AS = — 1 and A 7". = \. An examination of the weak

decays of all the strange particles reveals a pattern of violations:

AS= ±1 and A7; = + \, or AS=-2A7;.

This selection rule for strangeness-changing decays is consistent with Equation
(16-13), the Gell-Mann-Nishijima formula, by virtue of the conservation of
charge and baryon number.

Example

The conservation law for isospin is a vector constraint, as is the conservation of

angular momentum. We implement the law in strong-interaction processes as
follows, with comments appropriate in each instance:

77 + p — K° + A, a
> t = f) reaction, even though m~ p also has a t = § part.

K + p — > T) + A, a < = reaction, even though K~ p also has a t = 1 part.

A + A -f*
it + 7j, a violation of isospin conservation.

#*+ p -f*
77
+ -t- 2+ , a violation of conservation of isospin and strangeness.
+ + +
77 + p —» A^ + 2 , a pure £ = | allowed reaction.

Other systems are considered in Problems 18 and 19 at the end of the chapter.

16-11 Baryon and Meson Resonances

High-energy spectroscopy is concerned with the mass levels and quantum states of
baryons and mesons. These particle properties can be ascertained by investigating the
reactions of colliding hadrons. The products of a given reaction may exhibit new
hadronic states as resonances in the reaction cross section. We have seen resonances in

nuclear reactions, and we have interpreted the phenomena as excited nuclear states
representing unique short-lived configurations of the interacting nucleons. Hadron
resonances occur in a higher-energy range, as expected for the excitation of matter on
a smaller scale. The widths of resonant hadronic states are considerably larger than
their nuclear counterparts, and the lifetimes are correspondingly shorter, as ap-
propriate for the smaller size of the resonating systems. Typical widths and lifetimes
are of order 100 MeV and 10" 23 s, respectively. Thus, the hadronic excitations are in
the domain of the strong interaction, where the instabilities of the resonances are
many orders of magnitude stronger than the weak instabilities of the listed hadrons in

Table 16-1. The resonances are produced via the strong interaction and decay by the
same route. These systems exist with specific mass and quantum-number assignments
and are accorded hadron status on a par with the more familiar particles, despite their
extremely transitory nature.
Excited states of the nucleon are seen in the interactions of pions with protons.
Prominent resonances of the itN system appear as distinct bumps in the total cross
+
sections for the 77 /> and m~ p reactions

±
77 + p -* all possible final states.
 1611 Baryon and Meson Resonances 865

These processes are subject to the isospin conservation laws discussed in

Section 16-10.
The reactions can therefore be reduced to a description in terms of two basic cross
sections, corresponding to the two values of the total isospin quantum number = \ t

and t = f .
If we denote these quantities aso |/2 and a 3/2 we find that the observed
,

m ±p total cross sections are given by the formulas

+
o(tt p) = o 3/2 and a(ir-p) = %(o 3/2 + 2a 1/2 ). (16-18)

(Note that the formulas are just like the ones for the scattering amplitudes in
Equations (16-17). The results follow from a theorem that relates the total cross section
directly to the imaginary part of the amplitude for elastic scattering. These total cross

sections are also expressible in more familiar terms as sums of the squared moduli of
all the contributing amplitudes.) We can easily invert the relations to obtain a 1/2 and
a 3/2 :

§a(w p) - \a{m + p) = +
and o 3/2 a( ir p). (16-19)

In these formulas, the fundamental isospin cross section o t

refers to a hypothetical
process in which the colliding 77 iV system is prepared in a state of definite isospin t.
+
Recall that tt p is already such a state and that 77 ~p is a superposition of isospins \
and §.
+
The total cross sections for 77 p and ir~p are sketched in Figure 16-21, along with
the derived isospin cross sections a 1/2 and o 3 2
Both sets of quantities depend only on
, .

the 77 N collision energy. We show the 77

±
p information as a function of the pion
beam energy Kn and we use the total , CM energy £CM in the graphs of o 1/2 and
a 3/2- The latter variable is the same as the one used to display the various reaction
thresholds in Figure 16-16. The graphs on the left side of Figure 16-21 are obtained
from experiment, and those on the right are then constructed with the aid of
Equations (16-19). We are particularly interested in the second set of cross sections.
These graphs demonstrate a clear separation of the resonance bumps, and thus
indicate a unique isospin assignment for each resonant state.
The most striking feature of the irN system is the resonance peak in the cross
section at K„ = 190 MeV (or £ CM = 1.23 GeV). We see from Figure 16-21 that the
cross sections at this energy have the approximate values

+ =
o(tt p) = 200 mb and a{-n~ p) 67 mb.

The 3 : 1 ratio of these results is readily understood from isospin considerations. A =

t
§
assignment for the resonance is obvious, first of all, since o 3/2 is much larger than
o 1/2 . If we neglect o 1/2 at this energy, we obtain

+ =
0(77 p) 3a(77"/?)

directly from Equations (16-19). The elastic and charge-exchange scattering processes
can also be examined from the same viewpoint. If we neglect the t = \ amplitude
following ratios for the elastic and charge-
Xi /2 in Equations (16-17), we get the
 2

866 Elementary Particles

Figure 16-21

Pion-nucleon total cross sections. The graphs on the left pertain to the processes ir
± + p -» all
possible final states, and the graphs on the right refer to itN interactions in the separated
isospin states / = i and t = \,

200 200-

100 -

14 16 18
/•:,
M (GeV)

exchange cross sections:

9 9 i 1

The experimental results confirm this prediction and verify decisively the t = \
hypothesis for the resonant state.

Three other resonance bumps also appear with clearly established isospin quantum
numbers in Figure 16-21. The resonant states are found to have unique spins and
parities by analyzing the spatial distributions of particles scattered at the different
resonance energies. Furthermore, the bumps occur at specific values of the CM
energy, so that the resonances correspond to definite assignments of mass. Thus, a
given resonant state is defined by a mass level and a complete set of hadron quantum
numbers, including the usual spatial properties of spin and parity, and also the
internal attributes of isospin, baryon number, and strangeness. We recognize these
characteristics to be exactly the same as those possessed by the more familiar (and
more nearly stable) hadrons, and we therefore regard the resonances as full-fledged
hadronic particles. The four prominent resonances at energies below ECM = 2 GeV
are designated by the following symbols and specifications. The t = | states are called

+ +
A(l232,f ) and A(l950,^ ),

and the / = i states are called

+
AT(l520,f )
and A^(l680,f ).
 16- 1 1 Baryon and Meson Resonances 867

Figure 16-22

Meson-nucleon reaction yielding two or more

mesons in the final state. The detection of
two mesons provides information about the
meson- meson interaction.

Ei Pi

The parenthetical information gives the mass in MeV/c 2 along with the spin and
parity. Each of these hadrons has baryon number B = 1 and strangeness S = 0,
because each occurs as an excitation in the pion-nucleon system. The isospin
assignments tell us that there should be four degenerate particles for t = with f,
T. !

2> ;, and

A", A , A + .and A-

and two degenerate particles for t = £, with T

z
=
£ and \,

N <mdN +
r
'
.

The indicated charges of these baryons are in accord with the Gell-Mann-Nishijima
formula. Equation (16-13). Numerous other baryon resonances with strangeness
quantum numbers S = and £ ¥= are also known.
Meson resonances also occur, in states whose existence could be detected if
meson-meson collisions could be observed. Unfortunately, such experiments cannot
be performed directly because stable meson targets do not exist. It is possible to see
these resonances indirectly by investigating those meson-nucleon reactions in which at
least two mesons appear in the final state. Figure 16-22 illustrates this sort of process

and suggests how a particular pair of final mesons may be analyzed in order to gain

access to the meson-meson interaction. We can undertake such a study by measuring

events in bubble-chamber photographs, for example. Measurements of momentum
and energy for the selected pair of mesons can be used to determine a value from each
event for the invariant mass of the two-meson system. This quantity is defined in terms
of the kinematic observables shown in the figure by recalling the energy-momentum
relation for a single particle, Equation (1-35), and by introducing the analogous
formula

(m uc 2 ) = (£, + E2 f - <r
2
(p, + p 2 )~ (16-20)

for the case of two particles. We note that the expression m v2 c' is Lorentz-invariant
and is equal to the total energy of the two mesons in their own CM frame. The mass
m x2 is a useful variable to employ in a plot of the distribution of the measured events.
868 Elementary Particles

Figure 16-23

Mass distributions of pion pairs showing the p meson resonance at 770 MeV/c 2 .

Events

Events

07 09 1.1 1.3 1.1 1.3

n tt° Mass (GeV/c 2 ) (GeV/c 2 )

A resonance in the meson-meson system appears in such a plot as a peak in the

distribution, indicating an exceptional population of events for a specific value of the
invariant mass.
Evidence for the resonance known as the p meson is obtainable by an invariant-mass
analysis of the reactions

+
+ 77 + 77° +p
7T +p +
77 + 77 '
+ 77 + p.

Figure 16-23 shows two typical distributions in which a prominent peak appears at the
mass value 770 MeV/c 2 in the 77 + 77° system of the first reaction, and in both 77 + 77~
+ +
systems of the second reaction. No such phenomenon is seen, however, for the 77 77

combination in the second process. These results are consistent with a / = 1 isospin
assignment for the resonance, where the states with T, = —1,0, and 1 correspond to
+
the charged mesons p ,
p°, and p*. The p + state is observed in 77 77°, and the p°
+ + +
state is observed in 77 77 . The absence of an effect in 77 77 rules out the possibility
of a I = 2 assignment, and so, of the total isospins possible for two isospin- 1 pions,
t = 0, 1, and 2, only the t = 1 hypothesis agrees with experiment. Further analysis
shows the spin and parity of the resonance to be 1 ~, the quantum numbers of a vector
meson. The t = 1 p meson has strangeness S = and, of course, baryon number
B = 0. Other meson resonances are found in many different varieties with a profusion
of spatial and internal quantum numbers.
Vector meson resonances can also be seen in processes initiated by the collision of
beams of electrons and positrons. In these reactions electron-positron pair annihila-
tion takes place, producing electromagnetic energy, and systems of hadrons then
+
materialize out of this energy. The total cross section o(e~e ) includes the processes

+ —
e~+ e > all possible hadrons

and exhibits a rich spectrum of resonance peaks corresponding to uncharged hadronic

 16-11 Baryon and Meson Resonances 869

stateswith internal quantum numbers 5 = and S = 0. These meson resonances are

produced via the electromagnetic interaction and are vector particles since they bear
the same 1 ~ spin and parity properties as the electromagnetic field.

Example

+
Let us examine the hadrons A(1232, f ) and p(770, 1~) and show that both
occur as c"= 1 resonant states in their respective interacting systems. The baryon
+
A++ is a ~
+
resonance of the m p system. Since and p are 0~ and -^ tt
+
+
particles, the parity of the 77 /> orbital state must be odd in order to conserve
parity. It follows that the orbital quantum number c* must be odd, and only
/= 1 is allowed by conservation of angular momentum. The meson p + is a 1 ~
+ =
resonance of the 77 7r° system. In this case, c* 1 is required immediately so
that the two 0~ particles conserve both angular momentum and parity. The
meson p° appears in 77 + 7r~ but is forbidden to occur in 77°77°. This conclusion
follows from Bose symmetry, which demands an exchange-symmetric wave
function for the two identical pions. An c"= 1 pair of 77° mesons is not allowed
because the state would have odd spatial symmetry and would therefore be
exchange antisymmetric.

Example

Two different kinematic variables are use^ to display the baryon resonances in

Figure 16-21. The beam energy (or beam momentum) is the natural choice for
the presentation of cross-section data, but the total CM energy is more conveni-
ent for interpreting the resonances as particles of definite mass. We can readily
pass from one variable to the other with the aid of techniques discussed in
Section 1-11. Consider m -p collisions where the beam pion (mass m) has
momentum p and energy E, and where the target proton (mass M ) is at rest.

Thetotal momentum four-vector in the lab frame is

&> =
i(E + Mc 2 )/c

Let ECM be the total CM energy so that 0> transforms into the four-vector

in the CM frame. We invoke Lorentz invariance and obtain

E 2M 2
E 2 + 2EMc 2 + M 2
c
4

2EMc 2 + (m 2 + M 2
)c
L
870 Elementary Particles

using the relativistic relation between p and E. The result takes the form

r2
'CM
= 2Mc 2 {K + mc 2 ) + (m 2 + M 2
)c* = 2Mc 2 K + (m + Aifc'

when we introduce the pion beam kinetic energy K=E— mc 2 This formula
.

enables us to relate the energy axes in the left and right halves of Figure 16-21.

16-12 Quarks

An abundance of hadrons and an organizational scheme have begun to take shape in

our survey of the elementary particles. We have identified a few of the existing baryon
and meson species, and we have drawn special attention to the internal quantum
numbers that characterize the particles. More than a hundred different hadronic states
actually occur. All these particles can be grouped into families of common spin and
parity like the eight baryons and the eight 0~ mesons in Table 16-1. The
r,

groupings may be represented by plotting the isospin and hypercharge quantum

numbers Tz and Y, as in the octet patterns shown in Figure 16-20. We have noted that
higher symmetry, encompassing the inde-
this classification suggests the influence of a

pendent symmetries associated with the separate conservation laws of isospin and
strangeness.
It should be acknowledged at once that the hundred or more existing hadrons are
far too numerous to be regarded as fundamental particles. This remark obviously
applies to the baryon and meson resonances, since these states occur as short-lived
composite systems of interacting hadrons. We must concede the same point regarding
the proton and neutron, because we know that even these more primitive particles are
structured entities. The evidence for nucleon structure begins with the fact that the
magnetic moments of p and n are not equal to the values expected for elementary
Dirac particles. The proton and neutron are also known to have an extended size and,
by inference, an internal substructure. We learn about these properties in electron-
scattering experiments with nucleon targets, similar to the studies discussed in Section
14-3 in the case of nuclei. Thus, it is clear that the nucleons are no more fundamental
than the various resonances and that all hadrons should be treated on an equal
footing. We have already espoused this democratic point of view in Section 16-11.

The two notions of higher symmetry and hadron substructure were drawn together
into a single conceptby Gell-Mann. In 1961, he organized the hadrons according to a
generalization of the concept of isospin by invoking a rotational symmetry in an
internal vector space of eight dimensions. This extension of the familiar three-dimen-
sional isospin space was designed to incorporate hypercharge among the eight
necessary internal degrees of freedom. Gell-Mann called his mathematical framework
the Eightfold Way. The proposal played the role of a periodic table for the
elementary scheme was used to classify known varieties and predict
particles, as the
new hadrons. In 1964, Gell-Mann showed that the mathematical aspects of his
higher-symmetry scheme could be encoded in the quantum numbers of a hypothesized
set of three fundamental particles, called quarks. He demonstrated that the existing

baryons could be constructed from simple combinations of three quarks, and that the
existingmesons could be assembled by combining quarks and antiquaries. The concept
was originally developed as a means of synthesizing the quantum numbers of the
observed hadrons in terms of more basic elements. In this sense the quarks were
contrived to implement a model of the higher internal symmetry. Soon, however, it
 1612 Quarks 871

Murray Gell-Mann

became clear from experiment that quarks and antiquaries had real identities as
fundamental constituents in the substructure of hadrons.
Quarks and antiquaries are distinguished from conventional hadrons by the fact
that they are assumed to carry fractional charge and baryon number. The rules of the
quark model tell us from the outset that the postulated particles have values of Q/e
and B in one-third units. Three quarks, called u, d, and s, are introduced with the
following assignments of quantum numbers:

B=\ T, = S = r-i d/e=l

-1

We note that the entries in the last column are consistent with the Gell-
Mann-Nishijima formula, Q/e = Tz + Y/2. The corresponding antiquaries u, d, and
s have suitably conjugated quantum numbers as follows:

B = T, = 5 = Y= d/e =

We observe from the listings for Tz and S that the role of each quark is to supply a

singlenonzero quantum number in the synthesis of any chosen hadron. This use of
quarks as ingredients in a composition is called an assignment of flavors. Thus, the u
quark is u-flavored with isospin up (Tz = ^), the d quark is ^-flavored with isospin
down (T = — ^), and the s quark is ^-flavored with strangeness (S = - 1). These
z
872 Elementary Particles

Figure 16-24

Flavor assignments of quarks and antiquaries.

V V

As

>
d :

1 i
1
2
/',
1 1

:." o^

flavor designations are conveniently plotted on graphs of the hypercharge versus the z
component of isospin, as in Figure 16-24. The resulting triplet and antitnplet patterns

represent the basic structures of Gell-Mann's higher symmetry.

Let us consider the construction of hadron states in terms of our newly defined
building blocks. Quarks and antiquaries are assumed to be spin- ~ fermions, so that
odd and even numbers them are needed to make baryons and mesons. We use three
of
quarks (qqq) to assemble the quantum numbers of baryons, because of the B = \
definition for the baryon number of quarks, and we use quark-antiquark (qq)
combinations to construct the quantum numbers of mesons. Other compositions, such
as qqqqq with B = 1 and qqqq with B = 0, may also be considered. These so-called
exotic states are not essential for the purposes of this discussion.
The internal quantum numbers of the mesons are obtained by the blending of
flavors in the following qq systems:

+
77 = ml Y = S = V = 1

7T° = ^{dd — uu) 1)

\/2

7T~ = — du 1) -1
+=
K in 1
1

K° = dl 1
1

K° = sd -1
K = Ml 1
_ I
9

TJ
= —f=-(uu + dd- 2ss) (1 o (16-21)

The set of all possible combinations of three quarks and three antiquarks also includes
a ninth independent structure:

(uu + dd + ss) Y = S= T = (16-22)

^3

(This singlet state is separate from the octet of pseudoscalar mesons listed in Table
16-1. Note that the tt , tj, and tj' systems are formed by superposing uu, dd, and ss
 1612 Quarks 873

states.) It is implicit in each of these expressions that the spatial states of the
constituent particles must have total spin and orbital quantum numbers s = and
(= so that a vanishing total angular momentum is obtained, as required for a
spin-0 composite system. The odd parity of the 0" mesons is then due to the intrinsic-
even and odd parities of quarks and antiquaries. This property of opposite parities
holds true for all spin- \ Dirac particles and antiparticles.
Thethree-quark baryon structures are somewhat more difficult to assemble. A
convenient starting place is the t = \ A multiplet:

uuu,

A = -j=^(duu + udu + uud),

v3

A = -j=r(ddu + dud + udd ,

k~=ddd. (16-23)

Note that the uuu system has Tz = \ as required, and note that the successors to this
state follow by applying the systematic isospin-lowering operation u -* d to each
quark. There are exactly ten different combinations of the three quarks u, d, and s:

ddd ddu duu uuu >viih Y= 1

dds dus uus with Y=
dss uss with Y= —1
sss with Y = -2

Superposed permutations of these states can be put in one-to-one correspondence with

the ten members of an existing family of f resonances, whose members include the A
multiplet. The unique Y = — 2 system, identified as

Q~= sss,

is especially interesting because the proven existence of this hadron validates the
underlying higher-symmetry scheme. These three-quark expressions must be supple-
mented by spin and orbital configurations appropriate for composite states with spin
and parity | Positive parity is obtained if each quark is in an s state, and spin- 1 is
.

the result if the quarks are assembled with parallel spins. The procedure is illustrated

by the composition

A ++ = ««kT T T,

in which three .r-statequarks have parallel spins so that the z component of total
angular momentum corresponds uniquely to a ~ state.

Combinations of three quarks can also be deduced for the \ baryon octet of
Table 16-1 and Figure 16-20. We see at once that the flavor mixtures uud and udd
reproduce the internal quantum numbers of the proton and neutron. Since these same
+
forms appear, along with their permutations, in A and A it is necessary to take ,

specific combinations of permutations if p and n are to have their own independent

874 Elementary Particles

states. If we take

1 1

p = —r= ( uud — udu ) = —j= u(ud — du) (l6-24a)

ind
1 1

n = —j^idud — ddu) = —^d(ud — du)' (!6-24b)

\/2 i/2

we find that p and n are orthogonal to A + and A ensuring the independence of the
,

states. Strange baryons in the octet may then be constructed by the systematic
+
substitution of an ^-flavored quark. Thus, we derive 2 from p by substituting s for d
to get

2+= -7=- u ( us — su).

l/2

The ~ *
assignment of these baryons is achieved by assembling estate quarks in states
with two spins parallel and one spin antiparallel.
So far we have treated quarks only as bearers of flavor in a model of the states of
hadrons. We may wonder whether the constituents are just fictitious artifacts of the
model, or whether they really exist as observable particles. The latter question has to
be decided by experiment. If a free quark could be separated from others of its kind,
and if the quark could be bound in an atom, the distinctive one-third unit of charge
would be a readily detectable signature. Recent experiments conducted by W. M.
Fairbank have succeeded in isolating a fractional charge on a metal sphere; however,
no other similar studies have confirmed this observation. Millikan himself is supposed
to have seen, and discarded, a fractional charge on an oil drop as long ago as 1910.
Quarks bound in atoms could also manifest themselves in atomic emission spectra and
in mass spectrograms, but no such indications have ever been recorded. To date,
searches of all kinds have failed to offer convincing evidence, not only for the
occurrence of free quarks in bulk matter but also for the production of free quarks in
cosmic-ray events and in accelerator experiments.

None of these negative results is in conflict with the accepted belief that quarks
really do exist as bound constituents inside hadrons. Evidence for the validity of this

Figure 16-26
Figure 16-25 Construction of qq states by adding vectors in
Inelastic electron scattering as a probe of the (Y, T z )
plane.
baryon substructure. Y
Hadrons

ud
 16-13 The Electromagnetic and Weak Interactions of Quarks 875

picture has been gathered since 1968 in reactions of the form

e~ +p -* e~+ hadrons,

in which the inelastic scattering of electrons is studied at very high energy. Figure

16-25 shows schematically how such a process employs very-high-energy virtual

photons to probe the small-scale structure of the proton. The experiments indicate
that the nucleon contains point-like particles whose properties fit the description of u
and d quarks. The conclusion to draw from these findings is most remarkable. The
quarks are evidently confined in hadrons as permanently bound constituents and are
not found as liberated particles. This point of view is a fundamental feature of the
modern theory of the strong interaction.

Example

Quark-combining and flavor-bookkeeping may be visualized with the aid of

graphs of Y versus T z
. Let us refer to Figure 16-26 for illustration and construct
the qq composite states by the addition of vectors in the (Y, T ) plane. The
z
figure shows the quark triplet centered at the origin and the antiquark anti-
triplet centered at the location of the u quark. The indicated vector additions
generate the flavor-blended systems uu, ud, and us. If we relocate the center of
the antitriplet at the site of the d quark, and then at the site of the s quark, we
obtain the combinations du, dd, and ds, and then su, and ss. The nine
sd,
resulting composite systems have the internal quantum numbers of the octet
states in Equations (16-21) and Figure 16-20, and the remaining singlet state
described by Equation (16-22).

