Module 1: History of Atomic & Molecular Physics and basic backgrounds

Lecture – 1 :

Introduction to Atomic and Molecular Physics

Introduction

 The Atomic and Molecular Physics is the world of Atoms, Molecules, Ions, Clusters and Photons.
 It is the one of the most fundamental and important field in development of knowledge in
Physical and Chemical sciences.
 It is the oldest branch of Quantum Physics. The field contributed so much to the development of
quantum mechanics that until thirties of last century, atomic and molecular physics was
inseparable from quantum physics.
 It remains one of the most important subjects for the testing grounds of the quantum theory.
 In spite of being the oldest field, it has retained its freshness all along and is continuing to
contribute to the understanding of the fundamental laws of nature and also to the development
of new technologies.

Research in this area today encompasses the study of structure and interaction of atoms, molecules,
ions, biomolecules, clusters at wide ranging scales.

 Providing newer insights into practically all field of science and technology, such as:

Spectroscopy, Laser Physics & Technology, Plasma Physics, Nuclear physics, Non-accelerator
Particle Physics, Astrophysics, Condensed Matter Physics and Material Sciences, Metrology,
Biosciences, Atmospheric Sciences.

Chemical sciences mainly analysis and reactions, biological physics, energy research and fusion studies.

Varieties of applications:

Laser, X-ray technology, Nuclear Magnetic Resonance (NMR), Magnetic Resonance Imaging (MRI),
Electron Paramagnetic Resonance (EPR), Mossbaur spectroscopy, Laser atom cooling, Bose Einstein
Condensation (BEC), GPS system for navigation, Pollution detection, Various medical applications etc.

 Wide ranging scales make the field of Atomic & Molecular Physics more interesting today than it
was ever.
 We also see that the study of atomic and molecular physics is at the heart of every
interdisciplinary research.
 An understanding of the structure of atoms and molecules is therefore a prerequisite for
entering into several of the areas discussed earlier.
Various scales in Atomic and Molecular Physics:

In the following, we will come to know the characteristics of the atoms and molecules in various
conditions in terms of temperature, photon intensities and frequencies.

9
4
(Temperature range from 10 K to 10 K ) ~ 104 K

Fusion Plasma and stellar environment, Spectroscopy and dynamics of highly charged ions, Diagnostic
techniques for plasma ~ 10K

Molecular interactions in astrophysical ices, Formation of complex molecules in interstellar

environment, Fundamental question on formation of molecules which have relevance to origin of life

~ 101 K
6
Atomic and Molecular beams, Clusters ~ 10 K
9
Laser cooled atoms, Atomic clock based on Cs fountain, Nano-fabrication using cold atoms, ~ 10 K
Quantum degenerate atomic gases, Bose-Einstein Condensation, Fermi Sea, Quantum many body
physics, Matter wave optics, Atom interferometry, Atomic Physics as basis of condensed matter physics

Photon intensities used for interaction:

 
109  103 W / cm2  Obtained from normal light sources

High resolution spectroscopy for structure of atoms and molecules

 
103  109 W / cm2  Obtained from laser sources

Multi-photon processes, Multi-step excitation processes, Nonlinear optical processes, Rydberg and
Autoionizing Levels, Ultra-trace analysis ( single atom detection),

 
109  1015 W / cm2  High intense laser pulse sources

Intense field regime, Above threshold ionization, Multiple ionization, High harmonic generation (up to
300), Coulomb explosion, Atomic Stabilization

3
Spectral Resolution used for spectroscopy: ~ 10 Hz
 16
Ultra precision measurements, Atomic Clocks of accuracy 1 in 10 and better, Ultra-precision
15
magnetometry ( 10 Tesla detection) ~ 100 Hz 106 Hz
Parity violation experiments in atoms and molecules (non-accelerator particle physics), Study of
hyperfine interactions, Hyperfine structure and Isotope shifts, Measurement of properties of unstable
nuclei (Nuclear Physics via Atomic physics), Cold atom physics ~ 106  109 Hz
Fine structure in atoms and molecules, Atomic & molecular Interactions, State selective processes in
atoms and molecules ~ 10  10 Hz
9 15

Spectrochemical analysis, Material characterization, Photoionization and photo-fragmentation,

supercontinuum sources and their interactions

Excitation sources used for modern research:

Table-top instruments to high energy particle accelerator

3
Lasers : 10 eV to 6 eV photons, used for Rotational, Vibrational and Electronic Spectroscopy
Synchrotron Radiation Sources : 5 eV to 1000 eV photons: used to study Valence to Inner-shell processes

Ion Traps and Atom Trap : Used to study precision measurement in neutral atoms to highly charged ions,
U+91 in electron beam ion trap, Study of non-neutral plasma

Particle Accelerators : This is used to study the interactions of charged particles of MeV energies with
atoms and molecules

Systems used for investigations:

A few atoms and ions :

Precision measurements on unstable nuclei produced in an accelerator, Quantum Information

Processing using atoms

Small sized clusters :

Metallic and semiconductor clusters, Au 40 , Si20Ge20 , Approach to bulk properties, Basic for
functional materials

Large sized clusters :  H2On ,  Xe n , etc, n = 1000 - 5000

Used to understand the Van der Waals complexes, solvent interactions in gas phase

103 number of cold atoms or ions : Cold atom physics, Bose Einstein Condensation etc
Gas/liquid phase : Spectroscopic analysis, trace analysis, pollution detection, chemical and biochemical
interactions

In the following, some revolutions in the field of research and applications are highlighted

 The advent of laser opens up a new arena in many disciplines of science and technology.
 The power and precision of lasers have revolutionized the field of atomic physics and molecular
physics.

For example, lasers have made possible entirely new technologies for isolating individual atoms in
electromagnetic traps and cooling them to near absolute zero. This is known as Laser Atom Cooling.

The Nobel Prize in Physics 1997 was awarded jointly to Steven Chu, Claude Cohen-Tannoudji and
William D. Phillips "for development of methods to cool and trap atoms with laser light".

Briefly, when the atoms are brought essentially to rest in the trap by using laser, they can undergo a
quantum mechanical phase transition to form a superfluid.

This is known as a Bose-Einstein condensation, while remaining in the form of a dilute gas. This is a new
state of matter where all the atoms are in the same coherent quantum state. As a consequence, the
atoms lose their individual identities, and their quantum mechanical wavelike properties become
dominant.

This ohere t ea of ato s a e used to for a ato laser a alogous to the ohere t ea of
photons in a conventional laser.

The potential of this future technology hopefully can be exploited for the fabrication of microelectronic
and other nanoscale devices.

This can well be used for the development of quantum computer, the dream of many scientists.

Due to the high precision of lasers, it dramatically increased the precision with which the characteristic
wavelengths of atoms can be measured.

Modern standards of time and frequency are based on measurements of transition frequencies in
atomic cesium.

An atomic clock is an oscillator whose frequency is locked to the frequency of an atomic transition

The second is the duration of 9 192 631 770 periods of the radiation corresponding to the transition
between the two hyperfine sublevels F = 4 and F = 3 of the ground electronic state of cesium 133

These two sublevels correspond to parallel and anti parallel orientations of the spins S = 1/2 of the
valence electron and I = 7/2 of the nucleus of the Cs atom
In 1930s, I.I. Rabi and his students, at Columbia University invented this technique known as magnetic
resonance, by which they could measure the natural resonant frequencies of atoms. Rabi won the 1944
Nobel Prize for his work.

