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Frank Rösch
Nuclear- and
Radiochemistry
Volume 1: Introduction
2nd, extended edition

Author
Prof. Dr. Frank Rösch
Institute of Nuclear Chemistry
Johannes Gutenberg University Mainz
Fritz-Strassmann-Weg 2
55128 Mainz, Germany
E-mail: [email protected]
ISBN 978-3-11-074271-8
e-ISBN (PDF) 978-3-11-074272-5
e-ISBN (EPUB) 978-3-11-074280-0
Library of Congress Control Number: 2022938840
Bibliographic information published by the Deutsche Nationalbibliothek

The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie;
detailed bibliographic data are available on the Internet at http://dnb.dnb.de.
© 2022 Walter de Gruyter GmbH, Berlin/Boston

Cover image: agsandrew/iStock/Getty Images Plus
Typesetting: Integra Software Services Pvt. Ltd.
Printing and binding: CPI books GmbH, Leck
www.degruyter.com
Preface
Except for the element hydrogen with its most common stable isotope 1H, the nuclei
of all atoms consist of mixtures of protons and neutrons.1 For certain well-defined
nucleon compositions (i.e. protons + neutrons), nuclei are stable – they exist forever.
This holds true for one or more nuclei of the isotopes of almost all chemical elements
(except technetium, Z = 43) ranging from hydrogen (Z = 1) to bismuth (Z = 83). Yet,
there are less than 300 stable nuclei altogether.
In contrast, all the known elements beyond bismuth (i.e. from Z = 84 to Z = 119)
and many of the lighter elements (i.e. from Z = 1 to Z = 83) have isotopes comprising
nuclei of nucleon compositions not suitable to stability. This means that there are
more than 3000 unstable nuclei that must transform into new nuclei of more stable
nucleon compositions. This textbook is about the many atomic nuclei and their
characteristic states that form the atoms composing our physical world: stable nu-
clei (K), nuclei with excited nuclear levels (⊙K), unstable nuclei (✶K), nuclei at
ground state (gK), or metastable states (mK).2
Radiochemical transformations proceed in an exothermic way. The velocity of a
transformation is expressed by a transformation constant and/or half-life.
The transformation itself is accompanied by the release of various kinds of
emissions. It is the velocities and emissions of these transformations that stand for
the phenomenon of “radioactivity”.
The understanding of basic nuclear and radiochemical processes is a prerequi-
site to exploring the potential of radionuclides and radioactivity as a source of en-
ergy, as tools in fundamental research and analytics, for environmental purposes,
for industrial applications, in medicine, etc. For example, nuclear fission is one of
the most important sources of electricity, while the beta- and alpha-decay processes
are the essence of several molecular imaging processes adopted in diagnostic nu-
clear medicine and for patient treatments, respectively. These and several other
topics are addressed in the second volume of this textbook.
The first volume of this textbook introduces the basic aspects of these pro-
cesses. It focuses on explaining the fundamentals, rather than on specific details
and mathematical treatments. Mathematics, and in particular (quantum) physical
models, are referred to only when conventional physics cannot explain an impor-
tant experimental observation.
Thus, this textbook serves as a guide to qualitatively understand the essence of
radioactivity, considering questions such as:
 H consists of a single proton.

 K = Kern (German for “nucleus”).
https://doi.org/10.1515/9783110742725-202
VI Preface
– What makes a nucleus stable (or unstable)?

– What is the “motivation” for an unstable nucleus to transform?
– What are the velocities of these transformations?
– What are the different primary routes of transformation?
– What is the rationale of each route?
– What are the consequences of primary transformation routes in terms of sec-
ondary pathways and post-effects?
– How is a particular route explained by both experimental evidence and theoret-
ical models?
– What are the main properties of the emissions (or “radiation”) released during
a transformation?
– How are the emission parameters of certain radionuclides adopted for practical
applications, making them valuable tools in research, and industrial and medi-
cal fields?
– And finally, how can some of the particularly important radionuclides be pro-
duced artificially?
The intention of this textbook is to illuminate the concepts of radioactive transfor-

mations. Excellent textbooks on nuclear and particle physics and quantum mechan-
ics are available for more detailed discussions of many of the phenomena. For a
comprehensive description of specific aspects of nuclear- and radiochemistry, the
six-volume, over 3000 page “Handbook of Nuclear Chemistry”, A Vértes, S Nagy, Z
Klencsár, RG Lovas, F Roesch (eds.), second edition, Springer, 2011, can be recom-
mended. Thus, this textbook may be useful for bachelor’s students who are inter-
ested not only in nuclear sciences, radio- and nuclear chemistry, radiopharmaceutical
chemistry, nuclear analytics, nuclear energy, but also in nuclear medicine.
This textbook may also assist professionals working in the latter field (chemists,
physicists, physicians, medical-technical assistants), who handle increasingly nu-
merous radioactive isotopes in diagnostic and therapeutic nuclear medicine.
Mainz, December 2013