16-13 The Electromagnetic and Weak Interactions of Quarks

If hadrons are composed of bound quarks it follows that the interactions of hadrons
are fundamentally expressed in terms of the interactions of quarks. All electromag-
netic hadron processes are thereby attributed to radiative quark transitions accompa-
nied by the emission of photons. Likewise, weak hadronic processes are due to weak
all

quark transitions in concert with the emission of weak quanta. The analogy between
the electromagnetic and weak interactions has been introduced with the aid of
Feynman diagrams in Section 16-7. This parallel can now be developed further using
diagrams based on quarks. In fact, the overall success of weak interaction theory in
the context of the quark model constitutes a large share of the evidence that supports
the reality of quarks.
Figure 16-27 shows two examples of the electromagnetic interaction of quarks. The
diagram for electron-proton elastic scattering shows the exchange of a virtual photon,
where the indicated coupling of the photon is taken to each of the proton's u and d
quarks in turn. The hyperon decay 2° —» A + y is represented as a radiative quark
transitionfrom one uds system to another, where the emission of a real photon can
take u into u, d into d, or s into s, each with its own amplitude. These transition

amplitudes are determined by the coupling between the photon and the electromag-
netic current of each quark.
Weak processes have already made their appearance in the Feynman diagrams of
Figure 16-15. Recall that the exchanged weak quanta carry charge and that the
corresponding hadronic transitions are charge-changing phenomena in all the cases
876 Elementary Particles

Figure 16-27

Quark- photon couplings in ep elastic

scattering and 2° decay.

considered so far. The quark model offers a description in which the weak interaction
causes changes in flavor among the constituents of the interacting hadrons. We can
display these processes as weak transitions from one quark flavor to another, using
diagrams like the ones in Figure 16-28. Note that the hadron transitions n —» p and
p —> n proceed via the coupling of
—»
W and W +
to the weak charge-changing quark
currents d u and u —* d, while the remaining u and d quarks act as spectators. The
[3 decays of strange particles take place in similar fashion, as illustrated in Figure
16-29. In these instances, the quark flavor transition is associated with the
strangeness-changing charge-changing weak current s —* u. Strange particles also
decay to final states consisting only of hadrons. These nonleptonic modes have their
own quark Feynman diagrams. Again, Figure 16-29 describes such decays of the
strange hadrons in terms of the flavor transition s —* u.
Strangeness-changing decays are observed to be universally smaller in amplitude
than comparable strangeness-conserving decays. Processes suitable for comparison are

A p + e~ + vt n -* p + e~+ ve
and versus and
A' 77° + e~+ ve 77~—> 77° + e~+ V l

ere s —> u where d —» u.

Figure 16-28

Weak quark transitions in the fi decay of the neutron and in the neutrino reaction v^ + p
+
-»
n + n.
 16-13 The Electromagnetic and Weak Interactions ol Quarks 877

Figure 16-29

Quark Feynman diagrams representing the decays of strange particles. The upper three
diagrams show the /? decays A -* p + e "+ v and K -» ir~ + +
L t
e + vt or m+ + e + vr . The
lower three diagrams show the nonleptonic decays A -» p + m and A' v -» 77 + tt
'

N. Cabibbo has shown that these phenomena conform to a unified picture based on
Gell-Mann's higher-symmetry scheme. The ideas can be translated into the language
of quarks so that a direct comparison can be drawn between the weak quark currents
s —> u and d —>
Note that the strangeness change is AS = 1 for the one current and
u.

AS = The quarks s and d have the same charge, Q/e = -- j, and so

for the other.
a superposition of the two flavors is allowed. This mixing of strangeness states fixes a
connection between the violation and conservation of strangeness in the weak transi-
tions. According to the Cabibbo argument, the flavor change from s or d to u is such

that the accompanying emission of W~ always selects the specific rotated combination
of s and d given by the expression

<^cos + s sin#.

The coupling of the weak quantum to the corresponding Cabibbo current is shown
schematically in the left half of Figure 16-30. The flavor structure of the current can
be expressed as

0.
with (16-25)
d cos + s sin 9

This prescription stipulates that all s -» u transitions are reduced in amplitude relative

to d -» u transitions by the ratio of the respective coefficients sin #/cos 6. The

878 Elementary Particles

Figure 16-30

Couplings of generalized weak quark currents. The first diagram contains the Cabibbo current,
and the second introduces the concept of charm.

d cos 6 * s sin 8 -d sin 6 + scos

observed suppression of strangeness-changing decays is thus parameterized by a single

constant given by the Cabibbo angle 0. Good agreement with experiment is obtained
for a value of around 13°.

A problem arises when we consider the possibility of the two apparently similar
decays

K -> 77° + e~ + ve and K~-* 77~+ vr + ve .

The first of these processes is observed, as noted above; however, the second decay is

not known to occur. We see that the transitions in the respective quark-antiquark
systems are

su —> uu and su -» du,

so that the relevant quark flavor transitions must be

s —> u and s —> d.

Both are strangeness-changing effects; however, the one is charge-changing while the
other is charge-conserving. The observed suppression in the second case can be
explained by invoking the following flavor-transition mechanism, put forward by S. L.

Glashow, J. Iliopoulos, and L. Maiani. Their proposal calls for the cancellation of a
pair of conspiring contributions to the strangeness-changing charge-conserving current
and also introduces a new quark flavor called charm. The mechanism employs two
rotated combinations of s and d:

d cos + s sin and — d sin + s cos .

We note that the second expression is orthogonal to the first and that the first

expression is part of the Cabibbo current. A cancellation of contributions to the s — d

>

current takes place via the schematic procedure shown in Figure 16-31. The replace-
ment of s and d by the two rotated forms produces the indicated substitutions, in
which the s —> d transition appears with coefficient sin cos in the first contribution
and — cos 6 sin in the second. The argument goes on to hypothesize a new quark

flavor with Q/e = §, denoted by c. This new quark is conceived to be a partner for
the second of the two rotated combinations of ^ and d in a new charge-changing
 1 61 3 The Electromagnetic and Weak Interactions of Quarks 879

Figure 16-31

Cancellation mechanism for strangeness-changing charge-conserving quark currents.

d dcos0+ssm0 -d sm + s cos

s sin + d cos s cos - d sin

current:

0.
with
d sin 6 + s cos 6
(16-26)

Thus, two related weak quark currents are defined by introducing the rotations of the
two flavors. We show these flavor transitions together in Figure 16-30.
A charm quantum number C is also defined along with the introduction of the
c-flavored quark. Table 16-2 quantum-number assignments for the quarks u,
lists the
d, s, and and includes a new column ior the values of C. Like isospin and
c

strangeness, charm refers to another quantity conserved by the strong interaction. The
entries in the table tell us that the Gell-Mann-Nishijima formula for the charge must
now be modified to include C:

— = T + -
Y
+ —C (16-27)
-
* 2 2

a
Table 16-2 Quantum Numbers of Quarks and Antiquarks

B 1 T. 5 Q/e
i 1 i
1 2
II (1 ',
2 2 3

d
i 1
_ i II
1 I

3 2 2 i 1

2
A
1
- i
I

3
3

1
(1
1 2
c 3 3
1

u _ i
_ 3
J

3 2 2

d _ 1

2
1
1

3
i

3 2
;

I
_ 1
2 i

3 i i

c
_ 1 1

-1 j

"Flavors are listed according to baryon number, isospin and z component, strangeness, hypercharge,
charm, and charge. Evidence exists for a ^-flavored quark with Q_/e = - j, and speculation abounds for a
^-flavored quark with Q/e = -.
880 Elementary Particles

The charm hypothesis implies that the c quark should manifest itself in the existence
of hadrons containing the new flavors c and c. These quantum numbers may occur in

c- flavored baryon and meson systems, such

as udc and cu, or in hidden-charm cc states.
The first charm came with the discovery of the J/4>
definitive evidence for
resonance in 1974. This unusual vector meson was seen in independent experiments
performed by the research groups of S. C. C. Ting and B. Richter (hence the split
personality implied in the name of the particle). The resonance was detected in the
+
collisions of high-energy particles as a very sharp yield of e~e pairs at an energy
/-.',
M = 3.1 GeV in the two-lepton CM frame. Hadronic decays of the resonance were
also in evidence, but not to the degree expected for such a massive unstable hadron.
This suppression of hadronic modes suggested that the observed meson must be
composed of new quark flavors unlike those found in the available hadrons. The
resonance was identified as a bound cc system, with an energy below the threshold for
decay into any as-yet-unknown particles of nonzero charm. Thus, the J/\p meson was
interpreted to have charm C = like the other known hadrons. The cc system was

given the generic name charmomum. The bound charm degree of freedom was expected
to become observable if enough energy could be added to dissociate a cc state into
separate c- and c-flavored hadrons. An intensive search for charm in other forms
immediately yielded other charmonium states and eventually led to new c-flavored
nonstrange mesons with compositions cu and cd, as well as ^-flavored strange mesons
of the cs variety. Charm spectroscopy flourished from the start and has continued to
yield a flood of information about systems containing the c quark.
New beyond charm have also come to light since 1977. Another vector
flavors
meson known as the T resonance was discovered in high-energy collisions as a narrow
pairs at E CM = 9.5 GeV. The circumstances of this
4
peak in the yield of fi jti

discovery were just like those associated with the J/\p meson. The T meson was
therefore interpreted as a bb bound system, in which a new quark b was introduced,
with Q/e = - \ to fit the analysis of the resonance and to suit the analogy with
,

charm. A whole family of similarly defined T states has subsequently been observed.
One of these recent discoveries was found at an energy above the threshold for decay
into pairs of b- and ^-flavored hadrons. Yet another quark t, with Q/e = j, has also
been postulated to act as a partner for b. Direct experimental evidence for the
existence of this new flavor is anticipated at higher energy.
High-energy electron-positron colliding beams are ideal for the production of such
uncharged vector mesons as J/\p and T. These resonances make their appearance in
processes of the form
+ -*
e~ 4- e hadrons
+
and are seen as conspicuous features of the total cross section a(e~e ).

Electron -positron storage rings have been constructed at several laboratories around
the world to serve as factories for c- and ^-flavored particles. Observations of cc and bb
systems are presented convincingly in the ratio of cross sections

+
a(e e )
R =-T^-+ -* ^TT> (
16 - 28 )
aye n e fi )

plotted as a function of £CM , the e'e

+
CM energy. Figure 16-32 shows a graph of R,
indicating the 1 charmonium states and the T family at their various resonance
energies. The // system is expected to occur on such a graph at higher values of the
energy.
 16-14 The Eleclroweak Interaction 881

Figure 16-32

Ratio of cross sections o(e~e + )/o(e ~ + -+ /n^/x

+
) versus e~
+
CM energy. The two
charmonium states and the first three T states are off scale. The fourth T decays into b- and
b- flavored hadrons.
tins)
J/<i, i//(3685) n = 1234

R 4

20 25
(GeV)

The t and b quarks are designed to contribute t and b flavors in the composition of
whole collections of new hadrons. Quantum numbers and conserved quantities have to
be defined accordingly, extending the lists given in Table 16-2. The new quantum
numbers associated with / and b have been given the names truth and beauty. These
two new species of flavor terminate a succession of three pairwise generations of
quarks,

(«,</), (e,s), and (t,b),

and complete the parallel with the already-introduced three generations of leptons

(<">",)» (M~,*v), and (t-,pt ).

We note that the pairs of Q/e values are (f ,

— 3) for the quarks and ( — 1,0) for the
leptons. The symmetry between these two groups of particles is a striking coincidence
to be explored later on.

16-14 The Eleclroweak Interaction

Several areas of are shared by the electromagnetic and weak

common ground
interactions. We have learned that both types of phenomena can be treated theoreti-
cally in terms of the fundamental couplings of currents and quanta. The hadrons

participate in these processes through the electromagnetic and weak currents that
represent the flavor transitions of quarks. A similar picture based on currents has also
been presented earlier regarding the behavior of the leptons. The likenesses between
the treatments of the two interactions encourage the view that the two theories may
have a common origin in a single body of principles. The electromagnetic-to-weak
882 Elementary Particles

analogy has been entertained since the time of Fermi, and the possibility of a single
theory has evolved during the intervening decades.
Wehave also noted that the electromagnetic and weak interactions are very
and range. Electrodynamics describes a force of infinite
different as to their strength
range mediated by the exchange of zero-mass photons, while the weak force is known
to have an extremely short range so that the exchanged weak quanta are presumably
very massive. It would seem that th^ analogy between the two interactions should
break down over these rather substantive distinctions. Despite the enormous disparity
in strength and range, it has been shown that the two forces actually do represent
different manifestations of a single unified interaction. The electroweak theory that draws
together the electromagnetic and weak interactions is in agreement with all experi-
mental tests and is currently regarded as an established theory. This unification of
forces may be compared to the outcome of Maxwell's theory, in which the principles

of electricity and magnetism are united in a single formalism. New physical laws are
at work in the unified theory. These ideas have had a revolutionary influence on all
recent developments in particle physics.
Our presentation of the electroweak theory is divided into two parts. First, in this

section, we describe the structure of the theory and examine the observable conse-
quences in the interactions of quarks, leptons, and quanta. We continue to rely on
Feynman diagrams to illustrate our descriptive approach. Later, in Section 16-16, we
turn to the deeper questions of principle that underlie the whole successful formula-
tion.

The unified theory of the electroweak interaction is a renormalizable quantum field

theory in which the interactions of quarks and leptons are mediated by a unified
electroweak field having four charge-specific degrees of freedom. Four different
charge-bearing quanta are associated with this generalized field. The quanta

W\ W°, W , and B°

are required to be massless particles by the guiding principle of the theory, just as the
photon is required to be massless in the theory of the electromagnetic interaction. Two
of thesequanta become the expected and W~ W weak interaction. The
of the
remaining two are neutral and can therefore be mixed in various combined states. The

couplings to the electromagnetic currents of quarks and leptons select a particular

combination of B" and W {)
for identification as the photon:

y = fl°cos W + W°sm 6W . (16-29)

This relation has the form of a rotation defined by the weak mixing angle 8W a ,

parameter of the theory to be determined by experiment. Another rotated combina-

tion of B° and W°, orthogonal to y, identifies another neutral entity:

Z = - 5°sin 6W + W°cos $w . (16-30)

This expression defines an independent neutral weak quantum and leads to effects not
anticipated by any previous discoveries in weak interaction phenomenology.
One of the two vital ingredients of the electroweak theory is the principle by which
the quanta are introduced originally as massless particles. The other is a mechanism
by which the weak quanta W +
, W~ , and Z acquire mass while the electromagnetic

quantum y retains its requisite zero-mass property. The guiding principle is known as
 1614 The Electroweak Interaction 883

gauge symmetry, and the mass-acquisition mechanism is called spontaneous symmetry

breaking. The renormalizability of the theory is achieved through the one ingredient,
and the short range of the weak force is obtained through the other.
The predictions of this remarkable theory include a relation between the masses of
the charged and neutral weak quanta,

m if
cos0„,, (16-31)
,n z

and a relation between the fine structure constant a = e

2
/4Tre hc and the Fermi
constant GF of Section 16-7:

a = — —-j(m w
77 (he)
c
2
an6w ) . (16-32)

These formulas involve the weak mixing angle, a quantity determined by the analysis
of a variety of weak processes. Equation (16-32) can be used to predict the mass of
W± in terms of the known quantities a and G F and , Equation (16-31) can then be
applied to predict a result for the mass of Z. Both of these masses are expected to be
quite large, of order 100 GeV/c 2 , in keeping with the very short range of the weak
force. Equation (16-32) is especially interesting in this regard because the relation
connects the strengths of the two unified interactions. The dependence on the large
mass mw demonstrates clearly how the extremely small size of GF is associated with
the extremely short range of the weak interaction.
The electroweak theory includes electrodynamics. Hence, all the predicted cou-
plings between the photon and the electromagnetic currents of the fundamental
charged particles have their usual form. The theory also describes all the usual
charge-changing weak transitions in terms of the anticipated couplings of W± to the
various charge-changing currents. These charged currents are shown in Figure 16-33.
Note that the quark flavor transitions involve the modified quarks a", s', and b' . These

Figure 16-33

Coupling of W~ to the weak charged currents of quarks and leptons.

u - c - t
 .

884 Elementary Particles

Figure 16-34

Weak neutral currents of quarks and leptons coupled to Z.

flavors with Q/e = — \ are combinations of d, s, and b, obtained by making

rotations like the ones introduced in Section 16-13. (An extended Cabibbo-rotation
scheme is presently in use to accommodate the three generations of quarks. This new
flavor-mixing procedure replaces the single Cabibbo angle 9 of Section 16-13 by four
different angles. One of the four plays a direct role in the parametrization of
CP- violation.)

Figure 16-35

Neutrino scattering processes involving contributions due to weak neutral currents. A charged-
current term also occurs in vr e —* ve e~, but not in v e~ —* v e~

vP + e — v„ + e

vu + P "*
"u
+ P
 18-14 The Electroweak Interaction 885

The theory also predicts a new weak phenomenon brought about by the presence
of the neutral quantum Z. This fourth quantum in the theory couples to charge-conserv-
ing weak currents, also called weak neutral currents, as illustrated in Figure 16-34. An
entire body of new weak processes is introduced by this piece of the unified interac-
tion, with probabilities determined by the unambiguous predictions of the unified
theory. The couplings to the weak neutral currents are distinct from electromagnetic
couplings, which also involve charge-conserving currents, because of the parity-violat-
ing effects in the weak interaction. Examples of such neutral-current phenomena are
shown in Figure 16-35.
Several different ideas had to be brought together by several people to build this
intricate theory. Yang conceived the guiding principle, and Schwinger proposed the
unification concept, both in the 1950s. The fourfold structure of the unified electro-
weak was devised by Glashow in 1961. The mechanism by which the weak
field

quanta acquired their mass was incorporated in the theory by S. Weinberg in 1967,
and a very similar model was put forward a year later by A. Salam. Little attention
was given to these contributions at first, because the crucial renormalizability of the
theory was regarded as doubtful. Skepticism gave way to enthusiasm in 1971,
however, when a proof of this property was carried out by G. 't Hooft. The theory
received support from experiment in 1973, when neutral currents were discovered in
neutrino reactions of the type

\+P v + hadrons.

Further confirmation of a piece of the theory came in 1974 with the discovery of
charm in the J/4> resonance.
The keystones of the electroweak theory, the new quanta W± and Z, were not
discovered until 1983. An accelerator with especially high energy had to be con-
structed to create these massive particles, and the CERN proton-antiproton collider
was dedicated to that purpose. The essential innovation in the design of the collider
was a technique developed by S. van der Meer for accelerating and storing antipro-
tons at very high energy. Collisions were achieved between 270 GeV protons and 270
GeV antiprotons, and evidence of the weak quanta was found, in experiments
conducted by C. Rubbia and others. The basic production mechanism was interpreted
to be quark-antiquark annihilation, as illustrated in Figure 16-36. The detection of

Figure 16-36

Production of weak quanta in proton-antiproton collisions.

e "e

Hadrons Hadrons
886 Elementary Particles

the particles, first W and then Z, was performed through the materialization of the
massive quanta into pairs of leptons. Quoted values for the two masses have been
given as

mw = 80.8 GeV A 2 and mz = 92.9 GeV/c 2 ,

in striking agreement with the predictions of the theory.

Example

The experimental value of sin~#,„ is around 0.23, and so W is about 29°. We can
use this result to make predictions for m w and m z . Let us rewrite Equation
(16-32) as

17 (X

m w c 2 s\r\6,., = 3 '

}/2G F/(hc)

and let us recall from Section 16-7 the expression for GF in terms of the proton
mass:

GF 1.03 X 10
5

o\2

The combination of formulas results in the following prediction:

m^^sind,,, = i/
1
—p=r-. —VI 37 —— Mx
5 p
2

i/2(1.03 x \0 )

= (39.7)(0.938GeV) = 37.2 GeV.

The masses of the weak quanta are then found to be

37.2 GeV A 2
in
ir 78 GeV A'
sin 29°

and

78 GeV A''
90 GeVA 2
,

cos 29°

where the second prediction is based on Equation (16-31). Both results are in
agreement with the findings from CERN.

16-15 Color and the Strong Interaction

Two immediate questions confront us when we adopt a theory of hadrons based on

the quark hypothesis. The quarks are taken to be real constituents, permanently
bound in hadronic states and not observed as liberated particles. If we accept this
view, we must ask how the mechanism of permanent confinement works. The quarks are
also known to have spin- ~ properties. If we accept the fact that they behave as
 16- 15 Color and the Strong Interaction 887

fermions, we must ask how fermion antisymmetry is obeyed in the formation of baryons.
These questions lead us to the concept of color and to the theory of the strong
interaction where color plays the main role. (In this context color is a fanciful name
for a new quantum number. The concept is unrelated to any attribute affecting our
visual senses.) The fundamental treatment of the strong interaction involves the
dynamics of color in the binding of quarks. Accordingly, the theory is called quantum
chromodynamics. Strong processes occur among the observable hadrons as outward
manifestations of this basic interaction of confined constituents.
Let us begin with the issue of fermion antisymmetry and illustrate the problem by
referring to the hadron A++ . Recall from Section 16-12 that one of the states of this
spin- 1 particle is described as

A + + = uuul T T,

where each u quark is in an s state with spin up. The description in its present form
violates the Pauli principle, because both the space and spin factors in the wave
function are symmetric under the exchange of quark variables. Color is introduced at
this point to contribute an additional quark degree of freedom. If we assign a different
color to each quark, we
see that the violation of the exclusion principle disappears
++
since no two of the quarks in A are in the same flavor-space-spin-color state. We
need three different values for the color quantum number to accomplish this trick. (In

fact, there are three colors of quarks in all, for a variety of reasons. One of the pieces
of pertinent information from experiment is discussed below.) The quark colors are
conventionally designated by means of the indices R, and B, using notation Y,
inspired by the three primary colors red, yellow, and blue. We assume that this same
threefold multiplicity is attached to every quark flavor, so that we have color triplets of
quarks (u R u Y u B ), (d R d y d B ), (sR s Y sB ), and so on.
, , , , , ,

We can now return to the A + + problem and construct an eigenfunction for three u
quarks. The desired expression must be exchange symmetric in space and spin, and
exchange antisymmetric in color. The Slater determinant of Section 9-5 can be
adapted to these properties by writing

u R {\) u Y {\) u B (\)

u R (2) u Y {2) u B (2) (16-33)

u R (3) u y (3) u B (3)

Six terms are written in Each is a product of three quark factors,

this eigenfunction.

whose flavor and color are explicit, and whose estate and spin-up specifications are
implicit in the quark labels (1), (2), and (3). We note that the expression remains
unchanged when the color indices are rotated through the cycle

because of the cyclic symmetry of the determinant. The color portion of the eigenfunc-
tion is called a singlet since its unique form is maintained under such rotations. In this
respect color acts like charge and combines in a color-neutral system to make a hadron.
Color-singlet states are assumed for all hadrons. This stipulation prevents the added
888 Elementary Particles

color degree of freedom from causing an undesired proliferation in the number of

observable hadronic states. The color-singlet property is ensured for baryons if the
three flavors are taken with colors R, Y, and B in equal parts, as in Equation (16-33).
Color-singlet mesons also call for equal-parts admixtures of color. For instance, the
color composition of the m+ state ud is expressed as

+
?7 = -j^{u R d R + u ydy + u B d B ), (16-34)

where the flavors u and d refer to J-state constituents and where the usual s = spin
eigenf unction (1/ y2)(T i ~~ IT) is implied. Note that the baryon state in Equation
(16-33) is antisymmetric under exchange of any pair of color indices and that the meson
state in Equation (16-34) issymmetric under the same operation. We obtain color-
singlet expressions for all known baryons and mesons by adhering throughout to
color-antisymmetric and color-symmetric constructions in the two situations.
Experimental evidence for three colors of quarks is found in electron-positron
annihilation into hadrons. We have already introduced the cross-section ratio R in
Equation (16-28) and Figure 16-32 to express the energy dependence of this process
+ +
relative to the energy dependence of e~e -* n~fi The quark model takes the .