I 1949, Ra i’s stude t Nor a Ra sey suggested that aki g the ato s pass t i e through the
oscillating electromagnetic field could result in a much more accurate clock. In 1989 Ramsey was
awarded the Nobel Prize for his work.

The discovery and the technology development of this atomic clock lead to the most important
application in today’s orld, a glo al syste of a igatio k o as Glo al Positio i g “yste GP“ .

Researchers at the Lincoln Laboratory of the Massachusetts Institute of Technology (MIT) were able to
deter i e the satellite’s or it pre isely y o ser i g Doppler shift of its radio sig al. “i e the satellite’s
orbit could be precisely determined from the ground, it established that positions on the ground could
also be determined by homing in on the signals broadcast by satellites.

On June 26, 1993, U.S. Air Force launched the 24th Navstar satellite into orbit, completing a network of
24 satellites known as the Global Positioning System, or GPS.

This i redi le e te h ology as ade possi le y usi g the orld’s ost a urate ti epie es:
atomic clocks that are precise to within a billionth of a second.
In this system, 24 satellites are orbiting 11,000 miles above Earth emits coded signals. Four atomic clocks
in each satellite keep accurate time.

Usi g Doppler shift, re ei er o the earth’s surfa e al ulates latitude, longitude, altitude, and time by
comparing signals from satellites.

This determines the location on the ground, accurate to within 30 meters, or 100 feet.

The Atomic spectroscopy is an important tool in Astrophysics. The analysis of the chemical composition
from the spectrum recorded from the heavenly bodies proved many theoretical predictions.

Supernova SN1987A was seen in February 1987. It occurred in Large Magellanic Cloud, 163,000 years
ago. Observing the star before the explosion proved the theory that core-collapse of a massive star
produ es super o a. The spe tru o ser ed fro this super o a sho ed the o positio of the star’s
outer layer. The analysis revealed an over abundance of nitrogen relative to oxygen and carbon as
compared to the sun which is the signature of CNO hydrogen fusion cycle.

Plasma, the fourth state of matter is an interesting research field to the scientist. Creating super hot
solid plasma state is a challenging task and provides greater understanding of fusion processes.

Resear hers orki g at the U.“. Depart e t of E ergy’s DOE “LAC Natio al A elerator La oratory
ha e used the orld’s ost po erful X-ray laser to build the first atomic X-ray laser pulse, as well as to
create in a controlled way the superheat (2-million-degree) piece of matter.

The atomic laser could be used to understand the working of biological molecules.

The creation of hot dense matter by intense laser pulse could be exploited to understand the processes
of nuclear fusion that power the sun.
Molecular spectrum is the signature and the fingerprint to identify the molecules. This has a deeper and
direct application to our human society.

Now-a-days several spectroscopic methods are used in medical science for diagnosis the disease. In the
following, a glimpse of these methodologies is given.

X-rays: the most common instrument used almost everywhere.

The first X-ray device was discovered accidentally by the German scientist Wilhelm Roentgen (1845-
1923) in 1895.

He found that invisible rays emitted from cathode-ray tube that penetrate paper and wood but could
not penetrate metal and bone. Roentgen used his device to examine the bone structure of the human
hand.

X-rays are produced when a target metal (such as tungsten) is bombarded by highly accelerated
electrons. These high energy electrons knock out the electrons from the deep energy levels such as K
and L shells, the other electrons in higher energy levels occupy these vacant spaces by radiating extra
energy in the form of X-rays.

X-rays penetrate the body and the image is stored on silver halide films

Bones and metals absorb or reflect X-rays – leaving the impression on the film, whereas the soft tissues
transmit X-rays. This contrast produces an image of bone or metal deep inside the body.

This helps to identify medical problems inside the body such as fractures of bones etc.

CT Scan or CAT Scan

The scanning mechanism is incorporated by involving a moving target or by revolving the X-ray source.
The scintillator, detector for X-ray, is used to pick up the signal and produced the image. By
superimposing several images, 2-dimensional and 3-dimensional images are computed.

Positron Emission Tomography This device measures the metabolic activity by measuring the decay of
the radioactive traces injected from outside in tissues. Fluorine 18 is used as radioactive element.

Diseased organs process the injected FluroDeoxyGlucose (FDG) at a higher rate than the normal tissues.
Positrons are emitted by FDG and emit g-radiation when collide with electron. g-detectors pick up the
signal and compute a 3-dimensional image of the body.

In this way, this methodology helps to identify the location of the diseased organs deep inside the body.

The scanner is typically a large, box-like machine with a hole, or short tunnel, in the center. The X-ray
tube is rotated and electronic detectors are located opposite each other in a ring, called a gantry. The
computer workstation processes the imaging information.

Raman Spectroscopy in medical science: When the monochromatic light interacts with molecular
vibrations, phonons or other excitations in the system, it results in the energy of the photons being
shifted up or down. The shift in energy gives information about the vibrational modes in the system.

The Raman Effect occurs when light interacts with a molecule. The light excites the molecule from the
ground state to a virtual energy state. When the molecule relaxes it emits a photon and it returns to a
different rotational or vibrational state. The difference in energy between the original state and this new
state leads to a shift in the emitted photon's frequency away from the excitation wavelength.

Raman spectroscopy is an invaluable technique for investigations of pharmaceutically and medically

relevant molecules. It is used in many fields where non-destructive microscopic chemical analysis and
imaging is required.
Both Biologists and Chemists use Raman Spectroscopy to identify chemical compounds, their functional
groups, and to determine the conformation of complex biomolecules, such as proteins and DNA.

The Raman and Surface Enhanced Raman Spectra can be exploited for biosensors.

1. The Raman spectrum of DTNB (1 mM DTNB in d2H2O);

2. SERS spectrum of BSA-IgG-AuNP;
3. SERS spectrum of TNB-BSAIgG- AuNP. Radiation of 633 nm was used for excitation.
Nuclear Magnetic Resonance (NMR) / Magnetic Resonance Imaging (MRI)

A nucleus with non-zero spin has angular momentum and a magnetic moment such as 1H, 31P, 13C, 19F

This nuclear magnetic moment interacts with the external magnetic field.

In resonance condition, this absorbs the energy.

To obtain the image: vary the external field as a function of position to localize signals.

This method is used to acquire the image inside the body especially inside the brain. Having the image
from different angles, the medical problems are located.

Matter is ade of fu da e tal uildi g lo ks , idea a e fro a ie t Greeks.

They speculated that earth, air, fire, sky and water might form the basic elements from which the
physical world is constructed.
They also developed various schools of thought about the ultimate nature of matter. Perhaps the most
remarkable was the atomist school founded by the ancient Greeks Leucippus of Miletus and Democritus
of Thrace about 440 bc.

For purely philosophical reasons, and without benefit of experimental evidence, they developed the
notion that matter consists of indivisible and indestructible atoms.

Today, we have come a long way developing many thoughts and ideas, carrying out several
experimentations and producing lot of evidences.

An understanding of the structure of atoms and molecules is therefore a prerequisite for entering into
several of the areas discussed earlier.

The basic atomic and molecular physics is the scientific study of the structure of the atoms and
molecules, its energy states, and its interactions with other particles and with electric and magnetic
fields.

Recap
In this lecture, we have understood the importance of the Atomic and Molecular Physics.

This subject is important to understand for the development of Quantum Physics.

The basic research in this field of research helped to develop methodology to understand the insight of
many other fields of research.

The concept developed in this field helped to develop many devices for medical and household
applications.

In the following lectures, we will go through the chronological development of the subject starting from
400 BC.
 Lecture – 2
Objectives : In this lecture we will go through the chronological development of the Atomic
physics. We will find out the thoughts and philosophical minds of ancient scientist

WE will come to know how the observations helped to develop the concept of atom.