Preface for the 2nd edition
Nuclear and radiochemistry is, compared to many other branches of chemistry, rel-
atively young. Beginning with Marie Curie’s identification of radium and coining of
the term “radioactivity”, the field of nuclear and radiochemistry is about 120 years
old (or young, if you will). Within this period, significant knowledge has been
gained. In the 12 years since the first edition of this textbook was published, no fun-
damental changes occurred which had to be considered in the present edition.
This second edition gives some modified explanations and makes several correc-
tions. I am extremely grateful to all the students and colleagues who added valu-
able comments.
If not indicated otherwise, data used throughout the first edition of this text-
book were from the AME2012 atomic mass evaluation. This database is regularly up-
dated, with new editions published in 2016 and 2020. The second edition of the
textbook refers to the 2020 database by M Wang et al., Chinese Phys. C 45 (2021)
030003 (https://iopscience.iop.org/article/10.1088/1674-1137/abddaf/pdf). Because
more and more the value of mass excess is preferred compared to mass defect,
the second edition highlights this value more than in the first edition (covered in
Chapter 2).
Finally, the readers’ attention is directed to the second volume of this teaching
book, which covers the many applications of nuclear and radiochemistry. An im-
pressive and steadily increasing number of chemists, physicists, physicians, tech-
nologists, radiation safety personnel, and many other professionals are handling a
variety of radionuclides for very different purposes. Volume 2 of the textbook is en-
titled NUCLEAR- AND RADIOCHEMISTRY: MODERN APPLICATIONS. Prominent sci-
entists illustrate in 13 chapters the most relevant directions, namely (1) Radiation
measurement, (2) Radiation dosimetry, (3) Elemental analysis by neutron activa-
tion, (4) Radioisotope mass spectrometry, (5) Nuclear dating, (6) Chemical specia-
tion of radionuclides in solution, (7) Radiochemical separations, (8) Radioelements:
Actinides, (9) Radioelements: Transactinides, (10) Nuclear energy, (11) Life scien-
ces: Isotope labeling with tritium and carbon-14, (12) Life sciences: Nuclear medi-
cine diagnosis, and (13) Life sciences: Therapy.
Vichuquen, December 2021 | Berlin, May 2022

Frank Rösch
https://doi.org/10.1515/9783110742725-203
Contents
Preface V
Preface for the 2nd edition VII
1 The atom’s structure I: Electrons and shells 1

1.1 The philosophy of atoms 1
1.2 The inner structure of the atom 4
1.3 The shell and the nucleus 7
1.4 Quantum mechanics 17
1.5 Mathematical explanations of the BOHR atom model 25
1.6 Outlook 32
2 The atom’s structure II: Nucleons and nucleus 37

2.1 The neutron 37
2.2 Nuclide notations and isotopes 39
2.3 Conventional parameters of the nucleus 42
2.4 Mass vs. energy of the nucleus: The mass defect 52
2.5 Outlook 57
3 Nucleons: Binding energy and shell structure 59

3.1 Stable nuclides and the Chart of Nuclides 59
3.2 Mass, mass defect, nucleon binding energy 62
3.3 The liquid drop model 68
3.4 The nuclear shell model 77
3.5 Outlook 91
4 From stable to unstable nuclides 95

4.1 Unstable nuclei and the Chart of Nuclides 95
4.2 Unstable nuclides on earth 100
4.3 Outlook 104
5 From stable to unstable nuclides: Mathematics 105

5.1 Transformation parameters 105
5.2 Correlations between radioactivity, number of unstable nuclides
and masses 111
5.3 Units of radioactivity 119
5.4 Classes of radioactive transformations 124
5.5 Outlook 140
X Contents
6 Processes of transformations: Overview 145