+— + —
reaction e~e * hadrons through the intermediate step e~ e > qq and lets the qq
pairs materialize into the various hadronic final states. Figure 16-37 shows this
hadronization mechanism in a schematic derivation of R. The different quark-anti-
quark pairs uu,dd, ss,.. have successive thresholds in the variable ECM Each pair
. .

contributes to the numerator of R with a factor of 3, owing to the multiplicity of

colors for each quark. We observe that, if the e~e* collision energy is far enough
above the threshold for a given qq, then the comparison of the processes

e + e
+ —> q + q and e~ + e
+ — > jx + /x
+

is rather insensitive to the difference in mass between q and ju. The energy dependence
for e e '—> qq therefore becomes the same as the energy dependence for e~ e + —> ju~/x + ,

and so the particular qq contribution to R becomes independent of ECM in this

+
regime. If the quarks are point-like, as the muons are, then the qq and fi~ jJl processes
differ only through the quark charge Q_ . This charge affects the coupling of the quark
current to the virtual photon in the manner indicated in the figure. We can
summarize these arguments in the derivation of R by writing

,_ M sElxf^OI 2

in 2

*- ,."l. r
o(e e -> fi fi )
,;
x (/i
| H ,e e
,*
)\
-3 E- q
\ e
^

j
<'"»>

The amplitudes in the intermediate step correspond to the diagrammatic model shown
in the figure. This a succession of rising plateaus as each qq threshold is
result predicts

exceeded. Our expectations are illustrated in the lower part of Figure 16-37. The
actual behavior of R in Figure 16-32 shows good agreement with the stepwise shape of
this prediction. We note particularly that the factor of 3 arising from color is needed
to make the agreement possible.
If we compare Figures 16-32 and 16-37 more closely, we see that R exhibits sharp
deviations from Equation (16-35) wherever the successive qq contributions have their
thresholds. Thus, as ECM decreases, the T family of bb states appears at the onset of
 16-15 Color and the Strong Interaction 889

Figure 16-37

Quark model for the ratio R in Figure 16-32. Quarks and muons couple to the virtual photon
with charges Q^ and e. Quarks contribute to the sum over q as indicated in the graph of R.

Hadrons

3^
Q

11
q - u, d, s, c, b 10 3
q - u, d, s, c 3

q = u, d, s

±
10 15 20 25 iO 35
Em (GeV)

the bb term in R, and then the cc charmonium states occur near the lower cc

threshold. We can estimate the masses of the constituent b and c quarks on these
grounds to be around 5 and 1.5 GeV/V 2
respectively. It is obvious that the succeeding
,

quarks s, d, and u are much lighter than b and c. It should also be noted that the
whole complex issue of quark masses is subject to interpretation, since the quarks are
not observed as free particles.
The original problem of fermion antisymmetry was resolved in the 1960s with the
introduction of the color concept by O. W. Greenberg, and by M.-Y. Han. and Y.
Nambu. Color dynamics was promoted a decade later as the basis for the theory of the
strong interaction by Weinberg and Gell-Mann, among others.
The strong interaction accounts for the binding of quarks and antiquaries to make
mesons and the binding of three quarks to make baryons. These bound systems of
color-bearing constituents are formed dynamically in color-singlet states, as noted
above. Quantum chromodynamics is the renormalizable quantum field theory that
promises to explain such phenomena. We devote the rest of the section to a purely
descriptive account of complex and compelling theory. The underlying principle
this

is again furnished by gauge symmetry, as in the theories of electromagnetism and

electroweak unification. The resulting formalism describes the strong interaction of
quarks in terms of transitions and couplings in the color degree of freedom of each
890 Elementary Particles

Figure 16-38

Quark and antiquark color transitions with the corresponding gluon couplings. The gluons
execute changes of color represented by pairs of color indices.

Y YR v u

Quark

V
YR

Antiquark

quark. These color-changing effects propagate from quark to quark by the transmis-
sion of the color-clwnging quanta that make up the mediating strong field. The quanta
are called gluons since they are devised to account for the binding of quarks. Figure
16-38 shows how the color quantum numbers behave when gluons are emitted in the
color transitions of quarks and antiquarks. Like the photon in quantum elec-
trodynamics, the gluons must occur in the theory as massless quanta because gauge
symmetry demands this property. Unlike the photon, however, the quanta of the
gluon field are not emitted from hadrons as observable particles because the gluons
carry color, and color is contrived to be permanently confined inside the hadrons.
Quantum chromodynamics and quantum electrodynamics, QCD and QED, are
analogous theories to the extent that their principles share gauge symmetry as a basic
concept. The gauge symmetries of the two theories are different, however, enabling the
gluons to have a certain very important feature not shared by the photon. Fundamen-
tal charged particles emit and absorb photons, and so the photon is said to be coupled
to the charge degree of freedom in QED. Since the photon carries no charge, there
exists no coupling of photons to photons. By analogy, gluons are coupled to the color
degree of freedom in QCD. The gluons must carry color since their couplings to
quarks are designed to cause quark color transitions. Consequently, gluons can
interact with gluons through their own intrinsic color quantum numbers. QCD
departs fundamentally from QED in this respect and leads to a remarkable property
called asymptotic freedom as a result. By virtue of the gluon-gluon interaction, the
coupling of color in QCD approaches zero strength at arbitrarily small distances or,
equivalently, at arbitrarily large momenta. This property has been established as a
rigorous consequence of the theory in investigations by D. J. Gross and F. Wilczek and
by H. D. Politzer.
The fact that the coupling of colors vanishes asymptotically at very short range
encourages the view that the same coupling may grow without bound for very long
range. This belief holds the key to the notion of color confinement, whereby free quarks
 1615 Color and the Strong Interaction 891

Figure 16-39

Meson photoproduction in a model of confined

quarks.

QQQ

I QQQ

are never seen, and observable hadrons are always found with quarks bound in
color-singlet (or zero-color) states. Quantum chromodynamics is a very complicated
relativistic quantum field theory. A few rigorous conclusions have been extracted from
the theory so far, while confinement remains the central problem to be solved.
Approximations to QCD and models of quark confinement have been rather
These studies support the idea that the configurational energy of a quark
successful.
system increases as the quarks separate. We illustrate the situation with the aid of
Figure 16-39 by showing the an incident y ray on a bound qqq baryon. The
effect of

added energy excites the quark system, producing a tendency toward quark sep-
aration, but no amount of additional energy can suffice to achieve quark liberation.
Instead, the added energy produces qq pairs in the strong gluon field so that the
originalbaryon fragments into a meson-baryon final state.
The ideas of QCD are readily translated for application to the phenomenology of
heavy-quark systems. The large masses of the constituent quarks allow the use of the
nonrelativistic Schrodinger equation in models based on a suitable central potential
energy. Expressions of the form

V{ r ) = + a. t r (16-36)
r
892 Elementary Particles

Figure 16-40.

Potential-energy model for heavy quark-antiquark binding and mass levels of charmonium.
The P !
states of the cc system exhibit spin-orbit splitting.

<:,
3

(0

Mass 1 12
(GeV/c 2 ) Spin and parity

can be applied to analyze the states of the cc charmonium system and the bb T system.
This type of potential energy function is sketched in Figure 16-40. The first term in V
mimics Coulomb attraction, in keeping with the analogy between QCD and QED,
and the second term supplies a linear barrier to simulate the effect of confinement.
The familiar angular momentum techniques of atomic physics hold for cc and bb.
Consequently, the resulting states are identifiable by the familiar spectroscopic
2
notation '
l
L. for total spin s, orbital angular momentum ( and total angular
,

momentum j. Thus, the having s = 1, c" = 0,

i
1 vector meson J/\p is a S l
cc state

and j = 1. The excited state i//(3685) occurs with the same set of vector-meson
quantum numbers. These two charmonium states are distinguished by their radial
quantum numbers n = and n = 2. A spectrum showing most of the known cc
1 states
and radiative transitions is included in Figure 16-40. A similar approach can be taken
with the bb system to analyze the family of T states.

The strong interaction, as just described, bears little resemblance to the old theory
which protons and neutrons are bound by the exchange of
of the nuclear force, in
mesons. This original problem in hadron physics is evidently not a fundamental
strong-interaction problem, simply because the interacting hadrons are not fundamen-
tal particles. Each hadron owes chromodynamics of permanently
its existence to the
confined quarks. The hadrons themselves are color-neutral, and so the exchange of
gluons does not occur from one hadron to another unless there is some overlap of the
hadronic quark systems. Hence, the fundamental strong interaction can become
operative in the force of attraction between nucleons at short range, but the complex
mechanism involves the participation of many quarks. This situation may be likened
 16- 1 6 Gauge Symmetries 893

to the relationshipbetween atoms and molecules. The fundamental electromagnetic

interaction accounts for the existence of atoms, and the van der Waals force then
binds the neutral atoms together at short range to form molecules. It is speculated that
a similarly successful theory of the nucleon-nucleon force can be derived from
quantum chromodynamics. It is also conceivable that the structure of nuclei may be
usefully cast in terms of quarks. Both of these objectives are currently under active
investigation.

Example

Equation (16-35) is easily applied to make predictions for the cross-section ratio
R. If we let the sum over q include uu, dd, and ss terms, we obtain

2
2
3E(^) -3[(t) + (-i)* + (-;f] = 2.

When the sum is extended to take in cc, and then bb, the results are

?(*)"-HS)'-?
and

*ffl"-H-;K-
These values of R are indicated on the right side of the graph in Figure 16-37.
We observe that each of the numbers would be reduced by one-third in the
absence of color.

16-16 Gauge Symmetries

Conservation laws and symmetry principles have appeared throughout the chapter
with the introduction of each new internal quantum number. Every case considered so
far has been an application of a global symmetry, where the relevant quantity obeys its
conservation law in a uniform manner over all space and for all time. To cite an
example, the conservation of isospin in strong reactions is attributed to a rotational
symmetry in which the rotations in the three-dimensional isospin space are indepen-
dent of locations in space and time. The conservation of charge in all reactions has
also been treated (so far) in terms of a similarly global symmetry principle. The
interactions of particles must be described in a way that accommodates all these
conserved quantities.
A more powerful concept emerges when a conserved quantity can be associated
with a local type of conservation law. Charge is a prime example of such a quantity.
A corresponding local symmetry then becomes operative and implements the conserva-
tion law in a manner that may vary from one space-time point to another. This
variability forces the system to include a mediating field whose response to the

symmetry operation is such as to compensate for the variation of the symmetry from
894 Elementary Particles

point to point. Thus, the required field enables the local symmetry to propagate
through the system and provide a mechanism for interaction. Gauge symmetry is

another name used to describe this behavior. The mediating field is referred to as a
gauge field, and the mediators There can be no limit
of the field are called gauge quanta.
to the space-time extent over which the symmetry may vary. Therefore, the
local
compensating property of the gauge field has to have infinite range, so that the gauge
quanta must be massless. A theory based on gauge symmetry is said to possess gauge
invanance, since observable properties of the system are not altered by the local
symmetry operation.
A gauge-invariant theory defines an interacting system. The interaction medium is
furnished by the gauge field, and the structure of the interaction is dictated by the
nature of the underlying gauge symmetry. The resulting relativistic quantum field

theory ultimately proves to be renormalizable by virtue of the constraints imposed by

the local symmetry. Theories of the fundamental interactions of particles are con-
structed from gauge principles in order to take advantage of this crucial property. The
electromagnetic, electroweak, and strong interactions are cases in point. We have
now we wish to devote an entire
already described the highlights of these theories, and
section to an explanation of the general principles.
Let us examine electrodynamics as the prototype of a gauge theory. Electromag-
netism is chosen because the gauge behavior of the theory is particularly straightfor-
ward to understand. We begin with the classical fields, and then we confine our
attention to a nonrelativistic particle when we extend the problem to quantum
mechanics.
Classical electromagnetic theory is completely contained in Maxwell's equations for
the coupled E and B fields:

V E • = — (Coulomb's law) (l6-37a)

o

<9E
V X B — — —^
1

= n J (Ampere's law and displacement current) (l6-37b)

7Tt
V X E + —- = (Faraday's law) (l6-37c)
dt

V*B = (absence of magnetic monopoles) (l6-37d)

We consider fields in vacuum charge and current densities p and J.

in the presence of

These quantities satisfy a local charge-current conservation law, obtained by differen-

tiating Equations (16-37a) and (16-37b) as follows:

——
8 1 dp
V E= •

dt e dt

and

V •
( V X B) -
1

—V
c
• —
dE
at
= ju V •
J.

When we use

V *(V X B) = and — = jii e ,

 1 6- 1 6 Gauge Symmetries 895

we obtain the desired local relation between charge and current

dp
—
dt
+ V'J = 0. (16-38)

Note that the result hinges on the presence of Maxwell's displacement current, given
by the dE/dt term added to Ampere's law. We recall that the prediction of
electromagnetic waves also follows because of this contribution.
The last two of Maxwell's equations involve no source terms and may therefore be
construed as kinematical relations among the various field components. We can use
vectorand scalar potentials to convey the effects of these formulas and thereby simplify
the whole system of coupled equations. A vector potential A is introduced by setting

B = V X A, (16-39)

so that Equation (16-37d) is automatically satisfied. A scalar potential 4> is then

employed to define

E= -V4>- —
dA
dt
(16-40)

so that Equation (16-37c) is also secured. This second result follows with the aid of the
identity

v x (v<?>) o.

We obtain a reduced, but still coupled, set of differential equations for A and <£ when
we return to the first two of Maxwell's equations and insert Equations (16-39) and
(16-40).
The potentials are not uniquely defined by this procedure. In fact, this is the place
where gauge symmetry makes its first appearance. We observe that B is not changed
in Equation (16-39) if we replace A by

A' = A + VA, (16-41)

and that E is not changed in Equation (16-40) if we also replace <f>

by

dA
$' = <}>-—. (16-42)
dt

The new quantity A(r, t) is introduced as an arbitrary scalar function of space and
time in the two expressions. These assertions hold because

V X A' = V X A
and

- V¥ - —
dA'
= - v<J> + V —
dA
- - - VA = - V* -
-
dA d
-
dA

The substitutions A -> A' and <J>

-» <£' in Equations (16-41) and (16-42) specify the
gauge-transformation properties of the electromagnetic potentials. We see that these

operations have no effect on the observable fields E and B, and we conclude that
896 Elementary Particles

classical electromagnetic theory is a gauge-invariant formalism. It is possible to exploit

this freedom in the definition of the potentials and generate uncoupled (or otherwise
simplified) differential equations for the determination of A and <$>.

These formal characteristics of the electromagnetic potentials takeon greater

significance when the quantum behavior of a charged particle examined in a
is

gauge-invariant theory. Let us focus on the nonrelativistic problem and start with the
Schrodinger equation for a free particle:

— 1

Zm\
-V
/ h

i
\

J
2

*=
8
a-77 *•
dt
(16-43)

The phase of the complex-valued wave function ^(r, ) is not a measurable quantity. /

We may therefore argue that the description of the particle cannot be affected if ^ is
replaced by a phase-altered wave function of the form

ia
¥'(r, = e *(r,t).

It is easy to see that ^' also obeys Equation (16-43), provided the phase a is a
constant. Let us suppose, however, that the phase is allowed to vary with r and t and
that the observable predictions of the theory are required to remain unchanged. In
this case the differential operators act on a(r, t) as well as ^, so that ^' no longer
satisfies the given free-particle equation. We express such a variable-phase alteration
of ^ as

*'(r,0 =««i A r "'>/*¥(r,0, <

(16-44)

where A is an arbitrary function and Q is a parameter to be identified in due course.

The prescription defines a gauge transformation of the wave function and creates
differences in the phase of ^f between different locations in space and time. We can

prevent these arbitrary effects from becoming observable by introducing the electro-
magnetic potentials to serve as gauge fields. If A in Equation (16-44) is taken to be the
same arbitrary function as in Equations (16-41) and (16-42), the gauge transformation
of A and <$> exactly compensates for the arbitrary phase variation of ty. The resulting
formalism for ty, A, and <j> therefore constitutes a gauge-invariant theory.
We have to modify the free-particle equation to accomplish these ends. If the
replacements

h h d d

ii
-V -> -V - 0A and ih—
at
-» ih —
dt
- Q<p (16-45)

are made in Equation (16-43), the Schrodinger equation becomes

i(7 v -« A
)
*"(^" a*)*- (1M6)

We now wish to demonstrate how this approach gives a gauge-invariant procedure for
the determination of ty. The gauge-transformed version of the left side of Equation
 16-16 Gauge Symmetries 897

(16-46) is analyzed in detail as follows:

-V - £A' ¥' = -V - Q(A + vA)| V - £(A + VA ,.W**

h
-V - Q(A + VA)

,<W*(Q vA )^ + e
,-

ft A/«
-V - Q(A + VA) *

- Q(A + vA) 'QA/A -V -

-V •
e QA *

= ,'QA/A
(QVA). -v - QaW
+ ,«W» -V - Q(A + VA) (DA ¥

-v - qa] 9.

The analysis of the right side of the equation proceeds along similar lines:

^'QA/A^
a--a*r|*-.
/ 3A
3A \ <9
/ dA \
M'

= ^'^ A/A ft £<M*.

Thus, the structure of Equation (16-46) is such that an arbitrary phase variation of ^
is reconciled by the corresponding gauge behavior of A and The phase-altering <J>.

factor therefore passes through all the operations in the equation, so that 4'' satisfies

the gauge-transformed version of the original equation for ty.

The interpretation of the parameter () becomes apparent when Equation (16-46) is

rewritten:

V - QA ^ \
+ Q.^ = ih — *. (16-47)
2m\ i I at

The familiar features of the Schrodinger equation for an interacting particle appear in
this result, as the second term on the left evidently contains a potential energy of the
form
V=Q<$>.

If we let be an electrostatic potential, we recognize Q to be the

the scalar potential <p

charge of the particle be the usual Coulomb interaction. Note that the term
and V to

Q$ty in the equation represents a coupling in which the particle and the gauge field
interact through the coupling parameter (). The remarkable conclusion to draw from
898 Elementary Particles

this demonstration is that the requirement of gauge invariance dictates both the
existence and the form of the interaction. Gauge symmetry operates in exactly the
same way in conjunction with the Dirac equation to generate the electromagnetic
interaction for a relativistic spin-^ charged particle. Quantum electrodynamics is the
resulting gauge-invariant theory.
Quantum chromodynamics is obtained as the theory of the strong interaction
through a different application of gauge invariance. We again consider local phase
variations in the spirit of Equation (16-44), and we also let the gauge transformations
act on the colors of quarks to produce changes in those degrees of freedom. There are
eight distinct color alterations possible among the three quark colors. Consequently,
eight gauge fields are needed, with gauge behavior different from Equations (16-41)
and ( 16-42), in order to compensate for the arbitrary phase adjustments of the quarks.
The color-changing aspects of the quark transformations are fundamental to the
gauge symmetry of QCD. These features set this theory apart from the simpler gauge
symmetry of QED. The result is a vastly more complex structure for the description of
the strong interaction. Eight color-changing zero-mass gluon quanta are associated
with the eight gauge fields. These gluons couple to the colors of quarks, and also to the
colors carried by other gluons, so that the gauge-invariant theory describes
gluon -quark and also gluon-gluon interactions. The latter situation has no analogue
in QED. The gluon-gluon interaction is the source of the property of asymptotic
freedom for gluon couplings at short range and is a crucial ingredient in the
mysterious property of color confinement. The gluon-gluon interaction comes about
because the various transformations of the internal degrees of freedom are not
commutative operations. Gauge theories based on noncommuting local variations of
phase are named generically after Yang and R. L. Mills, the first investigators to
make such an extension of gauge symmetry.
While one type of Yang-Mills theory implements a particular gauge symmetry
among the colors of quarks, another type invokes a different set of gauge principles for
the behavior of quark flavors. We are led in the first case to the theory of the strong
interaction, as just discussed, and in the second case to the theory of electroweak
unification. This second application of noncommutative gauge symmetry pertains to
local phase variations in which the noncommuting transformations occur within the
doublets of quark flavors

u t

a" s' V

and also within the doublets of leptons

e T

(Recall that the quark entries a", s', and b' represent rotated combinations of d, s,

and b in the generalized Cabibbo-rotation scheme for three generations of quarks. We

have already referred to this scheme in our discussion of Figure 16-33.) It is easy to see
that four different flavor transformations are called for and that the four required
gauge fields correspond to the previously introduced electroweak quanta. We illustrate
 16-16 Gauge Symmetries 899

this remark by itemizing the four types of quark and lepton transitions as follows:

u -» u + y/Z <?"-> e~ + y/Z

u -* d' + W+ e~~* ve + W~
d' -> u + W~ ve -» e~+ W+
d' -» d' + y/Z ve -> vt + Z

(We indicate the alternative emission of y or Z by the notation y/Z.)