Let us start from ancient thoughts of atom around 500 BC.

Ancient History of Atom

 The ancients have hypothecated that matter is made out of atoms for many millennia.
 The ord "ato '' o es fro the Greek ord a-to io hi h ea s u utta le'' coined by
the Greek philosopher Democritus of Adbera (Northern Greece) around 500 B.C.
 Democritus proposed that all material things are composed of extremely small irreducible
particles called atoms.

Democritus by Agostino Carracci (Ref: http://www.intermed.it/liceo/materiali/img)

However, the atomic theory was rejected by Aristotle, and thus, by almost everybody else for the next

two millennia

Aristotle (384 B.C. - 322 B.C.) Greek Philosopher

(Ref: http://space.about.com/od/astronomerbiographies/ig/Aristotle-Pictures-Gallery/Aristotle-from-
The-School-of-A.htm)
Development of Concept of Atom (17th through 19th Centuries)

 Robert Boyle (England) extended mathematics to chemistry and revived atomic theory.
 For him chemistry was the science of the composition of substances, not merely an adjunct to
the arts of the alchemist or the physician.
 He visualized elements as the indecomposable constituents of material bodies; and made the
distinction between mixtures and compounds.
 He further proposed that the elements were ultimately composed of particles of various sorts
and sizes, however, they were not to be resolved in any known way.

(1627-1691) Robert Boyle (England) (Ref: http://en.wikipedia.org/wiki/Robert_Boyle)

In 1666:

 Our modern understanding of light and color begins with Isaac Newton from series of
experiments that he published in 1672.
 He is the first to understand the rainbow — he refracts white light with a prism, resolving it into
its component colors: red, orange, yellow, green, blue and violet.
 This band is called a spectrum. This is the beginning of spectroscopy.

Sir Isaac Newton (1642-1726)

 (Ref: http://www.webexhibits.org/colorart/bh.html)

In 1749:

 Thomas Melvill(e) described how he had used a prism to observe a flame colored by various
salts.
 He reported that a yellow line was always seen at the same place in the spectrum; this was
derived from the sodium which was present as an impurity in all his salts.
 He is known as the father of Flame Emission Spectroscopy.

(Ref: http://en.wikipedia.org/wiki/Thomas_Melvill)

In 1777:

In 1780: Charles Coulomb (France) described the force between two electric charges with a
mathematical formula which looked er u h like Ne to ’s la of gra it :
 q1q2
FK
r2

Here, F is the force, K is a constant, q1 and q2 are two charges, r is the distance between them.

This force is attractive when charges q1 and q2 have opposite signs and repulsive when the charges
have the same sign.

In 1800: William Herschel discovers the Infrared Light.

His experimental setup for the detection of invisible solar radiation

In 1801: Thomas Y oung established the wave theory of light.

In 1802: William Wollaston discovers the Solar Absorption Lines.

 Wollaston was the first to employ a narrow slit rather than a circular aperture, or pinhole, prior
to the prism.
 With the slit positioned parallel to the refracting edge of the prism, he was able to observe a
number of black lines in the solar spectrum.
 He surmised that these lines were the boundaries between the primary colors of the
rainbow. He labeled several of the strong lines (A-E) and even some of the weaker ones with
lower case letters.

But Wollasto ’s i terest as i the olors the sel es, a d ot the dark li es, so he let the atter drop.

In 1803: John Dalton (England) formulated the modern version of the atomic theory. In his model:

 Matter is made up of small indivisible particles, called atoms.

 All atoms in a given chemical element are exactly alike, while the atoms of different elements
differ by atomic weight.
 Atoms can neither be created nor destroyed.
 A chemical reaction is just a simple rearrangement of atoms and the same number of atoms
must be present before and after the reaction.
In 1814: Joseph von Fraunhofer observes the solar spectral lines using an early version of the
spectroscope.

In 1821: Joseph von Fraunhofer builds the first diffraction grating, composed of 260 close parallel wires.

In 1814, Fraunhofer invented the spectroscope.

Solar spectrum with Fraunhofer lines as it appears visually

In 1827: Sir David Brewster produces absorption spectra in a laboratory.

He contributed in many ways in the field of optics:

 The laws of light polarization by reflection and refraction, and other quantitative laws of
phenomena.
 Experiments on the absorption of light. In this line of investigation, the prime importance
belongs to the discovery of the connection between the refractive index and the polarizing
angle; biaxial crystals, and the production of double refraction by irregular heating.
 Discovery of Subatomic Particles
In 1832: Michael Faradey showed that chemical changes occur when electricity is passed through an
electrolyte. He stated that electricity is made up of particles called Atoms of Electricity.

In 1891: Later, G. J. “to e suggested the a e Ele tro , fu da e tal u it of ele tri harge, to
des ri e the ato s of ele tri it , Mi hael Farada ’s 8 e peri e t.

In 1897: In 1897, J. J. Thomson determined the charge/mass ratio of these cathode ray particles
ele tro s a d fou d the alue of

e  1.76 1011 Coulomb

m Kg

In 1849: Leo Fou ault oti ed that Frau hofer’s D li e i the “u orrespo ded ith the right
yellow-orange line in lamps. To show that the two lines matched, he passed sunlight through the arc of a
lamp in order to view the superimposed spectra. To his surprise, he found that the absorption lines in
the solar spectrum became stronger. Additional experiments using carbon arc lamps showed that a
given medium could produce either emission of absorption lines.

Emission spectrum for sodium, showing the D line

In Mid 1850's: Farade studied ele tri al dis harge i partiall e a uated tu es, k o as Cathode
Ra Dis harge Tu es .

Conclusions drawn from these experiments:

 Cathode Rays start from cathode and move towards anode.

  The behavior of cathode rays is similar to negatively charged particles, so cathode rays consist of
egati e harge parti le alled ele tro s .
 Cathode rays ionize the gas through which they pass.

In 1853: Anders Angström measures the hydrogen spectral lines.

Hydrogen Spectra

 The Swedish physicist Anders Jonas Ångström presented similar theories about gases having
spectra in his work: Optiska Undersökningar to the Royal Swedish Academy of Sciences
 He pointed out that the electric spark yields two superposed spectra. Ångström postulated that
an incandescent gas emits luminous rays same as those it can absorb — a fundamental principle
of spectrum analysis.

In 1860: Gustav Kirchhoff and Robert Bunsen develop the Bunsen-Kirchhoff spectroscope that uses
both a slit and a collimator. This is the first spectroscope.

Gustav Kirchhoff (left) and Robert Bunsen (right)

In 1861: Bunsen and Kirchhoff performed experiments.: Co lusio : The dark li es i the solar
spectrum, observed by Wollaston and Fraunhofer, arise due to the absorption of light by gases in the
solar at osphere that are ooler tha those e itti g the light .

In 1860: Gustav Kirchhoff develops his spectral laws and the black body problem.

Kirchhoff's three laws of spectroscopy

 A hot solid object produces light with a continuous spectrum.

 A hot tenuous gas produces light with spectral lines at discrete wavelengths (i.e. specific colors)
which depend on the energy levels of the atoms in the gas.
 A hot solid object surrounded by a cool tenuous gas (i.e. cooler than the hot object) produces
light with an almost continuous spectrum which has gaps at discrete wavelengths depending on
the energy levels of the atoms in the gas.

In 1862: Anders Angström observes hydrogen in the spectra of the Sun.