6.1 Transformation processes overview 145
6.2 Primary transformation pathways 150
6.3 Energetics 152
6.4 β-Transformation processes (ΔA = 0) 156
6.5 α-Emission, cluster emission, spontaneous fission processes
(ΔA ≠ 0) 164
6.6 Successive and simultaneous transformations 168
6.7 Secondary transitions 171
6.8 Post-processes 175
6.9 Outlook 176
7 β-Transformations I: Elementary particles 177

7.1 Elementary particles 177
7.2 Quarks 182
7.3 Elementary particles relevant to β-transformations 184
7.4 Quantum theory of β-transformation phenomena 193
7.5 Outlook 198
8 β-Transformations II: β−-process, β+-process and electron capture 199

8.1 Phenomenon 199
8.2 Energetics of β-transformations 201
8.3 Kinetic energetics of β-transformation products 206
8.4 Velocities of β-transformations 215
8.5 Selection rules 219
8.6 Excited states 227
8.7 Examples and applications 229
8.8 Outlook 235
9 α-Emission 239
9.1 Introduction 239
9.2 Mass balances in α-transformations 241
9.3 Pathways of α-emission 243
9.4 Energetics 246
9.5 Velocities of α-transformation 252
9.6 Quantum mechanics of α-transformation phenomena 256
9.7 Excited states 260
9.8 Example applications 262
9.9 Outlook 269
Contents XI
10 Spontaneous fission 277

10.1 Introduction 277
10.2 Occurrence of spontaneous fission 278
10.3 Pathways of fission 282
10.4 Energetics 294
10.5 Velocities of spontaneous fission 296
10.6 Follow-up processes of initial fission 298
10.7 Example applications 303
10.8 Outlook 304
11 Secondary transformations 307

11.1 From primary to secondary transformations 307
11.2 Photon emission 312
11.3 Conversion electrons 326
11.4 Pair formation 330
11.5 Energy and half life 331
11.6 Example applications of photon emission 334
11.7 Outlook 341
12 Post-processes of primary and secondary transformations 343

12.1 Post-processes paralleling primary and secondary nuclear
transformations 343
12.2 Post-processes due to the positron 346
12.3 Vacancies of shell electrons 354
12.4 Example applications of post-effects 363
12.5 Outlook 368
13 Nuclear reactions 373

13.1 Artificially produced radionuclides 373
13.2 General mechanism of nuclear reactions 376
13.3 Energetics 382
13.4 Yields of nuclear reaction products 388
13.5 Radionuclide production using neutrons 404
13.6 Radionuclide production using charged particles 414
13.7 Outlook 423
14 Appendix 433
Index 451
1 The atom’s structure I: Electrons and shells
Aim: The concept of atoms as the smallest, indivisible constituents of matter is in-
troduced. It arises from more than two millennia old Greek philosophy, reaches the
atom’s renaissance in the nineteenth century, and reflects the dramatic improve-
ments achieved at the beginning of the twentieth century.
Atoms are made of electrons, which exist in the shell of an atom, and a set of
different particles located in the atom’s nucleus. To understand the chemical prop-
erties of an atom, the electron shell structure – i.e. the number, characteristics, and
transitions of electrons in various shells – is essential. To a large extent, this under-
standing needs a significant reflection on quantum physics.
Developments of concepts of ancient and modern atom theory are introduced,
turning from the atomic philosophy of being the ultimate particle to concepts of
the atom being a substance of various, subatomic particles. The latter ideas are il-
lustrated as a scientific need to understand pioneering experiments in chemistry
and physics, i.e. to correlate experimental evidence and subsequent theoretical
explanation.
The latter is meant to serve as an introduction to (quite similar) considerations
relevant to the structure of nucleons in the atomic nucleus.
1.1 The philosophy of atoms
1.1.1 The beginning: Just philosophy
The concept of an atom was approached about 24 centuries ago when ARISTOTLE
(384–322 BC) suggested that all existing matter is built of four components: air,
water, fire, and earth. PLATO (427–347 BC) added a fifth element, the ether, which
allows for interaction and transformation between the others. The five Platonic sol-
ids are illustrated in Fig. 1.1. Interestingly, they are each composed of just one of
only three single abstract geometric figures (equilateral triangle, square, and a reg-
ular pentagon), which when assembled form the tetrahedron, hexahedron, octahe-
dron, icosahedron, and dodecahedron.
At almost the same time, the Greek philosopher LEUCIPPUS (ca. 450–370 BC) and
his scholar DEMOCRITUS (460–371 BC) proposed a material world made of indivisible
components. Assuming that every material could be divided into smaller parts, and
these again into even smaller fragments; finally, a level of indivisible things is
reached. They called them atomos, which is the Greek name of atoms, the indivisi-
ble. The philosophers ascribed them with defined properties, namely to be:
– very small,
– and thus invisible,
https://doi.org/10.1515/9783110742725-001
2 1 The atom’s structure I: Electrons and shells
– indivisible,
– hard,
– of different forms (however without color, taste, or smell),
– moving spontaneously and continuously (in an empty space, i.e. in vacuo or in
“ether”).
FIRE EARTH AIR WATER ETHER
tetrahedron hexahedron octahedron icosahedron dodecahedron
Fig. 1.1: The five Platonic solids. Each is composed of a number of identical isosceles surfaces:
tetrahedron (4 triangles), hexahedron (6 squares), octahedron (8 triangles), icosahedron (20
triangles), dodecahedron (12 pentagons).
To conceive of the ultimate building blocks1 as having “different forms” included the
elegant idea that the matter built of them finally reveals properties of the “atoms”,
which themselves remain invisible. Ultimately, the building blocks are not only the
composites of our material world, they are responsible for its properties.
1.1.2 2000 Years later: Experimental evidence
It took more than 22 centuries until this conceptual idea was proven experimentally.
Chemists like LAVOISIER (1743–1794), PROUST (1755–1826), and DALTON (1766–1844)
realized that individual chemical elements combine mass-wise to form compounds
according to a set of rules.
Conservation of mass (LAVOISIER): The overall mass represented by all reaction