The historical obstacle to a successful weak interaction theory looms up at this
juncture. Gauge symmetry demands zero-mass quanta and produces a renormalizable
formalism, while phenomenology requires massive quanta, in apparent conflict with
renormalizability. The impasse is resolved ingeniously by adopting gauge symmetry as
the underlying dynamical principle and by assuming that the ground state of the
theory does not possess the adopted symmetry. The procedure is called the spontaneous
breakdown of gauge invariance. Remarkably, this breaking of the local symmetry
leaves the renormalizability of the gauge-invariant theory intact. The miracle con-
tinues, as the spontaneous breakdown of gauge symmetry causes the appropriate
gauge quanta to acquire mass. This central ingredient of the theory comes into play
through the so-called Higgs mechanism, a phenomenon discovered by several people
including (and named after) P. W. Higgs. The credits for assembling these pieces of
the puzzle have already been given in Section 16-14 to Glashow, Weinberg, Salam,
and 't Hooft.
The application of Yang-Mills theory to t leclioweak unification is too involved to
describe any further in this text. Let us be content to illustrate spontaneous symmetry
breaking in the context of a simpler gauge symmetry instead. We reconsider local
phase transformations of the sort defined in Equation (16-44) for this purpose.
Let us suppose that the system includes a relativistic charged scalar particle whose
wave function is 3>(r, t). In the case of a free particle, $ obeys the Klein-Gordon
equation
2 2
h \ 1 d^
-V $ - — #— /

$ = -m 2c 2 <&, (16-48)

as in Equation (16-3). We want $ to be subject to local phase variations of the form

*(r,0 -> $'(r,<) = ^ A < r

'"/*4>(r ,
/)

Gauge invariance requires that we again incorporate the gauge fields A and $ and
assume the gauge behavior given in Equations (16-41) and (16-42). The interaction of
the particle with A and is then described by the modified Klein-Gordon equation
<f>

-V - QA| $ - — ih— - Q_4>\ $ = -m 2c 2 <$ (16-49)

when the replacements in Equations (16-45) are made. If we define the real and
imaginary parts of $ by writing

= $, + z0 2 ,

we see that <!>, and 4>

2
satisfy Equation (16-49) independently.
900 Elementary Particles

Figure 16-41

Mass-squared paraboloids m 2 (<5> <I> 2 ) i

,
= fi
2
+ \(<&
2
+ $|) Ior p
2
positive and negative. The
parameter X is taken to be positive.

The mechanism for breaking gauge invariance can be introduced formally by

letting the mass parameter m contain a contribution proportional to the probability
density 4>*<J>:

,2 _
= „22
/i + A<&*0

hi

2
(<D,,<I>,) = m2 + a(<I>
2
+ <I>
2
). (16-50)

This hypothesis injects an ingredient of nonlinear behavior that couples the de-
termination of <J>, and <b 2 through Equation (16-49). We observe that the expression
4>*<I> is independent of the phase of and is therefore left unchanged by local phase
variations. Consequently, w 2 ($,, <I>
2 ) is a gauge-invariant quantity so that the incor-
poration of ml in Equation (16-49) does not conflict with the governing principle of
gauge symmetry. Figure 16-41 shows two versions of the paraboloidal surface given by
m as a function of <!>, and <&.,. We are interested in the lowest energy state of the
system, and we suppose that this state occurs for the smallest possible value of the
mass m. If we take the parameter ju 2 to be positive, we find

"'. /la when O, = $ 2 = 0.

We note, however, that smaller values of m are obtained if )n

2
is allowed to be negative.

The figure tells us that the least nonnegative result for rn

2
is given by m = 0, when «t>,

and <&
2
lie anywhere on the circle

$2 + $.
2
— with jli
2
< 0. (16-51)
A

This conclusion determines only the modulus of $, while the phase of $ is left

unspecified in accordance with gauge symmetry. If we now select a particular for

 16-16 Gauge Symmetries 901

the ground state of the system, such as

*.= $., = 0, (16-52)

A

we see that the choice immediately breaks the

symmetry by singling out a specific phase
in the solution. This spontaneous breakdown of gauge invariance affects the range of
the gauge fields. The broken symmetry manifests itself through finite-range potentials
A and 4> whose quanta are no longer massless. The Higgs mechanism operates in
similar fashion to give mass to the weak quanta ± W
and Z in the electroweak theory.
The mechanism is more complicated since the electroweak gauge transformations are
more intricate than the simple phase variation considered here.
Spontaneous symmetry breaking is not an uncommon phenomenon in nature. The
example most often cited is that of a ferromagnetic medium of infinite extent. Such a
system has an underlying rotational symmetry in three-dimensional space and presents
a ground state in which all spins are aligned in the same direction. The choice of
direction is arbitrary since the rotational symmetry allows a continuous range of
possible alignments. This symmetry is broken spontaneously when a particular
alignment of spins is chosen. The following example is taken from nonrelativistic
classical mechanics and gives an even simpler illustration.

Example

Spontaneous breakdown does not always have to be associated with gauge

invariance, or with other forms of continuous symmetry. Let us consider as an
alternative a classical mass-on-a-spriug in one-dimensional motion, with poten-
tial energy

k X
V(x)
V
= -x 2 + -x 4 .

'
2 4

This expression includes the usual harmonic term with spring constant k and an
additional anharmonic contribution with positive parameter X. The system is in
stable equilibrium at x = 0, provided k is positive. In general, we find a

vanishing force wherever the potential energy has zero slope:

dV
= F(x) = - —
ax
= ~(kx + Xx 3 ) = -x(k + Xx 2 ).

The x = solution does not correspond to stable equilibrium if we allow k to be

negative. In this case, stability occurs at the points

+x ,
where x

Figure 16-42 shows the shape of V(x) in the two cases. We expect to find
symmetric stable minima on either side of x = for k < 0, because V{ x ) is

symmetric under the parity operation x -* -x. We break this symmetry sponta-
neously when we choose, say, x = +x to be the position of equilibrium for
902 Elementary Particles

Figure 16-42

Anharmonic potential energy V(x) = {k/2)x 1 + (A/4);c

4
for k positive and negative. The case
of negative k leads to a choice of stable minima at x = +x , where x = ^ — k/\ .

V(x) V(x)

k>0

small oscillations of the particle. Note that the broken symmetry is discrete, and
not continuous, in this illustration.

16-17 Grand Unification

Gauge theory has revolutionized our understanding of the elementary particles. The
general notion of local symmetry inspires a procedure that applies in different ways to
each of the fundamental forces. Quantum chromodynamics is generally accepted as
the theory of the strong interaction, and electroweak unification is established as the
proper framework for the electromagnetic and weak interactions. These two gauge
theories, taken together, comprise the so-called Standard Model for the behavior of
quarks and leptons. No experimental contradictions and no mathematical incon-
sistencies are known to be in conflict with this combined theory.
Despite its resounding success the Standard Model is not regarded as the ultimate
fundamental theory, for a variety of reasons. The electroweak portion of the model
does not meet all the qualifications of a truly unified theory, since the precise
unification of electromagnetic and weak interactions is not completely specified. We
can see this immediately by noting that the weak mixing angle 6W is left unpredicted.
In fact, the arbitrary separate treatment of the strong and electroweak theories
involves an excessive number of such free parameters. The presumption of a 1 : 3 ratio
between the charges of quarks and leptons is another arbitrary and, hence, unsatisfy-
ing feature of the overall theory. We should be able to eliminate these elements of
arbitrariness, and gain more predictive power, by turning to a higher level of
unification based on a greater degree of local symmetry. The higher symmetry would
make the unified theory simpler and would introduce constraints reducing the number
of free parameters. Grand unified theories are designed to accomplish these objectives.
The theories are so named because they embed the Standard Model in a single gauge
theory and thus serve to unify the strong, electromagnetic, and weak interactions. This
speculative notion has an obvious appeal as the next step to take toward an ultimate
theory.
The proposed schemes for grand unification differ as to their specific details. It is

not yet possible to say that any of these proposals has emerged as the obvious choice.
One of the leading candidates is the model developed in 1974 by Glashow and H. M.
Georgi. Their theory may not be correct in all its predictions; however, there is reason
 16-17 Grand Unification 903

Figure 16-43

Variation of coupling strength with energy scale. Strong, electromagnetic, and

weak interactions
approach equal strength at m x c 2 the unification scale.
,

10
1 1Q 15 10 20
Energy scale (GeV)

to believe that the ideas contained in this simplest of models are at least pointing in
the right direction.
Scales of distance and scales of energy are decisive considerations in grand unified
theories. The unification concept presumes the existence of a regime of the variables
where the forces of interest obey the assumed symmetry In this domain the
exactly.

forces are expected to exhibit no differences in strength. Such a situation can be

realized only if the strengths of the interactions are able to vary from one regime to
another. Renormalizability is the all-important property of a theory that enables us to
investigate this question. In the case of the electromagnetic and weak interactions, we
suppose that the two forces possess their unifying symmetry at very high energies, so
far beyond the range of practical experiment that the rest energies of the weak quanta
are negligible by comparison. These conditions are such that the effects of spontaneous
breakdown become relatively unimportant and the underlying electroweak gauge
symmetry becomes exact. Hypothetical experiments at the very large scales of energy
would be able to probe matter electromagnetically and weakly over distance scales
very much smaller than h/m w c, the range of the weak force. In these domains the
electromagnetic and weak interactions would appear to have the same (essentially
infinite) range, and the interacting particles would seem to be very much alike. We

then become aware of the large differences between the two forces via the breaking of
2
gauge symmetry when we descend in energy toward values comparable to m w c .

We illustrate this state of affairs in Figure 16-43 by showing the behavior of the

various coupling strengths as functions of the energy scale. The curves labeled W and
B refer to the couplings of the gauge-field quanta W+ ,
IV ,W~, and B°. (Recall that
the electromagnetic and neutral -weak interactions are associated with mixings of W°
and B° to form the observed quanta y and Z.) Note that the curve falls with W
increasing energy scale, so that the couplings W
diminish in strength at short range.

This property of asymptotic freedom is expected for these couplings because of the
noncommutative nature of the W gauge transformations. It is known that the W and
904 Elementary Particles

15
B curves intersect at a very high energy, of order 10 GeV, indicated on the graph by
the quantity m x c 2 The
. behavior of the strong gluon interaction is shown, with the
label G, in the same figure. This coupling also enjoys the property of asymptotic
freedom and must also fall with increasing energy scale. Remarkably, the G curve
merges with the W
and B curves in the vicinity of the same high energy determined
by rn x c 2 This coalescence of the three independent couplings is ideally suited for a
.

scheme of unification of the strong, electromagnetic, and weak interactions. The

parameter m x is called the unification mass in such a framework. The grand unified
theory would be seen as an exact symmetry for scales of energy beyond m x c 2 where ,

forces of equal strength act between seemingly similar particles. A single curve
describes the strength of this unified interaction, as indicated by the high-energy
portion of the graph sketched in the figure.
Grand unified theories treat quarks and lcptons as fundamentally similar particles
in theregime where the higher gauge symmetry is exact. The well-known distinctions
between these particles are then supposed to evolve at the lower energy scales, where
spontaneous breakdown of the symmetry takes effect. The unifying interaction em-
braces the familiar gluon, photon, and weak gauge couplings to quarks and leptons,
corresponding to the usual lower gauge symmetries with their associated strong,
electromagnetic, and weak gauge fields. New symmetries are also present in the
unified theory, because the higher level of unification includes operations that
transform quarks into leptons. Each of these transformations involves a certain change in

color and flavor, and each of the possibilities calls for the introduction of a new kind of
color-changing flavor-changing gauge quantum. The additional quanta give rise to
unanticipated interaction phenomena with couplings prescribed by the particular
higher gauge symmetry chosen for grand unification.
The model of Georgi and Glashow defines gauge transformations within the
following five- and ten-fold collections of colors, flavors, and leptonic quantum
numbers:

(u)r,y,b
{d)R,Y,B
(
u )r,Y, B
and (16-53)
(d)/i,Y,H
V
+
e

These assignments group the quarks u and d together with the leptons e~ and ve The .

other two generations of quarks and leptons participate in the model in similar
fashion. When we analyze the unified interaction for all possible quark-to-quark and
lepton-to-lepton transformations, we reproduce the usual strong, electromagnetic, and
weak gauge couplings. Some of these familiar couplings are shown in Figures 16-33
and 16-38. In addition, we also generate new classes of quark- to- lepton and quark-to-anti-
quark transformations. Some of these so-called leptoquark and diquark transitions are
illustrated in Figure 16-44. Note that the transformations occur with the emission or
absorption of color- and flavor-bearing quanta, represented by the symbols X and Y.
These quanta have Q/e values equal to \ and \, respectively. Note also that the
indicated transitions violate the conservation laws for baryon number and lepton
number. The new gauge quanta acquire very large masses via the spontaneous
breakdown of gauge symmetry. Thus, the mass of X is selected in Figure 16-43 to
2
specify the energy scale m x c above which the higher gauge symmetry becomes exact
,

and below which the effects of spontaneous breakdown become important. It is

 1617 Brand Unification 905

Figure 16-44

Couplings of X and Y gauge quanta in quark-lepton and quark-antiquark transitions

Changes of color are included in the diquark couplings.

d Y u UR dR
Leptoquark transitions Diquark transitions

least, that the value of m

noteworthy, to say the x should lie so many orders of
magnitude beyond m w the mass of the weak gauge quantum.
,

The embedding of the three familiar forces in a single unified interaction imposes
restrictions on several of the arbitrary features of the Standard Model. In particular,
the adoption of a single coupling strength for a single gauge symmetry fixes the
relative strengths for the couplings of the G, W, and B quanta. This determination of
couplings is made initially at energy scales beyond m x c The three curves in Figure
.

16-43 can then be followed below the unification scale to ascertain the strengths of the
couplings in the longer-range regime of current experiment. The same procedure can
be used to predict a value for the experimentally measurable weak mixing angle. In
the Georgi-Glashow model, the result is

2
sin 0„,= f (16-54)

at the unification scale. The value then evolves with the coupling strengths at longer
range to yield a prediction much closer to the experimental figure, sin 6W = 0.23.

The model and Glashow is an example of a grand unified theory in

of Georgi
which the charges of quarks and leptons are related. This relation provides an
argument for the quantization of electric charge. We note that the five- and ten-fold
assignments of quark and lepton quantum numbers have sums of charges given by

and

where the factors of 3 are due to the three colors. Both of these equalities imply the
relation

£,= i£,- (16-55)

In fact, the model goes on to explain why such sums of charges must equal zero for any
assignment of quark and lepton quantum numbers. We can use this property of the
model to argue that the charge relation is a necessary consequence of the higher level
of symmetry. One more element of arbitrariness in the Standard Model is thus
removed by the adoption of a unified interaction.
906 Elementary Particles

Figure 16-45

Diagrams that contribute to proton decay.

Nonconservation of baryon and lepton numbers is built into the Georgi-Glashow

+
theory. We can see this feature by noting that u, d, and u are assigned along with e

to the same collection of interconnected particle states. Similar constructions are found
in other models of grand unification. This provision leads us directly to the most
striking conclusion of the grand unified theories, the prediction of baryon- and
lepton-number violating nucleon decay. Figure 16-45 shows two of the possible mecha-
nisms for the proton decay mode
+
p -> 7T° + e .

We note that the diagrams contain the vertices from Figure 16-44, connected by the
exchange of the superheavy X and Y gauge quanta. A prediction can be made for
the proton lifetime t\, based on the specific choice of unification model. (Actually, the
prediction is somewhat blurred by uncertainties stemming from the parametrization of
the strong interaction and the treatment of the hadronic bound states.) The resulting
formula for 7\ depends sensitively on the unification mass mx . It is remarkable that
30
values for t. in excess of 10 years are obtainable for input selections of mx larger
14 2
than 10 GeV/c . A mean life in this range is amenable to experiment, and a
unification mass in the corresponding regime is in line with the scenario described in
Figure 16-43. This consistent set of circumstances is favorable for a decisive experi-
mental test of the ideas of grand unification.
The possible violation of baryon number is an intriguing development, particularly
in view of the comparable situation regarding the conservation of electric charge. We
have learned that charge conservation is associated with an exact gauge symmetry,
whose validity can be tested by setting very low experimental bounds on measure-
ments of the photon mass. Baryon number does not appear to have its origin in any
analogous unbroken gauge invariance, and so an exact conservation law would have
to correspond to an exact global symmetry. We are inclined to view this sort of
invariance as somewhat implausible, now that we have found a scheme, operative on
an extraordinarily small scale of distance, in which quarks and leptons look very much
alike. Baryon and lepton numbers cannot be regarded as sacred conserved quantities

in such a framework. We note in passing that the difference in quantum numbers

B — L continues to be conserved, at least in the context of the Georgi-Glashow
model.
Of course, the possible instability of the proton must ultimately be decided in the
laboratory. Several experiments have been mounted around the world to search for
 1617 Grand Unification 907

evidence of proton decay. Since the lifetime of an unstable proton must be very long,
an enormous sample of matter is needed to collect detectable numbers of decay events
in practical intervals of time. To illustrate, let us assume 10 30 nucleons in a ton of
material, and let us take the lifetime to be r
p
= 10
30
y. Under these conditions we
may one observable proton decay in the sample per year. One of the ongoing
find
experiments is located in an abandoned salt mine near Lake Erie. A volume of pure
water containing 8000 metric tons is monitored by phototubes to detect the light
radiated by the expected products of proton decay. The apparatus is buried deep
underground to reduce the detection of events due to cosmic-ray muons entering the
sample. Unfortunately, neutrinos cannot be eliminated, and their interactions can
simulate the desired p -> ir°e + events. In fact, the only decay candidates seen so far
are attributable to this source of background. The experiment to date has set a lower
+
limit for the partial mean mode greater than 10 32 years. This result is
life in the TT°e
at a factor of 10 larger than any of the predictions based on the simplest
least
Georgi-Glashow model.
Grand unified models belong to a general class of spontaneously broken gauge
theories that predict the existence of magnetic monopoles. These objects have been found
mathematically among the solutions of the classical field equations of the theory. The
prediction gives an enormous estimate for the mass, of order 10 16 GeV/c 2 and ,

provides a unique relation between the magnetic pole strength and the electric charge
of the particle. Such objects seem to occur very seldom, if at all, in the real world.
Only a single candidate has been seen in the laboratory, in an experiment performed
by B.Cabrera in 1982. Since their incidence is so rare, it is incumbent on the theory

that some reason be offered for their suppression

Proton decays also happen very infrequently (if indeed they happen at all), and so
the new baryon-nonconserving interaction contained in thegrand unified theories
must be extremely weak. Such 5-violating phenomena would have been more
prevalent during the hotter and denser early stages of the universe just after the Big
Bang. Hence, it is possible that cosmological relics of grand unification have been left
behind and are in evidence at the present time. A most notable case in point is the
observed excess of baryons over antibaryons, matter over antimatter, in the composi-
tion of the universe. A collection of effects, including 5-violation, may have generated
this baryon asymmetry dynamically, starting from an initial configuration of material
with zero net baryon number.
If we take B to be exactly conserved, then we can have unequal numbers of

baryons and antibaryons only if we postulate the known excess as an initial condition
on the Big Bang. Instead, let us adopt a grand unified theory in which B is violated
and insist on equal numbers at the start. Grand unification then takes its course,
beginning with very brief initial time intervals and very large thermal energies beyond
the unification scale at m x c Matter in this epoch is supposed to consist of quarks and
.

leptons in equilibrium with all the quanta of the higher gauge symmetry. Spontaneous
symmetry breaking eventually sets in as time evolves and the universe cools. Viola-
tions of C and CP are also introduced as essential ingredients in this scenario. Let us
illustrate their role by considering the decays of the superheavy gauge quanta, even
though these processes are not the only (or the most important) contributors to the
asymmetry. The diquark decay modes of X and X can differ because of C- and
CP-violations, so that the rates of production from

X— > q + q and X— > q + q

are not the same. Consequently, we can have equal amounts of X and X in the
 .

908 Elementary Particles

equilibrium period and still generate unequal numbers of quarks and antiquaries
thereafter. A small net excess of the one over the other would survive subsequent
processes of matter-antimatter annihilation and perhaps explain why our part of the
universe contains essentially no antibaryons.
Grand unification has many satisfying and promising aspects. Nevertheless, it is

conceivable that the strong, electromagnetic, and weak interactions cannot be unified
properly until the unification of forces takes account of the force of gravity. By the
same token, it is possible that a consistent quantum theory of gravity cannot exist in
from the other forces of nature. These areas of speculation belong to the next
isolation
more comprehensive stage in the problem of unification. The final solution of this
problem is called the Theory of Everything.

Example

The energy scale of grand unification is extraordinarily large, and the associated
scale of distance is extremely small:

hi 0.2 GeV fm •

15
= 2 X 10
16
fm.
10 GeV

We may wonder whether the effects of gravity are negligible in a relativistic

quantum theory at such short range. Let us argue that the gravitational
interactionbecomes important when the potential energy of two equal masses is
comparable with the rest energy of either mass, and when the separation is
comparable to the corresponding Compton wavelength. We express these com-
parisons by the two conditions

M 2

—h
G = Mc 2 and R =
R Mc

The combination of conditions provides a criterion for the scale of the mass M
in terms of the gravitational constant G:

5
Mc he
GM --2
= Mc 2 M, 2 _
h ~G

This argument determines the rest energy of the so-called Planck mass:

(1.05 X 10" 34 J s)(3.00 X 10 8 m/s)"

•

Mc = 2
n N m 2 /kg 2
6.67 X 10~ •

9
1.96 X 10 J
19
1.22 X 10 GeV
1.60 X 10- 10 J/GeV

The unification scale mxc 2 falls several decades short of this value. It is

noteworthy, however, that the unification mass mx lies closer to the Planck mass
than to the weak mass m w .
 Problems 909

Problems

1. Positively charged cosmic-ray particles approach the Earth from various directions and
are deflected in the Earth's magnetic field. Give a qualitative argument to explain why
more particles penetrate the field in the polar regions and why the particles tend to arrive
on Earth preferentially from the west.

2. Make a quantitative comparison of the forces of gravitational attraction and electrostatic

repulsion between a pair of electrons, and between a pair of protons. Note that the
separation of the particles drops out of the comparison.

3. Consider the collision of protons with protons in a fixed-target accelerator and in a

colliding-beam accelerator. Derive (he relation

A"
A = '(K'l 1 + 2
4 Mr

where K is the single-beam kinetic energy in the first machine, and K' is the total kinetic
energy in the second machine. Take the nonrelativistic limit of the formula, and compare
with the result found in Section 15-8.

Generalize the derivation in Problem 3 to the case of unequal colliding masses. Let K be
the beam kinetic energy for a particle of mass m incident on a target particle of mass A/,

and let K' be the total kinetic energy in the CM frame.

Assign momenta and energies for the emission of a photon by a free electron according to

the diagram, and show that the conservation laws of momentum and energy cannot be
satisfied. The conclusion implies that the photon must be virtual in this case. How is it

possible that the photon is real for the emission processes in Figures 15-16 and 16-4?

(P. E) (P,e)

(Po. E )
 .

910 Elementary Particles

6. Represent the g-factor for electron spin as in Figure 16-6, and draw all Feynman
diagrams of order a and a~.

7. Show that the spherically symmetric meson wave function

g~'/ r

is a solution to the static version of the Klein-Gordon equation.

8. Calculate the minimum energy of photons incident on a fixed proton target for the
photoproduction of neutral pions in the reaction y + p — w° + > p.

9. Let neutrons be incident on a fixed proton target and calculate the threshold kinetic
energies for each of the pion-production reactions

In + n + tt*,

n + p -» I n +p + it ,

\p + p + n~

Table 16-1 gives sufficiently accurate values for the masses of the particles.

10. Calculate the momenta of the final particles in the charged pion decays

+ — n* + —
it > i> and tt* * e* + vr .

Assume that the pion is at rest and neglect the neutrino masses.
11. Consider the decay of it mesons in flight and obtain expressions for the maximum and
minimum energies of the emitted y rays in terms of the it velocity.