In 1868: Anders Angström publishes a compilation of all the visible lines in the solar spectral.

In 1882: The beginning of a new era in the analysis of the spectra.

 Rowland constructed a ruling grating and published a photographic map of solar spectrum.
o
ten millionths of a millimeter, known as Angstrom unit. 1   108 cm  1010 m

Diffraction Grating

In this lecture we have gone through the chronological development of the concept of Atom.

Various philosophical thoughts and experimental observations helped to put them together and
provided the basic understanding of light and matter. In the next lecture we will find out the need
for quantization of light and matter.
 Lecture – 3
Objectives In this lecture, we will start in the year 1885 when the first observation of matter
quantization started. We will see that how the development of different model of atom emerged
from different experimental observations. We will come to know that the quantization of matter
was the heart of the model for atom.

In 1885: J. J. Balmer, despite being a mathematician, arrived at an empirical formula for computing the
visible spectral lines of the hydrogen atom measured by Angstrom.

h m2
 2 2
m n

for n  2, h  3.6456 107 meter and m  3, 4,5,6, and so forth.

Balmer predicted several lines with the help of this formula, those were confirmed by his colleagues,
Hermann Wilhelm Vogel and William Huggins. The best agreement for the Balmer series was,

o o
for m  3 H  6562.08   calculated  6562.10   observed 
o o
for m  4 H   4860.8   calculated  4860.74   observed 
o o
for m  5 H   4340.0   calculated  4340.10   observed 
o o
for m  6 H   4101.3   calculated  4101.2   observed 
In 1888 Rydberg

 In search of a general formula, Rydberg found that if the frequency of a series be plotted against
the consecutive whole numbers, a smooth curve which is approximately a displaced rectangular
hyperbola is the result.
c
 He attempted a solution of the form,  n    
n

1
n   wave number of a given line (cm -1 ).
n
  , c,  are the constants.
n=2, 3, 4, .....

This formula did not provide the desired accuracy for an entire series, he revised this equation,

N
 n   
n   
2

N ,   Constants,    Limit of the series.

The important fact about the formula is that N takes the same value in all series in all elements. It is
interesting to observe that, by placing   0 , it edu es to Bal e ’s fo ula fo h d oge ato .

N is later known as Rydberg constant R  1.097 107 m1 .

R
 T  n  is called the term values. So, any line of hydrogen atom spectrum is the difference between
n2
two term values, known as Rydberg-Ritz combination principle.

1  1 1 
  T  2   T 1  R  2  2  n1 and n2 are the integer numbers.
  n1 n2 
Following tables provide different series for hydrogen spectrum:

n1 n2 Name Lowest line Convergence toward

1 2 Lyman 121.50 nm 91.13 nm  UV 
Series
2 3 Balmer 656.14 nm 364.14 nm  VIS 
Series
3 4 Pashan 1874.67 nm 820.14 nm  IR 
Series
4 5 Brackett 4050.22 nm 1458.03 nm  Far IR 
Series
5 6 Pfund 7456.09 nm 2278.17 nm  Far IR 
Series
6 7 Humphreys 12365.64 nm 3280.56 nm  Far IR 
Series

20th Century

In 1900:

 Max Planck (Germany) introduced the quantum theory to explain the shape of the curve
(temperature versus color) of a glowing solid.
 He found that light cannot be converted into heat (energy) by any arbitrary amount, but only as
discrete packets which he called quanta (known as photons today). For light of wavelength  ,
the energy per quanta is given by:

hc
E


where h is a o sta t hi h e o alled Pla k’s o sta t.

and value of h  6.6262 1034 Joule  sec

In 1905: Albert Einstein (Germany, USA) published papers on special relativity which included the
famous equation relating energy E to mass m :

E  mc 2

Here, c is the speed of light. Thus, the mass of any particle has an equivalent energy and a photon,
viewed by Planck as a packet of pure energy, has an equivalent mass.

In 1904: J. J. Thomson proposed a odel of ato . According to this model:

 Electrons are embedded within spherically distributed, positive charge.

 Both positive charge and the mass of the atom would be more or less uniformly distributed over
its size.
 Tho pso ’s odel as o pa ed to a British dessert called plum-pudding, and hence the name
plum-puddi g odel. Tho so ’s pape as pu lished i Ma h 9 editio of the
Philosophi al Magazi e , the leadi g B itish Jou al of the da .
 I Tho pso ’s ie …..the ato s of the ele e ts o sist of a number of negatively electrified
o pus les e losed i a sphe e of u ifo positi e ele t ifi atio ….. .

o
Approximately 1010 meters  1   0.1 nanometer

Problems of this model:

 How does the atom emit radiation ??

 This model was disapp o ed late Ruthe fo d’s Gold foil e pe i e t.

In 1909: R. A. Millika de eloped the fa ous Oil-D op E pe i e t to dete i e the ha ge of the

electrons from the charge of the oil droplets and found that the charge is integrated multiple of
electrical charge.

1.6 1019 Coulomb ; the change of electron.

Also, with the help of this experiment, the mass of the electron was calculated as

m  9.10 1031 Kg

In 1909: Ernest Rutherford (England) demonstrated that the atom is mostly empty space with a small
positively charged nucleus containing most of the mass and low mass negatively charged particles
Tho pso ’s ele t o s o iti g this u leus. Rutherford could experimentally identify nuclear particles
with positive charge that he called protons. Although he could explain the charge of atomic nuclei with
the right number of protons, the mass of the nucleus for large atoms was always larger than the sum of
its protons. Therefore he postulated the existence of a neutral particle with a mass nearly the same as
the proton which, when added to the protons in the nucleus, would give the right mass. Rutherford
called this hypothetical particle the neutron. Late 9 Ruthe fo d’s olleague Ja es Chad i k as
able to detect the neutron experimentally.

The Rutherford Experiments

Rutherford discovered  (alpha)-particles (nuclei of helium atoms with +2 charge))

In 1909, he with co-workers (Hans Geiger and Ernest Marsden) experimented with streams of alpha
particles passing through a thin gold foil.

The foil thickness was ~ 8.6 106 cm

Concept of the Experiment:

Experimental Result:
Observations: Almost all  particles went through the gold foil with very slight deflections.

A very, few  particles were reflected – scattered by more than of 90 .

Conclusions:

 Since most  particles passed through the atoms without being deflected - An atom must be
having mostly empty space.
 The  particles occasionally strike a small strongly scattering region. This region could be a
concentrated positive charge.
 Since atoms have no overall electrical charge (atoms are neutral), there must be just enough
negatively-charged particles outside the nucleus to just balance the positively-charged nucleus.

Therefore,

 The Rutherford's experiment suggested that the atom consists of mostly empty space with a
very small positively-charged nucleus, outside which are just enough negative charges to equal
the positive charge in the nucleus.
 Since the electrons do not crash into the nucleus but exist in stable atoms, this suggests a
planetary model with negatively charged electrons circulating around a positive core.

Planetary Model
 Positive charge in the center of the atom with almost all mass concentrated within this positive
charge - nuclei.
 Electrons - negative charge- are attracted to the nucleus about which they orbit (just as planets
orbit the sun due to attractive 1 force).
r2
 Sizes
o nuclei ~ 1014 m
o atom ~ 1010 m (from the mass density and number of atoms in a mole – A ogad o’s
number)
The problems of this model:

 Since electron travels in a circular orbit, it is constantly accelerated (even though its speed is
constant.) Thus, the electron emits Electromagnetic radiation, which carries away energy. The
energy of the atoms is reduced. Thus the atom has a lower potential energy and moves closer to
the nucleus.

 The Other problem with this model is that the spectrum of the emitted EM radiation would be
continuous. Classical approach gives the following expression:

1
 e2c 2  2
1 1
  
16  0 m 
3 3 3
2 2
r r

o As r decrease, the emission wavelength changes continuously, so this model predicts

that the emission spectrum of atoms is broad.
o But sharp spectral lines are observed, not a continuum.
o Thus, classically, the Rutherford Atom is Unstable.

In 1913: Neils Bohr (Denmark) developed the first successful model of the atom. Taking the picture
f o Ruthe fo d’s odel, Boh fi st i t odu ed the e e g le el ua tizatio of ato o side i g the
following assumptions:

 An atom consists of a dense stationary positively charge nucleus situated at the center with the
negatively charged electron revolving around it in circular orbits without emitting energy. The
force of attraction between these charged particles is electrostatic which is equal to the
centrifugal force on the rotating electron.

1st Postulate: By Coulomb's Law, Electrostatic attractive force and Centrifugal force acting on the
1 Ze2
electron 
4 0 r 2
 mv 2
Centrifugal force acting on the electron  where, Ze  Charge of Nucleus,
r ,

v  Velocity of Electron , r  Radius

mv 2 1 Z e2

r 4 0 r 2
Z e2
 v2 
4 0 mr
1 Z e2
 mv 2 
2 4 0  2r

2nd Postulate: An electron can revolve only in those orbits whose angular momentum is an integral

2 
multiple of h i.e.  . Electrons in these orbits are not changing its energy, these states are called
stationary states and the energies associated with these states are called energy levels.

where, h  6.6262 1034 Joule  sec is the Planck's constant.

mvr  n
n
v ;
mr
2
n 
2
Ze
  
 mr  4 0 mr

4 0 n 2 2
r
mZ e2
So, Radius of the Orbit
4 0 n 2 2  0 n 2 2
 2 
4 mZ e 2  mZ e 2

o
For hydrogen, Z  1 , The radius of the smallest orbit  r1  5.29 1011 m  0.529 

n2 o z cm
rn  0.529   Velocity v  2.18 108
z n s
3rd Postulate: An electron can jump from one stationary state to other either by absorbing the
energy by the process known as absorption or emitting the energy by the process emission. The energy
of the radiation should be corresponding to the energy difference between the two stationary states
involved in the process.

E  E f  Ei  h  hc


where, E f and Ei are the initial and the final energy states of the electron,  and  are the frequency
a d a ele gth of the photo s a o di g to the Pla k’s ua tu theo .

In 1913: Franck & Hertz independently proved the quantum nature of atomic energy levels.

The Franck-Hertz Experiment: The heated filament ejects electrons into the tube, which can be either
evacuated (vacuum) or filled with Hg vapor.

 A variable (positive) accelerating voltage, VA  , is applied to the grid (a wire mesh).
o The electrons acquire kinetic energy

K  eVA

 There is (negative) retarding voltage Vr  between grid and collector.

Only electrons having enough kinetic energy will overcome this potential and reach the Collector and
contribute to current measured with an Electrometer.

 If Vr  VA no electrons can reach the Collector, so no current would be measured.

 If Vr  VA , then, if the tube is highly evacuated, most of the electrons would reach the Collector,
and have energy e VA  Vr  .
 If the tube contains some gas, the electrons can loose energy via collisions with the gas atoms .
 Such collisions are inelastic, i.e. electrons lose energy, which is transferred to internal energy of
atoms in the gas.
 Thus, even in the case when Vr  VA , it is possible that the electrons would not be able to reach
Collector, and contribute to the current.
 Franck and Hertz observed the Collector current as a function of VA   Vr  when tube was filled
with various gases (result for mercury gas is shown here).
 At first, the current increased as was expected for a typical vacuum tubes, but at
~ 4.9 V current suddenly dropped.
 Then, the increase resumed until 9.8V , and so on.

Failures of Bohr Model

 Bohr model was a major step toward understanding the quantum theory of the atom - not in
fact a correct description of the nature of electron orbits.
 Some of the shortcomings of the model are:
1. Fails describe why certain spectral lines are brighter than others => no mechanism for
calculating transition probabilities.
2. Violates the uncertainty principal (discussed later) which dictates that position and
momentum cannot be simultaneously determined.
 Bohr model gives a basic conceptual model of electrons orbits and energies. The precise details
can only be solved using the Schrödinger equation (discussed later).

Correction for Motion of the Nucleus

 Spectroscopically measured RH does not agree exactly with theoretically derived R .

 But, we assumed that M  m  nucleus fixed. In reality, electron and proton move about
o o e t e of ass. Must use ele t o ’s edu ed ass  m  :

nM

mM

M 
 As m only appears in R , must replace by: RM  R  R
mM m
  It is found spectroscopically that RM  RH to within three parts in 100, 000 .
 Therefore, different isotopes of same element have slightly different spectral lines.
 Consider 1H (hydrogen) and 2H (deuterium):

1
RH  R  1.09677 107 meter 1
1 m
MH
1
RD  R  1.097074 107 meter 1
1 m
MD

 The wavelength difference is therefore:


  H  D  H 1  D 
 
 H 

 H 1  H 
R

 RD

 Called an isotope shift.

o
 H  and D are separated by about 1  .
 Balmer line of H and D.
 Intensity of D line is proportional to fraction of D in the sample.

Figure shows the Balmer line of H & D

Recap : In this lecture we understand the development of empirical formula by Balmer to describe the
hydrogen atom spectra. We now know the Thompson model for atom.

We know how this model was nullified by the experimental observation of Rutherford.

We see the planetary model of Rutherford and its drawbacks.

However, the independent experimental observations by Franck-Hertz further supports the idea of
quantization energies of matter.
 Lecture – 4
In this lecture, we will discuss the development of quantization of matter and light.

We will understand the need for quantum mechanics for describing the light matter interaction in the
microscopic level.

We will find the microscopic region where the wave particle duality is valid and application of
uncertainty principle in this regard.

We also find the development of famous Schrodinger equation to describe the quantization of
energy levels of atoms.

In the last two lectures, we have gone through the chronological development of thoughts to understand
the matter (atom & molecules) and the radiation (light).
The motion of the matter in macroscopic domain (dimension  104 cm )
and the nature of light as wave are completely described by Classical Physics.

* In classical Physics,
(i) The events around us can be observed and directly measured with instruments.
(ii) There is a close link between our perception and the explanation.
(iii) For any dynamical physical system its state can be determined with the knowledge of its initial
state.
(iv) The matter (macroscopic quantity) is treated as localized entity with the state having defined
positions and velocities at any instant of time. So, the matter is having “particle nature” and
follows the Newtonian Mechanics.
(v) Radiation/light is treated as classical electromagnetic wave developed by Maxwell. This is the
kind of wave nature of light.

Maxwell’s Equations are:


E   Gauss ' s Law 
0
B  0
B
 E    Faraday ' s Law 
t
E
  B   0 J   0 0  Ampere ' s Law 
t
where, E & B are the electric and magnetic field components;
 is the charge density;
0 &  0 are the permeability and permittivity of the free space respectively;
1
and  0 0 
c2
In free space, i.e. no charge and current, Maxwell’s equations become,
 B
E  0 ;  E  
t
1 E
B  0 ;  B 
c2  t
Decoupling the electric and magnetic field from the above equations
1 2 E 1 2 B
2 E  ; 2 B 
c2  t 2 c2  t 2
Solution of these are,
E  x, t   E0 e 
i Kx  t 
j

B  x, t   E0 e 
1 i Kx  t 
k
c

2
where K  is the propagation constant.