12. The reaction used to detect solar neutrinos is the endoergic capture process

37
vr + r,7
Cl -* Ar + «".

Compute the threshold energy for incident neutrinos using atomic mass data from
Appendix A. One source of solar neutrinos is the proton fusion reaction

'H +'H - H 2
+ *
+
+ vf .

Calculate the maximum energy of neutrinos produced for protons at rest, and determine
whether the chlorine detector is sensitive to these neutrinos.

13. Neutrinos and antineutrinos are intrinsically left- and right-handed, respectively, if the

particles have zero mass. Use this fact to prove that the w" decay mode tt -* vv cannot

possibly occur for massless neutrinos.

14. Let 77 mesons be incident on protons at rest and derive a formula for the beam energy at

the threshold for the production of a final state of total mass M. Consider the reactions

7T~+ p -> n* + tt~ + n and w" + p -» K* + 2~

and compute the threshold energies in each case.

15. Consider a tt beam, and a K beam, incident on a proton target in separate

experiments to produce E baryons. Identify the threshold reactions and calculate the
threshold beam energies for each experiment.

16. Draw a bubble-chamber picture for the reaction K ~+ p —» it ~+ 2 + , in which 2+

decays by its proton mode, and the y rays from tt° decay convert to e~ e* pairs inside the
chamber.
 Problems 911

Assume that the neutral kaon states

K°
17. and obey the matrix Schrodingei

equations

'

Mi
2
A K° m u K°
c dt .K° _ V 772 . .K°

and

ih d Ks ms '

Ks
7 2
~dt Ki. 77! • KL

Use the transformation between these sets of states to derive the relations

, ms = m — \Juv , and m, = m + \[uv ,

1 + e

where e is the CP-violation parameter.

Why should the reaction d + d — a + » w° not be observed? The experimental upper

bound on the cross section for this process is of the same order as the observed cross section

for d + d —* a + y. Explain qualitatively why these two reactions are expected to proceed
at comparable rates.

19. The 277 system has nine different charge combinations 2 + + 2 + 7r°, 2 + ?r~,.... How 77-
,

many independent amplitudes for elastic and charge-exchange scattering are there in this
system, and how are the amplitudes charac,c:iisd° How many independent amplitudes
are needed to describe the production of 27;' states in K~ p collisions?

Determine the ±
20. ir p cross section ratios, expressed as

+ + 2 2 2
\x(v P,* p)\ --

Ix(t~>, *"/>) I
: \x(^°n,^'p)\ ,

under the assumption that the isospin amplitudes X\/> anc' X3/2 are ecl ua ^ ar) d under the
assumption that X3/2 vanishes.
±
21. Calculate the values of the pion beam kinetic energy in it p reactions for the observation
+ +
of the ttjV resonances A(1232, V\ A^(1520, f"), 7V(1680, | ), and A(1950, \ ).

22. Show that, for a system of two pions, the isospin / and the angular momentum f are
correlated so that / and ( must be either both odd or both even.
23. Refer to the three-quark formulas for the states A++ A+ A , , , and A ", and use the flavor

substitution u —» s to deduce expressions for all possible strange baryon states. Identify the

quantum numbers T, and Y for the resulting ten hadrons, and plot their locations on a
graph of Y versus Tz
.

24. Construct all nine qq systems vectorially, using the addition of vectors in the (Y, T. ) plane.

Show that the result contains states with quantum numbers in the antitriplet pattern, and
note that a sextet (six-fold) pattern of quantum numbers remains when the antitriplet is

removed.
25. Continue the vectorial construction begun in Problem 24, and generate all qqq systems by
applying the method of vector addition to the composition q{qq). Specifically, construct
the q(qq) states by adding the triplet of q vectors in the (F, Tz ) plane to the antitriplet
and sextet results obtained from the qq system. Show that the final 9 triplet-antitriplet
states form octet and singlet patterns and that the final 18 triplet-sextet states form octet

and decuplet (ten-fold) patterns.

 .

912 Elementary Particles

26. What combination of quarks is needed to construct the antibaryon Z ? Consider the
photoproduction of Z via the reaction

-
Y + p -* E + X,

and deduce the identity of the least-massive particles comprising the unspecified system X.

Calculate the corresponding threshold energy for photons incident on target protons at
rest.

27. Draw quark Feynman diagrams to represent the decays w + —» n + e

+
-¥ vr , K+ — » ir° +
_
e* + ve K" — /i + K + -> m + + and 2~-» n +
f
,
M>
i» tt°, 2 -» n + e~+ vt , <rr~

28. Identify all quantum numbers for the c-flavored hadron systems udc, cu, cd, cu, Id, cs,

and cs.

29. Draw P'eynman diagrams to show the effects of weak neutral currents in the processes

e + e' -* (i + fi^ e~ + p —> e + , p, and f + p —* v + hadrons.

30. Assume a value of 40 GeV/c" for the /-quark mass, and show how this undiscovered sixth
quark may contribute in the cross-section ratio R for electron- positron annihilation.

31. Gluons change the colors of quarks and antiquarks in the manner of Figure 16-38. Show
that eight different gluons are needed to describe all possible color transitions for three

colors of quarks and antiquarks.

32. The known 1 bound states of the bb system are designated as T(«5), where n = 1-4.

Explain the notation, assuming a central potential energy like the one shown in Figure
16-40. The explanation should include sketches of the radial functions corresponding to
the four different T states.

33. Use Maxwell's equations to deduce the equations satisfied by the electromagnetic poten-
tials A and <£ in terms of the source densities J and p. Assume that A and <j> obey the
subsidiary (Lorentz) condition

V A+ • -— 1 d<>
= 0,
c at

and show that decoupled equations result relating A to J and <J>

to p.

34. Consider expectation values taken in the states of a nonrelativistic particle of charge Q,
and show that (p — (?A) and (E — Q<f>) are invariant under gauge transformations.

35. Let the classical one-dimensional motion of a particle of mass m be governed by the
potential energy V(x) = (k/2)x 2 + (X/4)x 4 and , consider the case k < 0. Deduce the
frequency of small oscillations about the position of stable equilibrium, chosen to be at
the point x = +*,, as described in Figure 16-42.
 APPENDIX
TABLE
OF
NUCLEAR
PROPERTIES

Information is tabulated for selected isotopes

according to atomic number Z, chemical symbol, and mass number A. The atomic
mass M refers to the mass of the neutral atom, ^nd values of M
are listed in terms of
the atomic mass unit u. Other data quoted are the nuclear spin and parity i'\ the

isotopic abundance (%), and the radioactive half-life t 1/2 The last two items share
. the
last column in the table, depending on the stable or unstable character of the
particular nuclide. Unstable species art indicated by an asterisk next to the value of
A. Their half-lives are given in seconds (s), minutes (m), hours (h), days (d), and years
(y). Sources of information are Chart of the Nuclides, 13th edition (1984), and Atomic
Mass Evaluation, by A. H. Wapstra and K. Bos (1977).

A-!
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A-7
 BIBLIOGRAPHY

Some of the following references contain material at a higher level. A suitable adjustment of

level is made whenever any such material is used in this book.

Parallel Resources

Eisberg, Robert, and Robert Resnick. Quantum Physics of Atoms, Molecules, Solids, Nuclei, and
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Feynman, Richard P., Robert B. Leighton, and Matthew Sands. The Feynman Lectures on Physics,

Vols. 1, 2, and 3. Reading, MA: Addison-Wesley, 1963, 1964, and 1965.

Ford, Kenneth W. Classical and Modem Physics, Vol. 3. New York: Wiley, 1974.

Gasiorowicz, Stephen. The Structure of Matter. Reading, MA: Addison-Wesley, 1979.

Krane, Kenneth S. Modem Physics. New York: Wiley, 1983.

Leighton, Robert B. Principles of Modem Physics. New York: McGraw-Hill, 1959.

McGetvcy, John D. Introduction to Modem Physics. New York: Academic Press, 1983.

Richtmyer, F. K., E. H. Kennard, and John N. Cooper. Introduction to Modem Physics. New York:
McGraw-Hill, 1969.
Tipler, Paul A. Modem Physics. New York: Worth, 1978.

Weidner, Richard T., and Robert L. Sells. Elementary Modem Physics. Boston: Allyn and Bacon,
1973.

Young, Hugh D. Fundamentals of Waves, Optics, and Modem Physics. New York: McGraw-Hill,
1976.

Mathematical Sources

Boas, Mary L. Mathematical Methods in the Physical Sciences. New York: Wiley, 1983.

Dwight, Herbert Bristol. Tables of Integrals and Other Mathematical Data. New York: Macmillan,
1961.

Sokolnikoff, Ivan S. Advanced Calculus. New York: McGraw-Hill, 1939.

A-8
 Bibliography A -9

Background Readings

Bernstein, Jeremy. Einstein. New York: Viking Press, 1973.

Childs, Herbert. An American Genius: The Life of Ernest Orlando Lawrence. New York: Dutton,
1968.

Curie, Eve. Madame Curie: A Biography. Translated by Vincent Sheean. Garden City: Double-
day, 1937.

de Broglie, Louis. Matter and Light. New York: Dover, 1946.

Fermi, Laura. Atoms in the Family: My Life with Enrico Fermi. Chicago: University of Chicago
Press, 1954.

Heisenberg, Werner. The Physical Principles of the Quantum Theory. Chicago: University of Chicago
Press, 1930.

Hermann, Armin. The Genesis of Quantum Theory (1899-1913). Cambridge, MA: MIT Press,

1971.

Jammer, Max. The Conceptual Development of Quantum Mechanics. New York: McGraw-Hill, 1966.

Pagels, Heinz R. The Cosmic Code. New York: Simon and Schuster, 1982.

Pagels, Heinz R. Perfect Symmetry: The Search for the Beginning of Time. New York: Simon and
Schuster, 1985.

Pais, Abraham. 'Subtle is the Lord . .

.

': The Science and the Life of Albert Einstein. New York: Oxford
University Press, 1982.

Schwartz, Joseph, and Michael McGuinness. Einstein for Beginners. New York: Pantheon Books,
1979.

Segre, Emilio. From X Rays to Quarks. San Franciscu: W. H. Freeman, 1980.

Shankland, R. S. "The Michelson-Morley Experiment." Scientific American, pp. 107-114
(November 1964).

Swenson, Loyd S. The Ethereal Aether. Austin: University of Texas Press, 1972.

Thomson, George. The Electron. Oak Ridge: United States Atomic Energy Commission, 1972.

Classical Sources

Griffiths, David J. Introduction to Electrodynamics. Englewood Cliffs, NJ: Prentice-Hall, 1981.

Resnick, Robert, and David Halliday. Physics. New York: Wiley, 1977.

Sears, Francis Weston. An Introduction to Thermodynamics, the Kinetic Theory of Gases, and Statistical

Mechanics. Cambridge, MA: Addison-Wesley, 1955.

References on Relativity

Kacser, Claude. Introduction to the Special Theory of Relativity. Englewood Cliffs, NJ: Prentice-Hall,
1967.

Mermin, N. David. Space and Time in Special Relativity. New York: McGraw-Hill, 1968.

Taylor, Edwin F., and John Archibald Wheeler. Spacetime Physics. San Francisco: W. H.
Freeman, 1966.

References on Quantum Mechanics

Gasiorowicz, Stephen. Quantum Physics. New York: Wiley, 1974.

Merzbacher, Eugen. Quantum Mechanics. New York: Wiley, 1970.

Schiff, Leonard I. Quantum Mechanics. New York: McGraw-Hill, 1968.

A- 10 Bibliography

References on Statistical Mechanics

ter Haar, D. Elements of Statistical Mechanics. New York: Rinehart, 1954.

Huang, Kerson. Statistical Mechanics. New York: Wiley, 1963.

Landau, L. D., and E. M. Lifshitz. Statistical Physics. Translated by J. B. Sykes and M. J.

Kearsley. Reading, MA: Addison-Wesley, 1969.

Reif, F. Fundamentals of Statistical and Thermal Physics. New York: McGraw-Hill, 1965.

References on Atoms and Molecules

Bransden, B. H., and C. J. Joachain. Physics of Atoms and Molecules. New York: Longman, 1983.

Fano, U., and L. Fano. Physics of Atoms and Molecules: An Introduction to the Structure of Matter.

Chicago: University of Chicago Press, 1972.

Herzberg, Gerhard. Molecular Spectra and Molecular Structure: I. Spectra of Diatomic Molecules. New
York: Van Nostrand Reinhold, 1950.
Karplus, Martin, and Richard N. Porter. Atoms and Molecules: An Introduction for Students of

Physical Chemistry. Reading, MA: W. A. Benjamin, 1970.

Lengyel, Bela A. Lasers. New York: Wiley-Interscience, 1971.

Levine, Ira N. Quantum Chemistry. Boston: Allyn and Bacon, 1974.

Pauling, Linus, and E. Bright Wilson. Introduction to Quantum Mechanics. New York: McGraw-Hill,
1935.

Slater, John C. Quantum Theory of Matter. New York: McGraw-Hill, 1968.

Svelto, Orazio. Principles of Lasers. New York: Plenum Press, 1976.

White, Harvey Elliott, Introduction to Atomic Spectra. New York: McGraw-Hill, 1934.

References on Condensed Matter

Amoros, Jose Luis, Martin J. Buerger, and Marisa Canut de Amoros. The Laue Method. New
York: Academic Press, 1975.

Ashcroft, Neil W., and N. David Mermin. Solid State Physics. New York: Holt Rinehart and
Winston, 1976.

Blakemore, J.
S. Solid Stale Physics. Philadelphia: W. B. Saunders, 1969.

I >obbs, E. R., and G. O. Jones. "Theory and Properties of Solid Argon." Reports on Progress in

Physics 20:516-564(1957).
Feynman, R. P. "Application of Quantum Mechanics to Liquid Helium." In Progress in Low
'Temperature Physia, edited by C.J. Gorter, Vol. I. Amsterdam: North-Holland, 1955.
Kittel, Charles. Introduction to Solid Stale Physics. New York: Wiley, 1971.

London, Fritz. Superjluids, Vols. 1 and 2. New York: Dover, 1961, and Wiley, 1954.

Lynton, E. A. Superconductivity. New York: Wiley, 1962.

McKclvey, John P. Solid-State and Semiconductor Physics. New York: Harper & Row, 1966.

Schrieffer, J. R. Theory of Superconductivity. New York: W. A. Benjamin, 1964.

Silvera, Isaac F., and Jook Walraven. "The Stabilization of Atomic Hydrogen." Scientific

American, pp. 66-74 (January 1982).

Wilks, J. An Introduction to Liquid Helium. Oxford: Clarendon Press, 1970.

Ziman, J. M. Principles of the Theory of Solids. Cambridge: The University Press, 1965.
 Bibliography A- 1

References on Nuclei

Bethe, Hans A., and Philip Morrison. Elementary Nuclear Theory. New York: Wiley, 1956.

Blatt, John ML, and Victor F. Weisskopf. Theoretical Nuclear Physics. New York: Wiley, 1952.

Cohen, Bernard L. Concepts of Nuclear Physics. New York: McGraw-Hill, 1971.

Enge, Harald A. Introduction to Nuclear Physics. Reading, MA: Addison- Wesley, 1966.
Evans, Robley D. The Atomic Nucleus. New York: McGraw-Hill, 1955.

Kaplan, Irving. Nuclear Physics. Reading, MA: Addison-Wesley, 1963.

Krane, Kenneth S. Introductory Nuclear Physics. New York: Wiley, 1987.

Mayer, Maria Goeppert, and J. Hans D. Jensen. Elementary Theory of Nuclear Shell Structure. New
York: Wiley, 1955.

References on Elementary Particles

Griffiths, David. Introduction to Elementary Particles. New York: Harper & Row, 1987.

Halzen, Francis, and Alan D. Martin. Quarks and Leplons. New York: Wiley, 1984.

Perkins, Donald H. Introduction to High Energy Physics. Reading, MA: Addison-Wesley, 1982.

Powell, C. F., P. H. Fowler, and D. H. Perkins. The Study of Elementary Particles by the Photographic
Method. New York: Pergamon Press, 1959.

Ryder, Lewis. Elementary Particles and Symmetries . New York: Gordon and Breach, 1975.

Segre, Emilio. Nuclei and Particles. Reading, MA: W. A. Benjamin, 1977.

Sources of Tabulated Data

Cohen, E. Richard, and Barry N. Taylor. The 1986 Adjustment of the Fundamental Physical

Constants: A Report of the CODATA To.k Group on Fundamental Constants. Elmsford, NY:
Pergamon Press, 1987.

Herman, Frank, and Sherwood Skillman. Atomic Structure Calculations. Englewood Cliffs, NJ:
Prentice-Hall, 1963.

Lederer, C. Michael, and Virginia S. Shirley, eds. Table of Isotopes. New York: Wiley, 1978.

Moore, Charlotte E. Atomic Energy Levels, Vols. 1, 2, and 3. Washington: National Bureau of
Standards, 1949, 1952, and 1958.

Particle Data Group. "Review of Particle Properties." Physics Letters 170B:l-350 (1986).

Thekaekara, M. P., R. Kruger, and C H. Duncan. "Solar Irradiance Measurements from a

Research Aircraft." Applied Optics 8:1713-1732 (1969).

Walker, F. William, Dudley G. Miller, and Frank Feiner. Chart of the Nuclides. San Jose: General
Electric Co., 1984.

Wapstra, A. H., and K. Bos. "The 1977 Atomic Mass Evaluation in Four Parts: Part I. Atomic

Mass Table." Atomic Data and Nuclear Data Tables 19:177-214 (1977).

General Reference Books

Besancon, Robert M., ed. The Encyclopedia of Physics. New York: Van Nostrand Reinhold, 1985.

Gray, H. and Alan Isaacs, eds. A New Dictionary of Physics. London: Longman, 1975.
J.,

Lerner, Rita G., and George L. Trigg, eds. Encyclopedia of

Physics. Reading, MA: Addison-

Wesley, 1981.
 "

ANSWERS

Chapter 1 Chapter 2

d, + d, u
2. 1.72 X 10' 7
W, 3.82 X 10
26
W,
1 I V-'

A c
5770 K, 502 nm
3 m, in, tan V;AT) *

iz^ + n
;

3.

5. /(> X 10
5
m 10. 355 nm, 1053 nm,

9. c/3 II. 0.5682c

_13
11. c/3, 3^8 m 12. 5, 1.70 X 10 J/K 5 m4 •

r) _1
15. 5.93 X 10 eV, 5 X 10™ s
13. (20 m, 20 m/c)
and (10 m, 10 m/c)
18. 5 X 10
19
s ', 1 X 10
18
m -2 -s"

1.32 eV, 337 nm

15. m/<r, $ c,
i

19. 5.80 X 10 6
m, 5.80 X 10"" m
21. 140 keV, 95°
16 1 mA, ,;; mA 25. 2(1 + m/M)mc 2

20 e + Je - m y 2

\/2
'
/l - ,/
2
/2c 2
'
26
E - /£ 2 - m y + 2e'
»/2b' o' /l - z/
2
/2c 2
7.0 GeV
1 + v'
2
/2c 2 '
1 + »' 2 /2c 2
v/2
Chapter 3
26. 1.13 X 10 "'
23
1. 6.6 X 10 moles" 1

{m^ 4 m' 5. 2.80 X 10~ 6

m, 8.46 X 10" H kg, 25
n
M 6. 42 nm
33 c/b, |c, c/5 10.

2 2
11. 0.74 s"'
35. /(m, + w,,) + 2K m.,/c
l

12. 1.90 X 10
H
" m, 5.90
5.9C X 10
28
m" 3 ,

38, (2 + m/2M)mc 2 , 279.7 MeV 0.0950 sr, 2.02 X 10" 7

A-12
 Answers A- 13

-27 -
16. 7.27 X 10 kg m/s, 4.35 m/s 27 E„ E„.\ \cc

17. £4 -» £ 3 ,
2m 2
-3a 2
2hm
28. 0, (-) ,0,(--) 2
£„ -» £ 4
(n > 6), 24 m a

£„ -» £ (« > 12) 48 5£,

5
29. — Tdcos /,
18. 0.239 nra 25w «

20. En - £, (n > 2),

24 h 5£,
sin /

£„ -» £2 (» ^ 5) 5a A

21. 2.847 X 10" m, -2529 eV Chapter 6

22. Al, Mn, Co

(1 + ^/1+ 2 EL
2
/pb 2 )
24. 656.1 nm, 102.6 nm, 121.6 nm IE
Chapter 4 - — (1 + /1 +2EL2 /fLb2 )

1. 7.8 nm, 0.18 nm for £< 0,

3. 134°, 78°
— (-1 +
* /

/l + 2EL2 / ib 2 l )

4. 110°, no
for E>
5. 3.97 X 1
' "'
W/nr,
1.73 X 10~ 6
N/C
2i>/?
— 2
(**
a<» a*
*)
7. 5 MeV
km
8. 98 MeV
9. 4£ , a /4
h- m m
I
2h J~2H
f..

2fiR
— r
2
(
—2 ) , sin —
2
(f>, no
„. , 3.67 X 10" lD
m
y m V i 10. 0.015 eV, 28 jam
kd
14. \\A\
2
cos-( — sin0) 11. 0, A

12. l/4w
17. 8 In 2 15. 0°,180°;

19. A — for |jc| < a

0°, 90°, 180°;
a
54.7°, 125.3°
Chapter 5
2 2
18. h , h
M 2 2
3. \A\
2
,
19.
»v,(4 + i)h| + 4(4 + i)l« 2 l ].

m 2 2
A(ff!,|a,| + w2 a 2|

6.
1

+ —
2m
1

»Vi(4 + i)
l

- 4(4 +
)»

i)|-|«ifl2i,
4
fl 77 k\m - m 2 t
\
\a a.,\ {

7. + 1
2 ma Chapter 7

9 kl
2
+ kf = l

1 2wx , _ I.
— Z - 2

-^(an--* -4 '*'''*
/t
10.
m, 4
]/a a
(2a )- ,/2
3
3 "X 2.
-9,^/A,
+
,

cos <• ' )

4. A(\ - p/2)e- p/2
a
" i M .,
E
— o
7. 4a, 5a, Z2
13. £erf(£) m, 2
2
14. 0.01 nm 9. 5/*
V, V * - 2x o 10. (Z/n)ac
+
T^
(
M + Zm,
11.
22. 0.056 nm M + m.
 1

A - 14 Answers

Chapter 10
14.