In the beginning of the 20th century, several experiments and observations could not be explained by
Classical Physics. These are
(i) Photoelectric effect
(ii) Compton effect
(iii) Phenomena on atomic scales such as classical explanation of Rutherford model, discrete energy levels
of atoms proposed by Bohr.
These facts forced the scientist to search for a near explanation of the mechanics.

(i) Photoelectric effect:

In 1886 and 1887, Heinrich Hertz showed that an electric discharge between the two electrodes
shown in the picture) occurs when ultraviolet light falls on one of the electrodes.
In this a metallic cathode and anode are placed in a vacuum chamber having a quartz (clear to UV
light) window. UV light having with frequency () is incident on cathode and the current generated
by this light is measured through a current meter.

Quartz
window
Ejected Incident
electrons light ()

Photo
cathode Anode

Current
meter
The first of these phenomena was discovered by Hertz and Hallwachs in 1887. The second was
announced first by Philipp Lenard in 1900

Observations:
(i) When the potential across anode with respect to cathode is varied, it is observed that after a
certain potential, the photocurrent starts and increased and slowly gets saturated.
(ii) The magnitude of the current depends on the intensity of the light.
(iii) Stopping potential depends on the frequency of the light. ( Kmax  maximum kinetic energy of
the photoelectron  eV0 ).

Photocurrent
I1
I2

+
- V0 0 +
Applied voltage

These observations cannot be explained by classical theory. The reasons are

(i) In the wave picture, the amplitude of the electric field E0 (fig 4.1) increases as the light intensity
is increased. The force exerted by this electric field on the electron is e E . It means the kinetic
energy of the ejected photoelectron should increase if the intensity is increased. However, from
the figure, it is clear that Kmax  eV0 which is independent of light intensity.
(ii) According to the wave theory, photoelectron should exit at any frequency of light if the exerted
force is greater than the binding force. However, observation is such that the photoelectrons for a
particular metal (cathode) are ejected only when the light frequency is greater than a particular
value, a cut off frequency  0 .

To overcome these discrepancies, Einstein took the idea given by Planck and assumed, that
 The light energy is a bundle of energy localized in a small volume of space.
 It remains localized even it moves with a velocity of light c. He termed the content of the
energy E as “PHOTON”, and is related to the frequency  .
E  h
 For the photoelectric effect, he assumed that one of such photons is completely absorbed by
one electron of the photocathode as if particle-particle interaction and derived the kinetic
energy of the electron.
K  h  W0

where, W0 is the work functions of the photocathode.

 The particle nature of light (quantization of radiation) was again realized to explain the
Compton’s experiment in 1923.

The X-ray of wavelength 0 was incident on a target. With a crystal diffractometer, the
wavelengths of the scattered X-ray were measured by changing the angle .

Scatter
(electron)

Scattering
angle ()
X-Ray
source
Scattered
Incident beam
beam Collimating
system
Crystal
(wavelength
selector)

Detector

 The scattered radiation consists of the primary wavelength 0 and a shifted wavelength  .
 The Compton shift     0 varies with the scattering angle.
 The classical theory predicts that if the radiation of wavelength  incidents on a particle, it
scatters and emits radiation of the same wavelength . No other wavelength is predicted by
this theory.
 Using the particle nature of the radiation, from the momentum and energy
conservation, the Compton equation is derived to explain the observation as,
h
  1  cos    c 1  cos  
m0c
h o
where, c   2.43 1012 meter  0.0243A
m0c

Details are discussed in the next lecture.

Dual Nature of electromagnetic radiation

 To describe the Compton observation, we need to treat radiation as localized particle, “Photon”. Here,
the radiation and matter interaction is particle-particle in nature.
 Wave picture is indeed required to explain interference, diffraction phenomena.
 In Compton’s experiment, the particle nature is used for the description of scattering. On the other
hand, the crystal is used to separate the wavelengths and this is based on diffraction (wave nature).
 Electromagnetic radiation behaves wavelike under some circumstances and particle like under other
circumstances. Both pictures cannot be used simultaneously.
 This wave particle dual nature not only exists for radiation. In fact subatomic particles also follow the
same.

Matter Waves :
In 1924, Louis de Broglie first proposed the existence of matter waves.
He supported the wave-particle dual nature of radiation and proposed the existence of matter
waves. In his hypothesis, he suggested that the wave aspect of the matter is related to its particle nature in
the same quantitative way that is in case of radiation.

The total energy  related to the frequency  of the wave.

E  h
and the momentum p is related to the wavelength  of the wave.
h
p

It is to be noted that the particle characteristics such as E and p are related to the wave characteristics like
 and   with Planck’s constant h.
It is interesting to see that, if we calculate the de Broglie wavelength of a cricket ball of mass 0.5
Kg at a speed of 100 m/sec.

h h 6.6 1034 J  sec o

    1.32 1035 meter  1.32 1025 A
p m v 0.5 Kg 100 m
sec

On the other hand the de Broglie wavelength of an electron with kinetic energy 100 eV.

6.6 1034 o
  1.2 1010 meter  1.2 A
5.4 1024 Kg  m
sec
o
If one has to measure these wavelength, the instrument with aperture a  1A .


 1.32 1025 for cricket ball
a

and  1.2 for electron
a
 
If  0 , the diffraction effects will be negligible and measurement is not possible.
a

So, what is the limit of measurement?

UNCERTAINTY PRINCIPLE

As discussed earlier, that in classical mechanics, the equation of the motion with given forces can be
solved by knowing the position and the momentum of the particle for all values of t.
To measure these observables one need to disturb the system. However for macroscopic particle,
this disturbance is small enough to ignore.
But for microscopic particle, simultaneous measurement can not be done beyond the accuracy
governed by Heisenberg uncertainty principle.
Precision of the measurement is limited by px x   h 
2  2 
where px is the uncertainty of knowing the component of momentum p in x-direction and x is the
uncertainty in locating the particle at coordinate x.

The second part is,

E  t 
2

where E and  t are the uncertainties of Energy E and time t.

This concept helps to understand the limitations of the classical theory and provides the regime where the
quantum mechanics is valid.

Failures of Bohr Model

Bohr model was a major step toward understanding the quantum theory of the atom - not in fact
a correct description of the nature of electron orbits.
Some of the shortcomings of the model are:
1. Fails describe why certain spectral lines are brighter than others => no mechanism for
calculating transition probabilities.
2. Violates the uncertainty principal which dictates that position and momentum cannot be
simultaneously determined.
Bohr model gives a basic conceptual model of electrons orbits and energies. The precise details
can only be solved using the Schrödinger equation.
From the Bohr model, the linear momentum of the electron is

 Ze2  n
p  mv  m  
 4 0 n  r

However, we know from Hiesenberg Uncertainty Principle, that

p ~ ~
x r
Comparing the two Eqns. above => p ~ np
This shows that the magnitude of p is undefined except when n is large.

o Bohr model only valid when we approach the classical limit at large n.
o Must therefore use full quantum mechanical treatment to model electron in H atom.

• One of Bohr’s postulates was the angular momentum of the electron is quantized, but there was
no explanation why the restriction occurred
• de Broglie assumed that the electron orbit would be stable only if it contained an integral number
of electron wavelengths

Idea is very similar to vibrations of a string tied both sides with wall.
Two nodes at the two ends
If these nodes join together, it becomes a circle and standing waves will generate nodes and antinodes.

• In this figure, three complete wavelengths are contained in the circumference of the orbit
• In general, the circumference must equal some integer number of wavelengths
– 2  r = n λ n = 1, 2, …
• The expression for the de Broglie wavelength can be included in the circumference calculation
– me v r = n ħ

This is the same quantization of angular momentum that Bohr imposed in his original theory

• This was the first convincing argument that the wave nature of matter was at the heart of the
behavior of atomic systems
• By applying wave theory to the electrons in an atom, de Broglie was able to explain the
appearance of integers in Bohr’s equations as a natural consequence of standing wave patterns
• Schrödinger’s wave equation was subsequently applied to atomic systems
 Schrodinger Equation :
In 1926, Schrodinger said, There is no reason to retain even Bohr’s electron orbits,
Basic equation governs wave motions and electron in a nuclear field.

If we consider, the electron as wave defined by de Broglie, we can treat the wave equation.

One dimensional wave propagation freely in space along x-coordinate

1  2 ( x, t )
2 ( x, t ) 
c2  t2

  x, t  represents the wave nature of the electron, WAVEFUNCTION

Since we are looking for a solution of stationary states, we separate the space (x) and time (t) part of the
wavefunction such as

  x, t     x  e2 i t

Now,

 2  2  2
 4 2  2  x  e2 i t and  e2 i t
 t2  x2  x2

Substituting in the wave equation we get,

d 2  x  4 2  2
   x
d x2 c2
4 2 p 2 c 2
   x
c2 h2

According to de Broglie wavelength,

c c pc h
   & p
 h h 
p

And the total energy (E) = kinetic energy + potential energy (V)

p2
V  E
2m
 p2  2 m  E  V 
Substituting this

d 2  x  2m
2
 2  E V    x
dx
2 d 2  x 
   E V    x
2 m d x2
2 d 2  x 
 V   x  E   x
2 m d x2

This is known as one dimension time independent Schrodinger Equation

For the quantum mechanical treatment, we will convert the classical dynamical quantities (px, py,
and pz ) to its corresponding quantum mechanical operators

  
px  i , p y  i , pz  i
x y z

E i
t

 Substituting we get

2
 2 2 2  
  2   2 
 V  x, y, z   i
2  x y z 
2
t

 Here, we introduce the WAVEFUNTION to represent the electron.

    x, y, z, t 

The wavefunction contains the information about the position and the time evolution of the
electronic motion. We will understand more about this later.

So operating equation -2, on the wavefuntion,     x, y, z, t  ,

  2   x, y , z , t   2   x , y , z , t   2   x , y , z , t  
2
  x, y, z , t 
      V  x, y , z    x , y , z , t   i
2  x 2
y 2
z 2
 t
2

 2  V   i
2 t
This Equation is known as Time dependent Schrodringer Equation, where

2 2 2
2    is the Laplacian operator.
x 2 y 2 z 2
The three dimensional Schrodinger Equation is
2 d 2  r  Figure-4.6
 V  r   E  r 
2 m d x2

If we take the potential of the electron due to

nucleus is

Ze2
V 
r
Where r is the distance between the electron and the nucleus and Z is the charge (Z = 1 for hydrogen).

Substituting the potential in the Scrodinger Equation,

the energy becomes

me4 z 2 1
En  
2 2 n2
Where n is known as the principal quantum number.
Details of this quantum mechanical calculation are given
later.

This energy is exactly the same energy expression

derived by Bohr. In this figure, E (n=1) = -110000 cm-1.

In this lecture, we came to know about the development of quantization of matter and light.

We came to know the need for quantum mechanics for describing the light matter interaction in the
microscopic level.

We understood the microscopic region where the wave particle duality is valid.

We also came to know how Schrodinger developed his famous Schrodinger equation.
Lecture – 5 Light – Matter Interactions
 In the previous lecture, we have learnt that the radiation or light is following
the Wave-Particle dual nature

 It can be treated as electromagnetic wave or particle nature like photon

 Similarly, the electrons can also be treated as particle and also as wave
corresponding to its momentum for describing the stable structure of atom.

 When both of them interact with each other, we have to understand the
mechanism to follow for describing the experimental observations such as Compton
effect, absorption and emission of light by atoms.

 In this lecture, the different kinds of treatment to understand the light-matter

interactions are described. We will start with the classical phenomenon and then proceed
to understand the quantum mechanical descriptions.

Classical treatment:
 In classical theory, we model the atom as a heavy nucleus with electron attached to it
with spring  the binding force between them.

 The resonant frequency for this system is 0

 If we treat the light as wave then the electric field can be represented as
E  E0 Sint

E E

t t
+

 The oscillating electric field will force the electron to oscillate. The displacement of
electron with respect to nucleus will produce an oscillating dipole.
 It is known that an oscillating dipole emit electromagnetic radiation with the same
frequency of vibration. This emission of light is known as scattering of light by matter.
 However, if the incident radiation frequency matches with the resonant frequency of
the system ( 0 ) then the resonance occurs. Energy transfer takes place.
 The oscillating dipole p(t )   e x(t )
Where e is the charge of the electron and x(t) is the time dependent displacement of
electron with respect to nucleus.
When this dipole oscillates, it emits radiation. As time passes by, due to the radiation loss
the emission dies or decays. This phenomenon can be modeled as a damping oscillator
whose solution will be x(t).
 The differential equation of motion of the damping oscillator with damping constant

x(t )   x(t )  02 x(t )  0
Where 02  k , here k is the force constant of the spring.
m
With the initial values i.e. at t = 0
the displacement x(0)  x0 and the velocity x(0)  0 , the solution is
[Cost  (
 (
)Sint ]
)t
x(t )  x0e 2
2
2 1
The frequency   (02  2
)
of the damped oscillation is slightly lower than the
4
frequency 0 of the undamped case.
 (
Taking  0 , we get x(t )  x0e Cos0t .
)t
2

Line profile of the emitted radiation

The damped oscillation x(t ) can be described as a superposition of monochromatic
oscillations with slightly different frequencies  and amplitude A( )

1
 A()e
it
x(t )  d
2 

1
The amplitude A( ) can be calculated by A( )   x(t )e
 it
dt
2 
The intensity
1
I (  0 )  A( ) A* ( )  I 0
(  0 )  ( / 2)2
2

x0
e-(/2)/t I(-0)

t
0 
Momentum of a Photon
E
Momentum vector magnitude  p 
c
E is the energy.
E h
p    h parallel to the direction of propagation.
c c

From relativity, we know that

E  m c2
p  mV
m0
m
2
1V
c2

E
p  mV  V
c2
Minkowski’s four dimensional space & time ( E & three comp. of p)
If the system is confined to a single particle so, E 2  p 2c 2 is invariant under changes of
ref. frame.
E 2  p 2c 2
E2 V2  2
 E  4 V c  E 1  2 
2 2 2
 c 
c  
 m2c 4 1  V 2 
2

 c 
m02 c 41  V 2   m2 c 4
   0
1  V 2   c2 
 
 c2 

Photon is a quantity of energy. If we consider photon as a particle, then the energy

E  mc 2 , with this infinite energy E .
So the only way of reconciling a speed V  c with a finite energy is to assume rest mass
m0  0 .
So, E 2  p 2c 2  0 ; pE
c
Rest energy  m0 c  0 for photon
2

So, K .E.  E  m0 c 2  E so for photon all energy is K.E.

Elastic Collisions of Photons – Compton Effect

The X-ray of wavelength 0 was incident on a target. With a crystal diffractometer, the
wavelengths of the scattered X-ray were measured by changing the angle .