16. (0,0,3ea) 2. 21 ps, 5.6 meV

2 l/2
Chapter 8
4. (1 4-
y ) , 3.8 X 10" 2
5. (b)l,(c)i
I. 6. (a) > e/1
2 (^ ,/)
i

8. 12.8 eV, 0.41

1 <?<£:
9. (c) 0.77, 0.64
2w6 (
.-' _ ^•'/4)'
10. 3.91 eV, 0.02 eV
4. 2, I
14. 120 K
6. 1.16 X 10 '
eV, ±0.33 nm 15. (b) U(meV) =
for Aw = ±1 0.3 nm 0.3 nm
1 9.6
7. (5/4a)c I

h } h
\

8. 2.24 mm (c)0.26 nm, -0.01 eV;

9. 5.59 GHz (d) 1.2 X 10
2
K
11. 0.25,0.067 17. 2.4 X 10" s and 7.6 X 10"
16
14. l/405a' compared with 1.5 X 10" s
r
b
15. 1.34 X 10" 'eV, 4.47 X 10~ eV 19. 0.39 meV, 2.0 meV
19. 4.39 X 10 "*' eV, 4.53 X 10" 5
eV 20. 8.3 X10
H rad/s, 4.5 eV
20. ±3, ±2, ±1, times \i
HB 21. A = 9.47 eV, a = 25.2 nm" 1

22. fi H Bm }
R = 0.113 nm
23. 9.43 X 10" 7 eV; 22. 0.128 nm
±11.59, ±8.28, ±4.97, ±1.66 24. 1.0, 1.3

times 10"
H
eV for j = \\
Chapter 1

±6.20, ±3.72, ±1.24

times 10
8
eV for j = \
3. 36, 3, £, 7

4. 96, 1,9
Chapter 9
11. 0.1 K, 6 X 10
5
K
2. 79.0 eV below
13. 6 X 10"
3. - 77.5 eV 21
17. 3.6km/s, 1.2 X 10 J/K
4. 6.s, 4/, 5d, Sp
18. 6.2 x 10" K, 3.3 X 10
a J/K
~'

5. 1.26, 1.84, 2.26

20. 4.8 K, 10 ' nm
7. 0.103 nm, 0.108 nm, 0.122 nm;
21. 2.1 X 10'' m/s
12.09 keV, 11.52 kcV, 10.19 kc-V

3? r Chapter 12
, ,

11.
4 4 I 2
'• (3) 2 2 2;
12. 1.85 eV, 3.37 eV, 3.84 eV, 3.88 eV, a 'v^fl '3v^ a
1 54 eV, 4.53 eV, 4.54 eV, 4.54 eV (b) -6e, -4e, -3e, -ze
13. 6.3 /xeV, 2132.4 fieV 2. (a)6,6;(b)£
16. 4, 3 (three ways), 4. (a)fl
3
,a
3
/V^,4a 3 /V3;
2 (four ways), 1 (three ways), (b) -6c, - 12c, -8e
1 7 7 J '
P 8. 1.6 X 10 6 m/s, 31 nm
19.
!

F2 10. 5 X 10 " s

20. S1/2 , $,, Z)3/2 , F2 14. 3 X 10" 42 , 2 X 10

32
, 1 X 10' 9

24. ± 1.74 pm for Aw = ±1;

15. 1.24 eV
 Answers A- 15

16. 100 26, -0.264/1^,4.793 fi N ,

17. 0.02 eV, 3.2 nm 4.793 fi N ,

-1.913 /u.
v
19. proportional to T~ '

Chapter IS
10~ 6
20. 8 X
4. 0.730 g

Chapter 13
8 5.302 MeV, 4.781 MeV
9. 5.304 MeV, 4.602 MeV
1. -0.9 m/s
11. 1.711 MeV
2. 131 m/s
6
13. 0.709 MeV, 1.144 MeV, 0.122 MeV
7. 3 X 10
15. 1.312 MeV, 1.505 MeV, 0.483 MeV
8 (a) 3.6 jU-eV;
_3 19. 4.67 neV, 1.95 meV, 81.4 m/s
(b)4.0 X 10- 3
J/m !
,4.3 X 10 J/m3
21 -1.191 MeV, 4.43 MeV, 1.531 MeV
9. 15 nm
25. 13.11 MeV, 13.89 MeV, 15.39 MeV
13. 2.6 X 10~ 9 T
26. 11.85 MeV, 7.48 MeV
15. 47 mK
27 0.0235 eV, 2120 m/s

Chapter 14
28. 22.8 MW •
h
29. 195.9 MeV, 185.4 MeV
1. 51 MeV 30. 0.189 MeV
2. 6.76 fm, 1240 MeV 31 22.37 MeV, 8.683 MeV
4. 20.18
33, 1.943 MeV, 1.199 MeV, 7.551 MeV,
5. 1.007825 u, 2.014102 u,
7.297 MeV, 1.732 MeV, 4.966 MeV
15.994915 u
Chapter 16
6. 8.551 MeV, 8.790 MeV,
8.505 MeV, 7.868 MeV, 8. 144.7 MeV
8. 39.9632 u, 55.9359 u, 9. 292.6 MeV, 279.9 MeV, 287.0 MeV
119.903 u, 207.987 u 10. 29.8 MeV/c, 69.80 MeV/c
9. 0.367 MeV, 0.4498 MeV, 12. 0.813 MeV, < 0.420 MeV
0.5590 MeV 14. 172.4 MeV, 904 MeV
12. 6.738 MeV, 7.368 MeV, 17.2 MeV 19. three, two
20. 1:1:0 and 0:2:1
2MRi
v,
13
2 (tt)
'
21. 190 MeV, 612 MeV,
h 9tt

IB. 1.31 (taking R = 1.2 fm)

885 MeV, 1407 MeV
19. (1 + krf) )/2k, 2.95 fm
2b dss, A + A, 6258 MeV
21. 10.63 MeV, 11.98 MeV 30 f beyond 80 GeV
24. 35. (l/2w)J-2k/m
 PHOTO
CREDITS

Einstein, page 3. Courtesy of Philip Rosen.

Space-travel cartoon, page 7. From Einstein for Beginners, by Joseph Schwartz, illustrated by-

Michael McGuinness. Illustration copyright © 1979 by Michael McGuinness. Reprinted by

permission of Pantheon Books, a Division of Random House, Inc.

Planck, page 74. Permission of AIP Niels Bohr Library.

Rutherford, page 123. Permission of AIP Niels Bohr Library.
Bohr, page 123. Permission of AIP Niels Bohr Library.
Electron diffraction pattern, Figure 4-4, page 187. From The Electron, by George Thomson,
published by U.S. Atomic Energy Commission, 1972. Permission of U.S. Department of
Energy. Courtesy of Oak Ridge National Laboratory.

Heisenberg, pag< 196. Permission of AIP Niels Bohr Library.

Schrbdinger, page 220. Photography by Francis Simon. Permission of AIP Niels Bohr Library.
Born, page 226. Permission of AIP Niels Bohr Library.
Probability distributions, page 365. From Introduction to Atomic Spectra, by Harvey Elliott White,
published by McGraw-Hill, 1934, and from "Pictorial Representations of the Electron
Cloud for Hydrogen-like Atoms" by H. E. White, in Physical Review 37, published by
American Institute of Physics, 1931. Reproduced with permission of McGraw-Hill and
American Institute of Physics.

Zeeman lines, page 376. From Introduction to Atomic Spectra, by Harvey Elliott White, published
by McGraw-Hill, 1934. Reproduced with permission of McGraw-Hill.
Dirac, page 421. Permission of AIP Niels Bohr Library.
Pauli, page 441. Courtesy of Philip Rosen.
Rotational spectrum, Figure 10-19, page 531. From Physics of Atoms and Molecules by B. H.
Bransden and C. J. Joachain, published by Longman, 1983. Reproduced with permission of
Longman Group Ltd.

A-16
 Photo Credits A- 1

Vibrational -rotational spectrum, Figure 10-20, page 531. From Atoms and Molecules: An Introduc-
tion/or Students of Physical Chemistry by Martin Karplus and Richard N. Porter, published by
W. A. Benjamin, 1970. Reproduced with permission of Benjamin/Cummings.

Molecular electronic spectrum, Figure 10-21, page 532. Photograph by R. Colin. From Physics

of Atoms and Molecules by B. H. Bransden and C. J. Joachain, published by Longman, 1983.

Reproduced with permission of Longman Group Ltd.

Two-dimensional hexagonal lattice, Figure 12-3, page 578. Photograph by W. J. Mullin.

Icosahedral structure, Figure 12-6, page 580. Photograph by W. J. Mullin.

Face-centered-cubic lattice, Figure 12-8, page 581. Photograph by W. J. Mullin.

X-ray diffraction pattern, Figure 12-14, page 586. From The Laue Method by Jose Luis Amoros,
Martin J. Buerger and Marisa Canut de Amoros, published by Academic Press, 1975.
Reproduced with permission of Academic Press.

Mme. Curie, page 741. Permission of AIP Niels Bohr Library.

Fermi, page 768. Permission of AIP Niels Bohr Library.
Lawrence, page 818. Permission of AIP Niels Bohr Library.
Feynman, page 824. Permission of AIP Niels Bohr Library.
Decays it —
> ju,
—> e, page 831. From Tlie Study of Elementary Particles by the Photographic Method, by
C. F. Powell, P. H. Fowler, and D. H. Perkins, published by Pergamon Press, 1959, and
from "Mesons" by C. F. Powell, in Reports on Progress in Physics 13, published by The
Institute of Physics, 1950. Reproduced with permission of Pergamon Press and The Institute

of Physics. Courtesy of F. H. Fowler.

Strange-particle processes, Figure 16-17, page 8">0 From Nuclei and Particles, by Emilio Segre,

published by W. A. Benjamin, 1977. Reproduced with permission of Benjamin/Cummings

and Lawrence Berkeley Laboratory, University of California.

Gell-Mann, page 871. Permission of AIP Niels Bohr Library.

 NAME INDEX

Anderson, C. D., 822, 830 Dirac, P. A. M„ 420, 821 Hartree, D. R., 446, 451
Andronikashvili, E. L., 649 Drude, P., 587 Heisenberg, W. K., 182, 195, 219,
Aston, F. W.. 683 Duane, W„ 107 668, 729, 822
Au scr, P., 164 Dillons, P. 1... 561 Heitler, W„ 509
Avogadro, A., 73, 123 Dunoyer, I.., 400 Hermite, C, 249
Dyson, F.J., 823 Hertz, G. L„ 168
Back, E., 426 Hertz, H. R„ 2, 100
Balmcr, ]. )., 146 Einstein, A., 2, 7, 29 7', 99, 107, Hess, V. E, 816
Bardecn, J„ 615, 635, 650 124, 171, 182, 539, 559, 560 Higgs, P. W„ 899
Becquerel, A. H.. 741, 751 Hofstadter, R., 679
Bcthc, H. A.. 806 Fairbank, W. M„ 874 Hund, E, 488
Blackctt. M. S„ 818 P. Fermi, 465, 668, 767, 796. 8 12
E., Hunt, F. L„ 107
Bogoliubov, N. N'., 648 Feynman, n,. P., 648, 823, 843
Bohr, N. H. D., 122, 182,268,668, Fitch, V. L„ 856 Iliopoulos, J.. 878
790, 796 FitzGerald, G. F„ 6
Boltzmann, L. E., 1. 76, 538 Fock, V., 446, 451 Jensen, J. H. D., 720
Bom, M„ 219, 226. 502 Franck.J., 168 Joliot.J. F., 742
Bose, S N . 465 Fran/, R., 595 Joliot-Curie, E. 742

Bi.iKK. W. H., 1115, 584 Fraunhofer, |. von, 145 |osephson, B I)., 658
Bragg, W L„ 105, 584 Frisch, O. R , 796
Brattain, \V II .
i>1 5 Kamerlingh Onnes, H . 634, 638
Bun, (... 791 Gamow, G., 755, 770 Kirchhoff, G. R , 76. 93
Brillouin, 1, ., 602 Geiger, H. W„ 132, 1 H Klein. O., 827
Bioun. R . 123 Gell-Mann, M., 843. 851, 854, 861, Kusch, P., 400
Butler, C C. 851 870. 877, 889
Georgi, H M„ 902 Lagrange, |. L., 90
Cabibbo, N . 877 Gerlach, W„ 390 Lamb, W F ... 123

Cabrera, B . 907 Germer, L. H 185, 584 ,

Landau. L. 1).. 640, 643, Lis

Chadwick.J., 667, 669, 677 Gibbs.J. W„ 538 Lande, \ . 129

Chandrasckhai , S., 571 Glaser, D. A., 818 Langevin, P., 124

Cockcroft.J. 1).. 784 Glashow, S. L„ 878, 885, 899, 902 Larmor, 383 |
,

Compton, A H., 108 Goeppert-Mayer, M .. 721) Laue, M. T. F. von, 104. 584

Condon. E. U„ 729 Goldhaber, M., 841 Lawrence, F. < >.. 8 17

( loopei .1 X . 635, 650 Gordon. W. S27 Lee, D. M.. 635, 664

Cowan, ( L., 762. 771 Goudsmit, S. A„ 393 Lee, T. D„ 839

Cronin, |
W., 856 Greenberg, O W„ 889 Legendre. A. M., 318
Curie, M. S., 74 1 Gregory, D., 579 Lennard-Jones, J. E. 520
( urie, P., 629. 741 Gross, I) | . 890 Libby, VV. E. 745

Grotrian, VV. R. W., 442 Liouville, 2,56

J.,

Dalton, ).. 73, si". London. F. W., 509. 517, 643

Davidson, ( | .
is".. 584 Hahn, O., 796 Lorentz, H. A. 6, 29, 375

de Broglie, L. V P R. 182, 219 Hamilton, W. R . 219 Lummei , O., 76

Debye, P. ). W. 95, 562, 566 Han, M. Y . SS9 Lyman, 1 ., 147

1-1
 1

1-2 Name Index

McMillan, E M . 817 Politzer, II 1) .890 Sturm, C. F, 256

Maiani, L., 878 Powell, C. F., 830 Sudarshan, E. C. G. 843
Maiman, 1 II . 174 Pringsheim, K... 7()

Marsden, I .. Ill Teller, E., 770

Marshak, R 1 > I I Thomas, L. H., 412
Maxwell, J. C, I, 538 Rabi, I I., 400 Thomson, G. P.. 185, 584
Meissner, F. V\ . 638 Raman, C. V., 107 Thomson, J.J. 100, 126, 587, 682 ,

Meitncr, I. . 796 Rayleigh.J. W. Strutt, 85, 94. 165 't Hooft, 6„ 885, 899
Mendeleev, I). I.. 12 I, 156, 668 Reines, F., 762, 771 Ting, S. C. C., 880
Michelson, \ A . I Richardson, R. C, 635, 664 Tomonaga, S. I., 823
Millikan, R A . 101, 128, 874 Richter, B., 880 Townes, C. H., 174
Mills. R I Rochester, <; 1) , 851
Minkowski, II , 60 Roentgen, W. K , 103 Uhlenbeck. G. E., 393
Morley, 1 U . I Rubbia, C, 885 Urey, H. C, 667
\lo[ sc. P, M., 525 Russell, II. N„ 482

Moseley, H. C.J., II)'-'. 447, 668 Rutherford, E., 122, 132, 61*7,669, van dcr Meer, S., 885
Mossbauer, R. 1... 781 741, 746, 751, 784, 815 van dcr Waals.J. I).. 517
Rydberg.J. R , 147 Veksler, V. I, 817
Nambu, \ 889 .

Neddei meyei S. H , Walton, E. T S., 78 1

Nishijima, K., 861 Salam, A . 885, 899 Weinberg, S„ 885, 889, 899
Saunders, F. A., 482 Weizsai kei , ( I v< in, 689
Ochsenfeld, R . 638 s< hmidt, I.. 725 Wheeler, J. A , 796
Oppenheimer, ) R 502 Schrieffer, |. R 635, 650
,
Wiedemann, (.'•
II, 595
Osheroff, I) I) ,
t, .

Scl linger, E., 219, 226, 344 Wien. W., 76

Schwinger, [., 823, 885 Wigner, E. P., 729, 79
Pais, A . 851, 854 Shockley, [., 615 Wilczek, I-.. 890
Paschen, 1. C. H F., 147, 126 Slater, | .
c . 146, 451 Wilson, G. I. R.. 817
Pauli, W., 376, 393, 120, I 10, I 17, Soddy, I'., 673, 746 Wilson, R. W.. 78
156, 164, 167, 762, 822 Sommerfeld, A.J. W.. 175, 587 Wu, G. S., 839
Penzias, A A . 78 Stefan, |., 76
Perrin, | B . 126 Stern, ().. 390, 406 Yang, C. N„ 839. 885,898
Petil, A I .
".i)l Stokes, <;. G., 124 Yukawa. II.. 826, 830
Planck, M K E I.. 7 1, 93, 538, Stoner, E. C, 448
Strassmann, I., 796 /.eeman, P., 375
 SUBJECT INDEX

Absolute frame. 1 Associated production, 848, 855 neutrinos, 834, 837

Absorption, 14H. 170 Asymptotic freedom, 890, 898, 003 neutrons, 784, 790
photon, 101, 148, 107, 170. 779, Atomic clock, 283 pions, 832, 810, 865
82) Atomic mass, 138. 683, 691 protons. 668, 783
x-ray, 458 Atomic mass unit. 685, 687 Beats. 209
Absorption coefficient, 158 Atomic number. 123. 131. 164, 440. Beauty, 881
Absorption inw section, 458. 712. 117, 668, 673 B decay, 740, 743, 759, 767. 8,31,

771 Atomic shell theory, 147, 466 834, 839, 842, 876
Absorption edge, 159 Atomic spei ti 3" decay, 759, 763
Accelerator, 078, 784, 810. 817 Atomic weight, 382 |T decay, 759. 763
7
Acceptor, 613, til ) Augei effect, 164. 777 (3 radiation, 667, 741, 752, 759
A< i, 170 Autoionizatic n. 165, 470 b flavor. 880
At tivation enei g) ,
Oos Avei age e • i g\ . 85, 93, 9 I. 556 Big Bang, 79. 836, 907
A. th u\. 746 Average value, 200 Binan fission. 796
Addition of angulai momenta, 405, Avogadro's number. 125, 178. 687, Binding energy, 447, 455, 512, 577,
418. 438, 483, 721, 755, 776, 749 652, 682, 689, 700
802 Axial vector, 838. 843 per nucleoli. 686, 797. 804
Aether, 2. 0, 8 Biot-Savart law, 410
Age of the Earth, 743, 750 Balmer— Rydberg formula, 147, 156, Blackbody, 75, 80
Alkali atom. 447, 455. 470 344 Blackbody radiation, 75, 93, 172,
Allowed region, 242. 252. 303 Balmer series, 146, 157, 370, 387, 538, 559
a decay, 740. 742. 751, 790 139 Bohr atom, 122. 148. 149
a particle, 132, 667, 735, 741. 751 Hand, 527, 502, 570, 596. 006 Bohr formula. 149, 155, 350, 368,
Ammonia molecule, 283, 5 I I degradation, 532, 537 476
Amplification ratio, 621, 6 13 gap, 576. 596. 606 Bohr hypothesis, 148, 152, 268
Amplitude, 270. 368, 102. 862, 805 head. 532, 537 Bohr model. 149, 163, 175. 201,
Analyzer, 403 Barn. 141, 713 344, 348. 360, 447
Angulai differential operator, 306, Barrier: Bohr orbit, 153, 162. 177, 201, 381,
314 rectangular, 273, 298, 756 447
Angular momentum, 135, 151, 300. single-step, 273, 298 Bohr radius, 153, 201. 348, 363
301. 307, 309, 320, 325. 375. Barrier penetration, 271, 750, 799 Boltzmann's constant, 85, 94
381, 393. 405. 181. 731 Baryon, 846, 858, 870, 887 Bond:
Angular momentum operator, 301). Baryon asymmetry, 907 chemical, 501
320, 330 Baryon number, 846. 861. 871, 879. covalent, 501, 508, 513, 576
Angular solution, 314 904 directed, 522
Anbarmonic oscillator, 901 BCS theory, 635, 050, 000 hydrogen, 583
Antiferromagnetism, 627, 630 Beam: ionic, 501, 511, 512
Antineutrino, 761 a particles, 132, 667. 669 Born-Oppenheimer approximation,
Antiparticle, 65, 111, 121. 821, 852 atoms, 390. 397, 400 502, 536, 622
Antiproton, 65. 820. 885 electrons, 678 Bose-Einstein condensation, 553,
Antiquark, 870 lieu \ ions, 077 643. 648, 653, 665, 666
Antisymmetric wave function, 238, kaons, 848, 855 Bose-Einstein statistics, 538, 540,
286, 465, 540 magnets, 390 552, 504, 573, 644, 047,666
Anlisymmetrization, 466, 471, 489 molecules, 400 Bose gas. 643, 666

1-3
 1 1 1

Subject Index

Boson. 465, 540, 557, 559, 564, 573, Collision, 50, 53 678,686,690,696, 715,729,
643, 665, 678, 830, 846 Collision time, 590 752, 783, 800, 805, 821, 892,
symmetry, 465, 167. 869 Color, 880, 808, 00 1 897
Boundan condition, 82, 236. 253, Color confinement, 880, 898 Coupling constant, 824, 844
274, 280, 310, 315, 597, 622, Color singlet. 887 CP invariance, 852
707 Combined reaction, 805 CPT invariance, 852
Bounded motion, '25 Complementarity, 71, 188 < quark, 878, 889
Bound si.ttc. 152, 155, 254 Complex exponential function, 208, Creeping film, 637, 650
b quark, 880, 889 223, 227, 272, 309. 314 Critical field, 638, 654
Bracket! sei ies, 180 ( Complex numbei . 207 Critic al mass, 801
Bragg angle, 105, 186 ( :oni|)onent, 484, 192 Critical temperature, 639, 666
Bragg refle< tion, 105, 186 Compound nucleus, 098, 790, 796 Critical velocity, 637, 641, 648
Breedei reactor, 802 Compton effect, 107, 107, 550, 669, Cross section, 134, 140, 180,771
Bn ii \\ ignei formula, 701 , 813 736 absorption, 458, 712, 771
Bremsstrahlung, 106, 823 Compton wavelength, 110, 115, 154, differential, 141, 679, 789, 828
Brillouin /one. 602, 625, 632 185. 827 elastic, 790
Brownian motion, 123, 78 1 ( Condui Hon band, 008 electron-positron, 868, 880, 888
Bubble chamber, 817, 850 Conduction electron, 570, 571. (.08, |>ion iiik leon, 864
632 reaction, 789, 805, 865
Cabibbo angle, 87 ( Condui livity: Rutherford. 141,678, 789
Cabibbo current, 877 electrical, 570, 588 scattering, 140, 789, 828
Cabibbo rotation, 877, 884, 898 thermal, 576, 588, 626, 632, 635 Crystal, 105, 575
Carbon atom, 493 Configuration, 449, 483, 488 covalent, 622
Carboi -.814 ( onjugate variables, 176, 195 ionic , 631
Carbon dating, 744, 812 Conservation: Crystal plane, 105, 186
Cathode ray, 103, 126, 379, 741 angular momentum, 151, 300, Curie, 748
Central-field model, 440, 449, 463, 331, 371,412,418,483,493, Curie's law, 629
477, 481, 695, 711, 714 703, 755, 760, 776, 784, 833, Current-current coupling, 843
Central force, 135, 151, 300, 301, 837, 869 Current density, 611, 632, 655, 660
317, 323, 345, 351, 357,443, baryon number, 810, 90 1 Curvature of an eigenfunction, 253,
701, 705, 714, 731, 838, 859 charge, 677, 893, 906 255, 333, 720
Centrifugal potential energy, 302, .ha. in, 879 Curvaturc-to-valuc ratio, 253
329, 769 energy, 44, 50, 53, 685, 754, 760, Cyclic variable, 310
r flavor, 878 779, 784, 827 Cyclotron, 817
Chain reaction, 796 isospin, 728, 735, 784, 862, 865,
Chandrasekhar limit, 57 1 893 Davidson-Germer experiment, 185
Characterise wavelength, 25, 145 lepton number, 767, 830, 8:',',, 904 de Broglie hypothesis, 182
Charai teristit x ray, 100, 101 , 117, momentum, 44, 50, 53, 754, 779, de Broglie wavelength, 183, 186,
457 784 188, 192. 193, 199, 539,554,
Charge conjugation, 852 nil. leon numbei, 078, 7 12. 78 1 573, 648, 672
(harged urrent, 883 ( parity, 371, 755, 770, 770, 784, Debye temperature, 566, 570, 574,
Charge independence, 728, 781, 833, 837, 800 593, 639, 052
826, 850 probability, 220, 342 Decay, 712. 715, 817, 821, 864
( Charge numbei 008, 673
. sli.mgrness, 818, 853, 80:',, 870, i hannel, 791
Charge symmetry, 720, 863 870 constant, 740, 81
Charm, 878 Constrained motion, 220, 309 ( (live, 746
Charmonium, 880, 880, 892 ( Constraint, 80 law, 745
Chatl o| the \udiclcy 07:'., 743 ( Containment, 800 probability, 7 10
(.11, molecule, 521 Continuous symmeti v. 001 I, lie. 710
Classical energy relation, 223, 263, (Continuum state, 255, 27 sencs 7 13, 718, 812
28:',, 280, 302, 309 Coopet |).m , 650, 659 666 u ansition, 713
(lassie ,,1 limit, 150, 210, 395 Coordinates: Deexcitation, 209. 157, 476, 740. 797
< .lassie ,il radiation, 200. :'>77 lefthanded, 326 Degenerate Fermi system, 567, 587,
Classification scheme, 810, 846 i ighthanded, 326 632, 696
Closed shell, 117. 151, 15:'.. 170. 510, space nine. 1 I. 26, 33, 38, 15 Degenerate stales, 292. 321, 331.
71 1, 718, 722 spherical, 303. 320. 333 340, 357, 371, 385, 395, 408,
Closed subshell, 110, 177, 180, 188 three-dimensional Cartesian, 288, 118, 110, 100, 175, 18.3. 715.
Cloud chamber, 817, 822 304 731, 8.5.3, 859
CM frame, 57, 780, 700. 820, 8 0., three-dimensional polar, 300, 301, Delayed neutron, 801
805 327, 333 Density ol siaies. 557, 565, 568, 574,
Cockcroft-Walton generator, 78 1, Correspondence principle, 159, 240, 50 1, 1 1

817 395 Depletion region, 615

( Coherenl radiation, 17 1 Cosmk radiation, 810, 822, 820, 830. Detector, 816. 817
( Collet live mode, 5 10, 50 t 851 Determinism, 193
( !olle< live model, 720 Coulomb barrier, 7',',. 799. 805, 812 Deuterium. 007
Collector, 020 Coulomb energy, 690, 736, 800 Deuteron, 067, 699, 705, 734
Colliding beams, 57, 50. 810. 808, Coulomb interaction. 131, 300 14 i d flavor, 871
880, 885 318, 409, 442, 181, 072. 1,7 1. Diamagnetism. 627, 629
 Subject Index 1-5

Diatomic molecule, 242, 502, 508, 306, 310, 323, 331, 351, 115. stimulated, 170
524, 574 449, 714 \-ia\ . 157
Differential operator. 223. 263, 283, isospm, 732, 859 Emissive powei . 75
289, 305, 306, 320, 329, 34 1 spin, 394 I mitter, 620
443, 827, 896 Eigenvalue equation, 251, 257, 307, Endoergic reaction, 784
Diffraction, 185, 188, 191, 199,230 315,320,330 Endpoint, 764. 836
Diode, 615 Eightfold Way, 870 Energy band, 590
Dipole transition amplitude, 270, Einstein coefficients, 171 Energy cell, 86
368, 374, 768 Einstein solid, 539. 560, 574. 622 Energy gap. 596. 633, 638, 640, 65 I,

Dirac equation, 420, 821. 827, 898 Electrical discharge, 126 654
I>ii,h sea, 822 Electric dipole: Energy level, 148, 151, 105, 170,
Dirac theory, 420, 670, 821, 873 moment, 269, 368, 374, 511, 513 233, 237, 246. 268, 310. 324,
Direct energy, 506 radiation, 368. 775 357
Direct reaction, 792 selection rule, 270, 366, 371, 386, nuclear, 729, 742, 787, 794
Discrete angular momentum, 153, 399, 418, 441, 462, 475, 481, shell-model, 715
178, 183,310. 320 493 single-particle. 149, 10 1, 695, 715
Discrete energy, 94, 148, 237, 254, transition, 270, 368, 386, 475, x-ray, 462
310, 330 774 Energy level diagram, 148, 156, 238,
Discreteness, 73, 111 Electricquadrupole momem, 700. 246, 359, 409. 419, 450, 607,
Discrete orbit, 148, 153 702. 737 730, 742, 822
Discrete symmetry, 902 Electromagnetic current, 824, 843, Energy operator, 263
Disintegration chain, 674, 743, 748 875, 883 Energy release, 742, 754, 763, 765.
Disintegration energy, 754, 763 Electromagnetic energy density, 79 797, 804
Dispersion, 211, 562, 625 Electromagnetic field, 268, 368, 823, Ensemble, 538, 543, 572
Dissociation energy, 516, 527 826, 869, 894 Equal-spacing rule, 246
Distance of closest approach, 134, Electromagnetic interaction. 100, Equilibrium position, 212. 525
341 368, 732, 767, 773, 816,821, Equipartition of energy. 85, 93. 1 19
Distinguishable particles, 541, 572 823, 832, 839, 842, 849, 860, Equivalent electrons. 488
Distribution, 86 869,875, 881,894,898,902 Error integral, 249
angular, 133, 139, 324, 360,679 Electromagnetic modes, 79, 81, 95 Even function, 237, 247, 326
blackbody, 75, 93 average ener,^ , 79. 85, 94 Event, 11,26,38,42,60
Fermi, 551,680, 696 number, 79, Exact symmetry, 903
frequency, 75, 1 19 Electromagnetic spectrum, 104, 114 Exchange, 465, 54
gaussian, 215 Electromagnetic theory, 2. 3, 7, 11. antisymmetry, 465, 471, 488, 734,
227
intensity, 191, 882, 894 887
Maxwell-Boltzmann, 86. 91,1 19, Electromagnetic transition, 842, 875 symmetry, 465, 471, 488, 734, 869.
171. 549, 814 Electromagnetic waves, 2, 3, 7 888
Planck, 93. 172 standing, 79. 80. 95 Exchange force, 475
probability, 191. 193,209,227. Electron, 73, 126, 835 Exchange integral, 506
324, 335. 360, 449 charge, 128, 130 Excitation, 165, 269. 448, 457, 476
velo( ity, 814 mass, 128, 130 collision.il, 167, 457
wavelength, 77, 1 19 Electron affinity. 512, 535 radiative, 167. 269
Distribution function, 86, 91, 543 Electron capture, 764 Excitation energy, 167, 672, 729. 792
Donor, 612. 633 Electron diffraction, 185, 679 Excitation spectrum. 636, 642, 005
Doping. 608, 633 Electron-electron repulsion, 142, Excited slate, 155, 773
Doppier effect, 22, 67. 781 475, 481 Exclusion principle, 446, 449. 456,
Double slit, 189, 191. 227 residual, 482 464, 467, 074. 690, 095, 711.
Double-well oscillator, 533 Electronic energy, 530 714, 822, 887

d quark, 871. 889 Electron-neutrino, 834 Exoergic reaction, 784

Dulong-Petit law, 561, 575 Electron-positron pan, 114 Exotic state, 872
Electrons: Expectation value, 260, 335
Effective charge, 163, 444, 450 in a metal, 570, 576, 587 angular momentum, 336
Effective mass, 603, 610. 633 in a solid, 576, 596 electric dipole moment, 269, >8

Effective potential energy. 302. 329, Electron spin, 375. 393, 394, 405, energy, 263
714 410. 420. 425. 438, 446 function of r, 363
Eigenfunction, 233, 251, 320, 445 Electron spin resonance, 399 momentum, 261. 263

angular momentum, 320, 331 Electroweak interaction, 881. 898, position, 261 , 363
energy. 233. 265, 290. 307. 331 902 potential energy, 261. 365
isospin, 734 Electroweak quantum. 8X2, 885. 898
momentum, 272 Electroweak theory, 882, 899, 902 Faraday's law, 662, 894

simultaneous, 310, 320. 331 elm experiment, 126, 179, 379, 682 Fermi, 672

spatial. 471. 734 Emission: constant, 843, 883

spin, 471, 734 electron, 743, 760 energy, 567. 608, 616, 632, 652,

two-particle, 284 meson, 826, 831 696

Eigenvalue. 233, 251,257 photon, 148, 167, 170, 271, 779, gas, 587. 695
angular momentum, 310. 320. 823, 875 momentum. 589
positron, 743. 760 selection rule, 769
energy. 233, 255. 264, 284, 290, spontaneous, 170 sphere, 589, 606, 652
 . 1

1-6 Subject Index

Ferm; Geometric si Incident wave. 270

Georgi-Glashow model. 902 Independent-electron theon. 4-44.

temperature Gerade wave function. 504 461

m amplnuC' g-factoi Independent-nucleon theory, 695.
velo< h Lande, 429. 495 711. 714. 720. 794
Fermi— Dirai 10, 549, neutro Index of refraction. 21
nuclear. 132, 070 Indistinguishabilhv, 464, 539, 569
Kern: orbital 724 Induced djpole moment. 513, 517
proton. 432. 070 Induced fission, 799
spin. 390. 100, 421, 429, 670, 724. Inequivalent, electrons, 488
Inertia! frame. 2
Glashow— Iliopoulos— Maiani Instability, 744. 745. 751. 849. 864
Fermi theory 767 8 )-' mechanism. 878 Insulator, 570. 006
(.lass. Integrated circuit, 575. 015
Ferron .
Global symmi Intensity 139. 190. 227. 270. 367.
Feynman diag (,luon. 890 - -

Good quantum number, 412. 420. Interaction:

101 474. 183, 703 central. 300. 444. 449
76, 110, 41«. 179, Goudsmit-L'hlenbec k h\ pothcsis. Coulomb, 134. 300. 345, 348, 441.
191 594 481. 570. 072. 07 4. 078,686.
ii lure constant, 1 ")4. 1 13, Gtand total angular momentum. 433 090. 090. 715. 729. 752. 783.
Grand unificatioi 321, 892. 897
741, 796 (.land unified theory, 002 electromagnetic, 100. 368. 732.
Flavoi Gravitational interaction, 571. 810. 707."- - -23.832.839.
-

908 842,84 -
37! 881.
Fluctuation, 124 ty, 571
- ence, 107. 741, 770 Grotrian diagram, 4 42.170. 178, elec iron— phonon, 051
Flux quantization, ;
479 electroweale 38 398 902
Forbidden region, .' 12 i Ground slate. 155. 237, 215. 249, gluon-gluon -

257 4 17, 149. 715,77 gluon-quark, 890. 898

Fountain eff< (.roup velocity, 209. 61 i gravitational. 810. 908
Four-vector. 00 hyperlinc. 432. 700
momentum—energy, 63, 71, 113, Hadron Lennaid- Jones. 520. 535. 577, 635
magni 30,385,411,425,
Hadronization, 888 '.27

Fractional baryon number, 871 Half-life, 674 7 4',. 71", 7 meson-meson, 867
Fractional charge, 871, 874, 905 Harmonii oscillator. 176, 202. 240. noncentral. 4 13. 481
ni 796 270. 524, 901 nudeon—nucleon, 670. 699. 709,
Franck-Hertz experiment, 108. |x| Heat capai il

Free electron theoi 575 388 020. 646 •

spin-orbit, 410. 416, 426,461,
rice particle, 222, 271, 601 Heitler-London wave function. 509, 47" •

Fundamental interaction, 815 spin-spin. 432. 199

Helium atom, 142, 169 strong. -
12, 839, 846.
Fusion, 174, 1 lie i mite differential equatioi -
-

di. 805 Hermite polynomial, 2 I unified. 882, 904

ternary deuteron, 805 Higgs inn hanisn universal Fermi, 8 13
High-energy physics, 815, 816 van del Uaals. 501. 512. 51" !

Galilean relativity, .'7, 640 Higher symmetry, -

weak. 711. 702. 707. 808. 816.
7 Id. 773 H, molecule, 501, 508, 534, 541, i

7 rav. 114, I 57 - • '102

Gamow—Teller selection rule. 770 H; molecule. 501, 502. 534, 590 Interference. 189, 221, 227
Gamow-Teller transition, 770 Hole. 457. 462, 191,61 Internal conversion. 165. 777
Gas discharge tutx-. 126, 1 15 Hole current. 615 Internal quantum number, 7 .

H ,() molecule, 521 358,87 893

coupling, 897, 903 Homonuclear molecule. 513 Internal svmmetrv 732, 858. 893
quantum, 894, 898, 903 Hund's rules Interval:
Gauge invariance, 89 1 Huygen's cm^uuc tion, 214 space. 9. 15. 16. 31

Gauge symmetry, -
Hydrogen atom. 49. 34 1 4 space-time, 39. 61
904 Hydrogen burning, 807 ume. 9. 12. 20. 30
Gauge theory, 894, 898, 902 Hyperchargi Intrinsic pantv. 832. 834. 839. 873
Gauge transformation, 895. 896, 912 Hvperfine structure. 431. 700 Invariant ma-
Gaussian wave packet, 215. 218 IGperon. 846 lm ersion frequency. 283
Gell-Mann— Nishijima formula, 861, Hvperon decay, 8 19. 876 Inversion svmmetrv. 837
Ionization. 155. 167
Generation: Identical particles - 19, 569 energv. 155. 453, 633. 712
lepton. 835, 881, 904 Identical-particle svmmem. 285. level. 458
quark. 881. 904 440. 4 Hi, 464 potential, 512, 535
(k-neration current. 017 Impact parameter. 135 Isobar. 674. 691. 729, 743, 759. 859
 Subject Index 1-7

Isobaric analogue states. 72 Lepton number. 767. 835. 90 1 Mass level diagrai
Isomer. 776 Leptoquark transition. 904 Mass matrix, 857
Isospin. 728, 858, £ Lifetime. 17. 746. 779. 791. 832. Mass numbei
Isospin multiplet: 849 Mass spei trometi
doublet. 7 12 LiF molecule, 512, 520. 535 Matrix mechanics, 195. 219
singlet. 73:5. 859 Light-emitting diode (i.EDi. 619 Mattel wave, 182, 185, 188, I'' I,

triplet. 733. 859 Linearis . 22 219. 220. 22t.

Isospin space. 732, 859. 870, 893 Liquid-drop model. 689, 726. 796. Maxwell— Boltzmann disli ibutii
Isospin symmetry, 728, 858 -
800 95. 119. 171. 519. 81 1

Isotope. 154. 673. 682 Liquid He. 539. 574. 634. 664 Maxwell-Boltzmann statistic

Isotope effect. 154. 639 Liquid helium, 517. 553. 634. 635 542. 546. 554. 500. Y,
Isotopic abundance. 676, 683 Localization, 111. 205. 228. 260, 204. Maxwell's equations. 2, i

311. 324. 335 655. 894

;; coupling. 48! 72 Local symmetry, 893, 902 Mean free path. 594. 627. 632, 772
Josephson effect. 658 London equation, 656. 666 Mean life. 747. 775, 779, 81 1

J/<!>
meson, 880 London force. 517 Measurement, 194. 195
Junction: Longitudinal wave. 624 Meissner effect. 638, 655, 662, 666
Josephson. 658 L orbit. 162 Meson. 540. 326.
p-n. 615 Lorentz contraction. 6, 15 388
p-n-p, 619 Lorentz force. 51. 378. 629 Meson exchange, 826
Lorentz frame, 30, 33. 38, 55. 60. Meson field. 826
Kaon, 839. 848 113 Meson theois. 82l
long-lived, 854. 856 Lorentz invariance. 39, 61, 851 867 Metal, 575. 587. 0ob
neutral. 852. 911 869 Metastable state. 172. 497. 776
short-li\ed. 854. 856 Lorentz transformation. 26. 29, 33, Michelson interferometer, 4, 66
Kaon decay, 849, 852 38, 45, 51, 56, 61. 113 Michelson-Morlev experiment. 4.

Kinetic theorv. 1, 538 Lorentz triplet, 377. 430. 496 15. 66

Klein-Gordon equation. 827 LS coupling, 483, 488. 701 Microelectronics. 615
910 L series, 162, 457 Microstate. 87. US
A: orbit. 162 L shell, 453, 461 Minkowski space, 60
K series, 162. 457 Lvman series. 1-/ '57 370 386 Mirror nuclides, 691. 729
K shell, 451, 461 Mirror symmetry, 838
Macrostate, 87, 1 !8 Moderator, so]
Lab frame, 57. 785. 790, 820. 851, Magic number, 677, 710. 714. 720 Molecular band, 527
865 Magnetic dipole: Momentum operator. 263
Lagrange multiplier. 90, 18 55 "
t moment. 380, 390, 701, 722 Momentum space. 643. 646
559. 564. 567. 573. 643 radial i< Monolaver. 573
X point. 636 Magnetic field: Morse potential energv . 525. 536
\ transition. 664 external, 375, 376, 380. 385. 425. Moselev's formula. 163
Lamb shift, 423. 823 732 Mossbauer effect. 781
Lande's interval rule. 491. 500 internal. 410, 426. 431 Multiplet, 376. 393. 446, 485, 490,
Larmor frequencv. 383. 398 motional, 41 731. 732. 859
Larmor precession. 383. 412. 426 Stern-Gerlach, 390, 399, 401 Multiplicity, 475
Laser, 170 Magnetic force. 390, 399 Multipole, 774, 813
four-level. 172 Magnetic interaction, 375, 380 185, electric, 775
helium-neon. 173. 497 495,627
411, 425. magnetic, 775
rubv. 172 Magnetic moment. 381, 390, 425. Multipole index. 775
three-level, 172 495, 627. 701. 825 Multipole paritv, 776
transition. 172 497 nuclear, 392. 432, 633. 670. 701. Muon, 17, 817. 830. 834
Latent heat. 636. 646 722 Muon deca\. 830, 835
Lattice: orbital, 381, 396 Muonic atom. 181
bodv-centered-cubic (BCC), 581, spin, 396, 399. 411, 421. 432 Muon-neutnno. 834
Magnetic monopole, 907
face-centered-cubic (F( X - I
Magnetic resonance, 397. 700 NaCI molecule, 501, 535
63 Magnetism 627 Natural width. 779
hexagonal-close-packed I HC'Pl. Magnetization, 576, 628 Nearly-free-electron model. 604
578 Magneton: Negative energ\ state, 821
honeycomb, 631 Bohr, 382, 432, 627 Neutral current. 885
simple-cubic (SC). 581. 632 nuclear. 392, 432 Neutral kaon decay, 852
square. 579. 631 Manv-bod\ problem, 440, 446 Neutrino. 761, 767, 821. 830. 834,
triangular. Maser, 1 74 840, 844, 853
Lefthandedness. 839, 841, 856 Mass-acquisition mechanism, 882. absorption, 762, 771. 834

Legendre polynomial, 318, 327 899 mass. 762, 764, 836

Length contraction. 15. 16, 31. 37 Mass action. 633 oscillation, 837
Lennard-Jones interaction. 520. 535. Mass-energy relation, 47, 53. 685 Neutron. 540. 570. 667, 669. 732.
577, 035 Mass formula, 691, 759,800 767. 796, 876

Lepton, 767. 830, 834, 843, 846, Massless particle, 48, 111, 841, 882. absorption, 712, 797

881, B98, 904 890. 894 capture, 700, 713, 809

1-8 Subject Index

Neutron excess, 798 parent, 743. 752. 759 Periodicity, 175, 319, 315
Neutron numbei ' .
Nuclide, 973 Periodic table, 123. 163, 376, 440,
Neutron-proton mass difference, 446, 449, 673
670, 706, 729 Observable, 299, 333 Permittivity, 633
Neutron separation enei Observer, 8, 11, 29, 38 Persistent current, 637, 638, 640
711, 737 Occupation numbei, 87, 449, 5 1 1. Perturbing interaction, 269-
Neutron yield, 799 919. 718 Pfund series, 180
Newtonian mechanics, I. 7, 27, 11. Octet, 891, 91 I Phase, 205,207, 227, 659, 896
baryon, 891. 879 transition. 575, 646, 664
Noble gas, 1 17, 155, 511, 517 meson, 891, 879 Phase space, 175
Node nt an eigenfunction, 237, 255, Odd lime lion, 237, 247, 326 Phase velocity, 206
152 Oil-drop experiment, 128, 179.871 Phonon, 539, 540, 560, 576, 593,
Noncentral force, 4 13, 1*1 Old quantum theory, 74, 178, 447. 621, 640, 648
Noncommuting transformations, 488 exchange, 651
One-bod) problem, 159.391 l"> '.
Photoelectric effect, 99, 116, 155,
Nonconservation: One-dimensional box, 231. 259, 287 167. 458, 539, 559
baryon number, 904 One-electron atom, 149. ill, ',18, Photon, 74, 100, 107, 111, 170, 190,
lepton numbei 90 . 1 357, 379, 395, 495 539, 559, 823, 826, 882
parit) Optically active electron, 147, 179, absorption, 101, 148, 167, 170,
Noi iii.il density, 648 481, 487 824
Normal fluid, 635, 648 Orbital: emission, 148. 167, 170, 824,875
Normalization, 228, 230, 239, '2 19. antibonding, 597 exchange, 824, 875
110,316.334,34! atomic , 359 scattering, 109, 116, 121, 194
168 bonding, 507 Photovoltage, 618
Normal modes, 529 hybrid, 522 Photovoltaic 618
cell,