Figure 1
Scatter
(electron)

Scattering
angle ()
X-Ray
source
Scattered
Incident beam
beam Collimating
system
Crystal
(wavelength
selector)

Detector

Scattered radiation is composed by two lines:

(i) a component at the incident wavelength 0 , called the
Thomson component. Scattered radiation has the same
frequency as the incident radiation.
(ii) a component of different wavelength   0   .

Conclusion from experiment

(i)     0 is always positive.
(ii)  is an increasing function of  .
(iii)  is independent of and the composition of the material
used for scattering.

Explanation
Elastic scattering between photons and free electrons (weakly bound to atoms can be
considered as free electrons) i.e. binding energy  h 0 .
Elastic Scattering  K.E. is conserved
X

Electron

O Z

Photon
h 0
Momentum =
c
Energy E  h 0

We have taken into account the fact that p & E are related by relativistic invariance
E 2  p 2c2  m02 c4 .
Before Collision After Collision
Energy h 0  h c h  h c
Photon 0 
0  h h h
Momentum h
c 0 along Oz c 
Energy  m0 c 2   m c2
Electron   p2c2  m02 c4 
Momentum = Zero p making an angle  with OZ

Conservation of energy and momentum

Energy h 0  m0 c 2  h   p2c2  m02 c4 
h 0 h
along OZ  cos   p cos 
Momentum c c
h
along OX 0 sin   p sin 
c
h 0 h
p cos    cos 
c c
h
  0  cos  
c
h
p sin     sin 
c
 Electron


Z

Photon
h 0
Momentum =
c
Energy E  h 0

h2 h2
2  0
cos   
2
p2    2
 2 cos 2 
c c

 02  2 cos2   2  0 cos  2 sin 2  

2
h
 2
c


c
 02  2  2  0 cos  
h2
2

 p c  h 2  02  2  2  0 cos  
2 2

2
From 1st equation p 2c 2  h  0    m0 c 2   m02 c 4
 
Equating these two,
  
2
h 2  02   2  2  0 cos    h  0    m0 c 2   m02 c 4
 
 h 2  0    m02 c 4  2h  0   m0 c 2  m02 c 4
2

 h 2 02  h 2 2  2h 2  0 cos   h 2 02  h 2 2  2h 2  0  2h  0   m0 c 2
 2h  0   m0 c 2  2h 2 1  cos    0

2h 2
  0   1  cos    0
2h m0 c 2
0  h
   1  cos   where m0  9.1 10 31 Kg
  0   0 m0 c 2
1 1 h
   1  cos  
 0 m0 c 2
h
   0  1  cos  
m0 c


  0 ;   0
h  2h
   1  cos      ;  
m0 c  m0 c
 h
  90 ;      Compton wavelength
o

 m0 c

So, we get
h
  0    1  cos 
m0 c
(i)  is positive.
(ii) independent of 0 .
(iii) depends on  only.

  1 pm
Hard X-ray
h  1 MeV

Energy of Compton Wavelength,

hc hc
  m0 c 2  rest mass of the electron
 h
m0 c
h 0  m0 c2 0     0 photons gives up very little energy.
h 0  m0 c2 0     0 photons gives up most of its energy.
 Absorption of Photons (Inelastic Collision)
Let us define h 12 is the energy difference between the two states of an atom with energy
E2 and E1 ( E2  E1 ground state) E2  E1  h12 .
If there is a collision between an atom and a photon and after the collision they form one
particle, then the initial momentum of the incident must be preserved by the final single
particle (momentum conservation). Or we can say that after collision the atom must
possess some kinetic energy that it did not have previously.
This kinetic energy can have been taken from the energy of the incident photon.
This is possible only when h  h12 . We have to determine the relationship between 
and  12 .
Atom

E2

Photon Atom - photon

Momentum = h system
c
Energy E  h E1

Considering the properties of the relativistic particles:

Before Collision After Collision
Energy h
Photon Momentum h
c
E1  m1 e2 W P c
2 2
 m22e4 
m1  rest mass
Atom Energy
Momentum Zero P
E2 E1  h 12
where, m2  
c2 c2

From the conservation of energy

h  E1  P c
2 2
 m22e 4      1

Momentum p  h same as photon      2 

c
E1  h 12  m2c 2

From (1)
  E1  h   p 2c 2  m22c 4
2

 E12  2 E1h  h 2 2  p 2c 2   E1  h 12 
2

h 2 2 2
 c  E12  2 E1h 12  h 2 122
c2
2h 12 E1  h 2 122   h 12 
  1     12 1  
2 E1h  2 E1h 12   2 E1 
 h 12 
  12 1  2
 2m1c 
So the incident photon frequency must be greater than the theoretical frequency of the
 E  E1 
spectral lines  2   12  .
 h 
h 12 1 to 10 eV 
2  1010
m1c 10 to 100 GeV 

Comment:
h 12
(i) In the optical transitions h 12  m1c 2 typically, 2
~ 1010 which means the shift
m1c
 
will be very small compared to other broadening 106 cannot be observed. Resonant

condition is applicable i.e. E2  E1  h .

(ii) When h 12 is not very small compared to m1c 2 , the shift is appreciable.

Emission of Photons:
Before Collision After Collision
Energy ~ h
Photon Momentum ~ h along Oz
c
Energy E2 W P c
2 2
 m12c 4 
Atom 0 p along Oz
Momentum E2 E E  h
m2  m1  1 2  2 2 12
c2 c c
 h
p 0  p 2 c 2  h 2 2
c
E2  W  h
 E2  h  W
 E22  h 2 2  2h E2  p 2 c 2  m12 c 4
 h 2 2  m12 c 4
 E22  2h E2  m12 c 4   E2  h 12 
2

 E22  2h E2  E22  h 2 122  2 E2 h 12

 2h E2  2 E2 h 12  h 2 122
2 E2 h 12 h 2 122 h 2
     12  12
2hE2 2 E2 h 2 E2
 h 12 
    12 1  2
 2m2 c 

Application to   rays
  rays  Very High Energy
1019 to 1022 Hz
Nuclear transitions also very high frequency
h12  m1c 2
Emission of   ray photon is interpreted as the radiative transition between two energy
states of the nucleus (analogous to optical transition).
Frequency Displacement  Line Width

Resonance absorption and emission is not possible as in the case of optical transition. By
increasing temperature it is possible. So to get the information about the nucleus from
this is difficult.
What Mössbaur discovered that by cooling the source and the absorber the intensity
absorption increased.
It means that, below a certain temperature emitted or absorbing nucleus is embedded in a
crystalline lattice and it is the white crystal which recoils.
Mass of Crystal  Mass of Nucleus ~ 6 1023
The velocity of recoil is negligible.
No recoil energy loss  extremely sharp lines (natural width) could be obtained.

Debye  Waller Factor

 E  3  2T 2  
f  exp   0   
 K  2  
where, T  Abs. Temp.
K  Boltzmann ' s Const.
  Degree Temp. of the Solid

There are three main hyperfine interactions that can be observed by Mössbauer
spectroscopy. They are (i) Isomer Shift, (ii) Quadrupole Splitting and (iii) Nuclear
Zeeman Splitting.

For example :
 
The isomer shift of Fe57 3  1  14.4 KeV in Ferricinium bromide is 2 108 eV .
2 2

h   0   h   2  108 eV
h 0  14.4 103 eV
 c

0 c  v
 v v
  
0 c  v c
 2 108
v c   3  1010
0 14.4 10 3

6 102
  0.04 cm
14.4 103 s

Mössbaur Spectrum of Ferricinium bromide