Nuclear binding energy, 685, 689, molec ulai, 598, 535 Physical state, 226,260
711 Orbital angulai momentum, 394, Pickup reaction, 794
Nuclear decay, 674, 7 in. 7 12. Mr, Pion, 817, 830
745 Orbital magnetii moment, 389, 390 parity, 832, 833
Nik leai densit) . 682 Orbital parity, 834, 838, 854 spin, 832, 833
Nuclear disintegration, 668, 674, Orbital state, 359, 406 Pion decay, 831,834
740. 742 Orbital symmetry, 598 Pion production, 832, 846
Nik leai iv itation, 072, 773, 779, Orbit equation, 137, 179 Planck mass, 908
783 Ordei parametei .
',",9 Planck quantum hypothesis, 74, 94,
Nik leai lone 668, 670, 1.71. 699 Organization ol panicles, 819, 849. 99. 193, 2 19, 271
711. 728, 74 1. 755, 799, 826, 858, 879 Planck's constant, 94, 192. 197. 152.
•'12 Orthogonality, 238, 256, 295. 337. 179. 196
i, mm-. 1)71. 989. 827 343, 354, 498 Plane k's formula, 94, 1 77
Nik leai isomei ism, 771) Oilbobi liuni 9, 'I Plasma, 806
Nuclear magnetii moment, 392, 132, Overlap integral, 599, 519. 599 Plutonium. 802
1,79. 701, 722 ( )vei lapping bands, 997 Polarizability, 518. 535
Nik leai mass. 682 Polarization, 377, 388, 562, 939
Nik leai model, 668, 672, 979, 689, Paii annihilation, 1 15, 898 Polarizer, 103
991,. 705, 714, 721), 799, 792, Pairing, 664, 977, 690, 722 Polai vector, 838, 843
791, Paii ing energy , 690 Polyatomic molecule, 521. 526
Nucleai radiation, 719, 711, 77:5 Paiiproduc Hon, I II, 822 Population inversion, 172. 497
Nik leai radius, 132, 142. 971. 678, Parahelium, 9,9 Positron, 114. 422, 822
! 799, 713, 777, 800 Paramagnetism, ',27. 9:',:', Pi isitronium, 1 15. 154
Nik leai reaction, 977, 735, 740, 78.3. Parity, 238. 2 17. 273. 325. 330, 371. Poynting vector, 189
789, 894 I'll, Mil, 722, 755, 779, 775, Precession, 383, 398, 413, 428
Nudeai lead,, i, 781, 799. 81)1 784. 837. 852 ['recessional state, 386, 398
Nmleat shell theory, 977. 991. 711, Partic le in a box, 234, 26 Pressure, 555. 599
714, 729, 791 Particle wave- duality, 182. 188 Probabilistic theory, 192. 219. 538
Nik leai spin, 432, 979, 799, 721. Partition luni tion, 91, 549. 572. 609, Probability, 220, 228, 3,34, 360, 402,
755, 799, 779 1,28 494, 538, 572. 749. 772
Nik leai structure, 1)97, 978, 789 Paschen-Bai k effec i, 126 Probability current density, 229, 277,
Nucle.u transformation, 98",, 712, I'asc ben sei les. 147. 1 57 294. 342. 659
749. 713. 749, 797, 78:5 Pauli paramagnetism, 629 Probability density, 228, 233. 235.
Nucleon, 979. 686 689 695, 732, Pauli pressure , 569 260, 283, 311, 333, 558, 573
797, 826, 846, 899, 864 Pauli principle. 166, 9,9. 17 1 Probability interpretation, 192. 193,
Nucleon— nucleon interaction, 972. 599. 5 12. 5 1',. ",-,7, 51,8. 576, 205,219,226,260,283,289,
989, 999, 705, 728, 829, 892 ,
,2 69 i
703 73 324, 333, 360, 464
Nucleon number, 673, 767, 846 833, 887 Propagation of waves, 205
Nucleon spin, 979 l> branch, 529 Proper length, 15, 31. 37
.I,, leosynthesis, 897 Penetration depth, 296, 657, 999 Proper lime, 13, 31, 38, 42
Nucleus, 132, 539, ",79. 997, 7 19 Periodic boundary condition. 597. Proton, 95, 128. 540, 570, 670. 732.
daughter, 743, 752, 759 622 875
 Subject Index 1-9

Proton chain, 806 total orbital. 471. 477. i- Regeneratii n

-
Proton cycle, total spm. 473. 477. 183, 189. 769 Relative coordinate, 1

Proton deca) Quantum panicle. 1 12. 188 Relative moi

Proton-electron mass ratio, 150, 434 205 Relativ istic coi re< tion. 175, 1

Proton number. 67 Quark. : 139

Proton stability, 846, 906 antilriplet, 872 911 Relativislk dynamii
Pseudoscalar meson. 8 i' charge, 871, 8

Pumping. 172, 497 mass, -

Relativists energy rclati
triplet. 872. 911 827 867
~
Quadi upole, _' 7 17 Quark confinement. 875, 88i Relativistic kinemai
quantization. 73. 94. 237, 253 Quark current. 875. 88 Relativists kini
angular momentum, 152, 17s. Quark model. 870, 875, -
Relativistic mass. 47, 819
510, 322. 385. 393. 394. '102 Relativistic momentum. 44. 421
4116. 432. 473. 483, 700 Quasar. 67 Relativistic quantum theory, 416,
Quasimomentum, 604 42o. 821
axis, 323. 385. 403 Q-value. 55. 71, 754. 763. 76: Relativistic wave equatii
Bohr condition. 152, 17- 805,809. 813 Relativity principles, 8, 26, 44
charge, 73. 905 Relaxation time 59
-
energy. 74. 94, 107, 148. 133. 175. Radial differential equation. 313. Renormalizability,
220, 237. 254. 268, 310, 329. 345. 348, 706, 714
324. 328 Radial differential operator. 305, Representation rule 22 .

flux. 662. 666 329 289. 305, 520, 329

isospin. 732. 859 Radial node. 331. 352. 449. 715 Repulsive core. 703. 738
magnetic moment. 392 Radial probability density. 334. 363 Resistance. 593. 634
matter. 73 Radial solution. 313. 329. 345. 348, Resistivity. 593. 638
Sommerfeld condition, 176, 181 445. 149, 707. 714 Resolution of ima^
spin. 394 Radiancy, 75 Resonance. 779, 791, 832
Quantized field, 823 Radiant emittance. 75 barvon. 832. 864. 873
Quantized oscillator, 94. 177. 246 Radiationless process. 164. 777 meson. 864. 880
Quantum: Radiation in matter. 116 nuclear, 791
of action. 175 Radiation scale parameter 777 Resonance radiauon. 167. 779
of energv. 94. 107 RadioactM!\. .74,740, Rest energy
of light. 99 742 Rest mass. 47
Quantum chromod\namics (QCD), artificial. 74 Reverse bu-
ss7. 889, 898, 902 naiura 1
. 667. 740 p meson. 868
Quantum electrodynamics QED) Radio astronomy, 435 Righthandedness, -

823 844 882 - I

894, 898 Raman effect, 167 Rigid rotator, 31 I

Quantum field theory, 822 821 Random event, 1"! 193 22 Root-mean-square (rms) deviation,
844 85 1, 882 889 894 746. 789 124. 262
Quantum interference, 227. 5 Randomness. Rotational energy, 324, 536
Quantum number. 153, 176 236 Range. 752 Rotational motion, 308, 501, 522.
245. 255. 287. 320, 376. 394. Range—depth relation, 708
4 15. 832, 8 6, 879 -energy cm ve, 752 Rotational symmetry, 323. \.~
angulai momentum, 310, 315, Range-mass relation. 827, 844 882 357. 386, 731 - 7 :

'
Rate equations. I 893
4H6. 721 "" 333, 841 Rayleigh scattering, 165 Roton. 642, "is 666
azimuthal, 310, 315, 35* RayleigrTs criterion, 197 Russell-Saunders coupling. 482
charm. 879 R branch. 529 Rutherford atom. 122. 132. 145
Reaction amplitud Rutherford scattering. 132. 134. 152.
( /'. 854 Reaction cross section. 789. 792. 805. 17'

grand total angular momentum. 365 Rydberg constant, 117. 37 1

433 Reaction kinematics. 53, 784, 820. Rydberg energy, 153. 347. 34H
h\ percharge. 861
internal, 7 - Reaction probability 789 Saturation. 101. 686
isospin, 732 Real photon Saturation current. 61s
magiK Reciprocal lattice. 586. 602, 632 Scalar potential. 895
molecular. 508 Recoil. 158, 779 Scale - '

nucleai spin. 432. 7 Recombination current, 617 Scattering:

orbital. 559, 369. 406, 488 Rectifier. 615 a-particle, 132. 13 1. 6l

principal. 351, 357. 449. 715 Recursion relation. 248, 271. 296. Bragg. 105. [86, 584, 602
radial node. 331. 352. 449. 714 355. 373 charge-exchange, 828
single-electron, 357. 395, 408, 445, Reduced mass. 151. 301. 345. 381. Compton, 107. 116. 120

447. 449. 461. lot,. 483, 488 706 Coulomb. 134

spin, 394. 401. 406. 421. 446 Reflected wave. 276 direct. 828
strangeness. 848. 861 Reflection, 273 elastic. 134. I'.". 679 783, 862,
total angular momentum. 466. coefficient. 27-, 838 -75
474. 48li. 484 symmetry. 325 electron. 678, 7'
 1

1-10 Subject Index

Sc attering (Continued) Solar spectral irradiance, 78 triplet, 472, 487, 489. 510. 734.
inelastic, 875
167, 783. Solid, 575. 576 769
neutron— proton, 828 molecular, 583 Spin-statistics theorem, 467
nucleon— nucleon, 703. 729, 828 two-dimensional, 579 Splitting, 375
photon, 109, 194 Solid angle, 139, 333, 789 beam, 391, 399, 401
pion-nucleon, 832, 862, 864 Solid helium, 560, 635 energy level. 385. 398, 415. 430.
Raman, 107 Sound velocity, 563, 566, 574, 627 434. 718
Rayleigh, 105 Space inversion, 326. 837, 852 hyperfine. 434
Rutherford, 132, 134, 152, 179. Space quantization, 391 inverted. 718
Space time, I, 26, 33, 38, 60 I line. 375. 377. 418. 430. 685
Thomson. 108, 111, 1 It) Space-time diagram, 40, 768, 823 spin-orbit, 415, 416. 461, 479, 718
x-ray, 108 Spec id, heat, 539, 500, 573, 588. Zeeman, 385, 425, 446
Si altering angle, 108, 1 33, 135 010 Spontaneous fission. 54. 799
Si hmidl hue. 72") Spec Hal absorptance, 75, 1 18 Spontaneous symmetry breaking,
Schrodingei equation, 219, 220, 231, Spectral band, 501, 523. 527 883. 899. 901. 904
283, 289. 303, 309. 312, 857, Spectral emissivity, 75, 118 Square well. 257, 296. 706. 715. 738
896 Spectral energy density, 79, 85. 93. i quark, 871. 889
time-independent, 233. 251, 284 171 SQl ID, 663
Schrodingei theory, 226, 231, 268, Spectra] line, 145, 270, 344, 307 Stability, 074. 092
357, 37"). 393, 120, 142, 117. Spectral radiant emittance, 75, I 18 island ol. 677
821. 891, 896 Spectral reflectance, 75 valley of, 075, 693, 759
Sc reening, 163, 1 1 1. 150 Spectroscopy notation, 359, 108, Standard Model. 902
Set oihI sound, 636, 650 111, 401, 474, 480, 484 Standing wave, 79, 80, 589. 601
Selection rule, 270 6,374, Spectrum, 75 Stationary state, 148. 149.220,231,
386, 399. 118, 111, 162, 17"). absoi ption, 145 251. 264. 268. 275, 290. 307.
181, Vi',, 71.9, 774 a-pai Ik le, 758 309, 323, 327, 330,334,345,
Self-consistent theory, Hi), 150 167 atomii , 115 357, 360, 39",
Semiclassical theory, 269, 368 I) 1,501,523 >' Si.hisik al met h.uiK s, 86, i
-

Semii ondui toi , 575, 606, 608 (3-ray, 700, 830 Stefan Boltzmann constant, 76. 98
doped, 998, 912 OUkhodv. 7o 'i I Stefan-Boltzmann law, 76. 98. 119
extrinsic, 008. 012 continuous, 75, 106, 145, 101. 760 Stellai abet ration, 35
intrinsic .
008 discrete, 106, 1 15. 101. 758 Stellai energy, 806
n type, 01 1 (le< tromagnetic , 101, I 14 Steradian, 139
// type, 01 1 ele< tronii .
">27 Stern—Gerlach experiment, 390, 394,
Semiconducioi devi, 1 615 emission, 145, 366 855
Semiempirical m.iss formula, 089, energy , 638, 12 Stirling's formula, 89, 91, 548, 551
712, 759, 800 frequent y, 75 Stokes' law, 124, 128
Separation constant, 232, 313 7-iay. 773 Stopping potential, 101
Separation ol variables, 231, 313, mass, 683 Strangeness, 846, 853. 861, 870
143, 11'. molecular, 167. 501. 527 Strangeness-i hanging decay 849,
Scncs limit, 147 optical, 447, 453, 171) 803, 876
1 flavor, 871 proton, 787, 813 Strange partii le, 8 18
Shear, 570 rotational, 527, 537 decay, 849, 876
Shell, 359, 367, 147, 1 19 rotational vibrational, 527 Sn ipping reaction. 793
inner, 102. 118, 457 solai, 78, 145 Strong interaction, 816, 821, 826,
outer, 102. 4 18. 476 wavelength, 77, 97 832. 839. 846, 849. 858, 864
Shell closure, 447, 453, 077, 711, \ ray, 106, 161, 117, 157 870. S80, 898, 902
718, 722 Speed ol light, 2, 8, 26, 34 Sturm— Liouville theory, 256
Shift: Spherical harmonic, 315, 320, 326, Subshell, 449, 721
blue, 24, 781 345. 115 ordering, 45
Doppler, 22. 781 Spin, 375, 393. 394, 405. 146, 164, Substructure, 8 It), 870
energy level, 385, 389, 4 14. 429 732, 700 Supen ondui toi , 634, 638, 65 I

frequency, 379, 383 Spin-dependent Fori e, 702 type-I, 663

hyperfine, 434 Spin magnetic moment. 393. 390, type-II, 663
red, 24, 07 399, 111. 421, 132 Supti fluid, 634. 635
spin-orbit, 111 Spin-orbital, 445, 449, 466 density , 6 19
Simultaneity, 10. 18, 31. II Spin-orbil coupling, 410, 121. 120. Superfluid 'He, 634, 664
Single slit, 189, 193. 199, 203,214, I I I 10 1, 179, 184. 490. 718, Superfluidity, 634, 635, 640, 643,
230 721 647
Single valued solution, 310, 315 Spin-orbit energy shift, 111. 118 Superheavy element. 677
Slatei determinant, 407. 471. 499. Spin-polarized hydrogen (II i 66 Superleak, 637, 649
542, 887 i,i,i, Supernova, 571
Solai cell, 618, 633 Spin -spin coupling, 432. 199 Superposition, 192. 208. 221, 265,
Solai constant, 78, 118 Spin si, He, 406 209. 297. 338, 367, 466, 703,
Solar neutrino, 836, 910 singlet, 172. 487. 189. 509. 734, 85 863, 872, 877, 882, 888
I

Sol. 11 neutrino unit, 830 769 Surface energv. 090. 800

 Subject Index 1-11

Sulfate tension, 802 momentum-energy, 15,63, 113 I i). ertaint) prim iple, 182, 195
Susceptibility, 628, 63:5 phase. 896 285. 311, 321. 321. 465, 5
Symmetric wave function, 238, 286, velocity, 31 ".lo. 669, 779. 827
465, 540 space-time, 29, 38, 45, 61 I Ingerade wave fun< lion, 50 1

Symmetrization, 466, 471, 489 rransistoi , 575, 615, 633 Unification, 816, 821, 882, 902
Symmetry, 238. 285, 292, 323, 325, Transition, 148. 166, 170. 268 Unification mass. 904
386, 728, 816, 837. 846. 852, allowed, 769 Unification scale. 903
858. 87(1, 883. 893, 902 charge-changing, 844, 875, 883 Unified theory, 882, 902
Symmetry breaking, 386, 732. 860 charge-conserving, 878, 885 i unci sal In mi mtci.u lion * 1 i

Symmetry energy, 690, 698 color-changing, 890, 898, 912 u quark, 871. 889
Synchrocyclotron, 819 diquark, 904 Uranium, 797
Synchronized docks. 11, 13,26 electric dipole, 270. 368, 386, 170,
Synchrotron, 8 19 774
Vacancy, 157. 191, 593
electromagnetic, 842, 875
\'.i< iiuiii. 822
Tachyon, 70 Fermi, 769
Valence, 123
Tauon, 835 flavor, 876, 881, 898
hand, 1)08
Tanon decay, 836 forbidden, 769
electron, 155, 177. 510, 608
Tauon-neutrino, 836 Gamow—Teller, 770
van del VVaals c ixsl.il, 622
Tau-theta puzzle, 839 hole, 462. 499
van dei VVaals interaction, 501, 5 12,
Temperature, 538 isomeric, 776
517, 893
Tensor force, 703 laser, 172
Vectoi meson, 869
Term, 484, 487, 488, 192 leptoquark, 904
Vectoi potential, 823, 895
Tetrahedral structure, 579 nuclear, 742. 746. 752. 759. 768,
Velocity addition, 3 1, 35, 56, 58,
Texture, 664 773
786
tflavor, 880 quai k-to-antiquark, 904
Velocity spat e, 92
Thermal neutron. 587. 796, 814 quark-to-lepton, 904
Vertex. 82 1

Thermal radiation, 75 radiative, 148, 155. 166, 170, 268,

Vibrational motion. 501. 521, 536
Thermal wavelength, 542, 554, 573 366, 386, 418, 768, 774, 824
Violation:
Thermodynamic equilibrium, 86 strangeness-changing, 876
baryon number, 90 1

Thermodynamic probability, 88 strangeness-conserving, 876

CP, 856, 881. 907, 911
Thermomechanical effect, 637, 649 weak, 767. 842, 875
parity, 839, 813, 885
Thermonuclear process. 806 Zeeman, 388
symmetry 837 .

Thomas precession, 412 Transition amplitude, 270, 368, 402,

Virial theorem, 366
Thomson atom, 131 768, 877
Virtual photon, 821, 875, 888
Thomson scattering, 108, 111, 116 Transition probability, 270, 368, 746
Viscosity, 124. 128, 630, 18
Thought experiment: Transition state, 269, 297, 367
Volume element. 289, 333
quantum theory, 197, 400 Transition temperature, 635, 638,
Volume energy, 689
relativity, 7, 1 1, 48 646, 653
Three-body decay, 761 Transmission, 273. 278, 756
Three-dimensional box, 288 Transmission coefficient, 278, 757 Wave equation, 82, 219, 221
Threshold: Transmitted wave, 276 Wave function, 191, 193, 220. 226.
energy, 65, 115, 120, 781, 815, Traveling wave. 205, 589. 626 231. 260, 306. 330. 39",
848, 851, 888, 910 Traveling-wave boundary condition, Wave mechanics, 2 19
frequency, 102 597 Wave packet, 209, 222
wavelength, 106 Triatomic molecule. 457, 521 Weak current, 843, 876, 881
Tight-binding approximation, 604 Truth, 881 Weak interaction, 744, 767. 808. 810.
Time dilation, 11, 30, 817 Tunneling, 277, 281, 502, 596. 658, 821, 830, 837, 83'). 842, 8 19.

Time reversal, 852 756 853, 875. 881. 902

Total angular momentum, 406. 474, Turning point, 251, 302. 333 Weak mixing angle. 882. 905
484, 700, 718, 721 21 cm 435line. Weak quantum. 811, 875. 882, 885,
Total orbital angular momentum. Twin paradox 25. 42 899, 903
470, 478, 483. 701 Two-body decay, 754 Weak transition, 707, 812. 875
Total spin angular momentum, 473, Two-body problem. 150, 301, 345 Weak vectoi field, 844
478, 483, 701 Two-body reaction, 783, 789 White dwarf star, 539. 571. 57 1

I quark, 880 Two-fluid model, 635, 647 Width, 779. 791

Transformation: Two-neutrino experiment, 831 partial, 792
of angulat momentum stales, 408 Two-particle system, 283 total, 792
of coordinates, 2, 26, 27, 29, 33, Wiedemann— Franz law, 595
326 u flavor, 87 Wien's law, 76, 78. 97
four-vector, 60, 851 Uncertainty, 182 Work-energy theorem. 51, 71

Galilean, 27 angulai momentum, 311, 321, Work function, 102, 120

gauge, 895,912 331, 337 World line, 40
lab <-» CM, 57, 786, 794, 820. 851, energy, 264, 311, 331, 779, 827
869 momentum, 195, 208, 266 X ray, 103, 161, 741, 764, 77:1

Lorentz, 25. 29. 33, 38. 45, 51,61, position, 195, 262, 206 absorption, 458
113 spin, 394 diffraction, 101, 186
1-12 Subject Index

\ ra\ {Continued) Yang-Mills theory, 898 normal, 376. 385. 496

emission, 457 Zeeman transition, 386, 430
scattering, 105, His. 584 Zeeman effect, 375, 377, 385, 425, Zero-momentum state. 644
X-ray level diagram, 162 195, 627 Zero- point:
\-i.i\ spectrum, 106, 161, 1-17. 157 anomalous, 375, 388, 393, 125 energy, 203, 237. 2 15
\-i.n tube, 105, 110, 11)1 lassie al model, 377 motion, 577, 635
 1

1 hydrogen 30 zinc 59 praseodymium 88 radium

2 helium 31 gallium 60 neodymium 89 actinium
3 lithium 32 germanium 61 promethium 90 thorium
4 beryllium 33 arsenic 62 samarium 91 protactinium
5 boron 34 selenium 63 europium 92 uranium
6 carbon 35 bromine 64 gadolinium 93 neptunium
7 nitrogen 36 krypton 65 terbium 94 plutonium
8 oxygen 37 rubidium 66 dysprosium 95 americium
9 fluorine 38 strontium 67 holmium 96 curium
10 neon 39 yttrium 68 erbium 97 berkelium
1 sodium 40 zirconium 69 thulium 98 californium
12 magnesium 41 niobium 70 ytterbium 99 einsteinium
13 aluminum 42 molybdenum 71 lutetium 100 fermium
14 silicon 43 technetium 72 hafnium 101 mendelevium

15 phosphorus 44 ruthenium 73 tantalum 102 nobelium

16 sulfur 45 rhodium 74 tungsten 103 lawrencium
17 chlorine 46 palladium 75 rhenium 104 rutherfordium*
18 argon 47 silver 76 osmium 105 hahnium*

19 potassium 48 cadmium 77 iridium 106 **

20 calcium 49 indium 78 platinum 107 **

21 scandium 50 tin 79 gold

22 titanium 51 antimony 80 mercury 109 **

23 vanadium 52 tellurium 81 thallium

24 chromium 53 iodine 82 lead
25 manganese 54 xenon 83 bismuth
26 iron 55 cesium 84 polonium
27 cobalt 56 barium 85 astatine
28 nickel 57 lanthanum 86 radon * Elements with disputed names

29 copper 58 cerium 87 francium ** Elements without names

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047160531X 01 * '

PHYS340

ISBN 0-4 7 1-6053 1-X