partners remains constant. For a chemical reaction, the total mass is divided among
all the species involved and, in the case of complete reaction, the mass of all reac-
tion products is equal to the mass of the reactants. If hydrogen gas and oxygen gas
undergo the oxyhydrogen gas reaction, then e.g. 4 g of H2 reacts with 32 g of O2
(together making 36 g) to form 36 g of water. This experimental evidence is the law
of conservation of mass (see Tab. 1.1).
 It would become obvious only more than 2000 years later that this is not really true; it is more
the number and the internal infrastructure of a well-defined, but small group of subatomic building
blocks called “elementary particles” which define an “atom”. These constructs indeed define the
physical and chemical properties of atoms and chemical elements.
1.1 The philosophy of atoms 3
Law of definite proportions (PROUST): Species undergoing a chemical reaction com-

bine not stochastically, but in characteristic ratios. Today, we know that this is ac-
cording to the number of moles, which in turn represent the number of species. In
the case where the two gases hydrogen and oxygen react to form water, hydrogen,
and oxygen combine in molar ratios of 2:1. According to their individual masses, this
reflects a mass ratio of 1:8 of the initial reactants. This experimental fact constitutes
the law of definite proportions (see Tab. 1.1).
Tab. 1.1: The laws of conservation of mass and of definite proportions exemplified for the formation
of water out of the two gases hydrogen and oxygen. The ratio between the two elements is 1:8 if
masses are counted, and 2:1 if moles are considered. Using the AVOGADRO number to convert moles
into numbers of atoms, it is obvious that the overall number of atoms of the reactants (H2 and O2) is
the same for the product (H2O), and that the number of both hydrogen and oxygen atoms starting the
reaction did not change, even if the reaction product is chemically a completely different species.
 H +  O !  HO
mass  × ( ×  g) +  × ( ×  g) = × ( ×  + ) g = (:) g
mass ratio H:O = :
 g =  g
mol  ×  mol of H  ×  mol of O × ( mol of H +  mol of O)
molar ratio H:O = :
atoms  × .⋅ +

+  × .⋅ +
= x ( × .⋅ +
+  × .⋅+)
total  × .⋅+ =  × .⋅+
H  × .⋅+ =  × .⋅+
O  × .⋅+ =  × .⋅+
These chemical observations allowed DALTON (1766–1844) to develop a “modern”

theory on atoms. The fundamental postulates in 1808 were:
– chemical elements consist of extremely small particles, the atoms,
– all atoms of one specific chemical element are identical, while
– atoms of different elements are different,
– chemical reactions reflect the combination or separation of atoms,
– within these reactions, atoms do not disappear, i.e. are not destroyed or created,
– no atom of one chemical element can be transformed into an atom of a different
chemical element,
– a chemical compound is a combination of characteristic atoms of one (e.g. H2),
two (e.g. H2O) or more chemical elements,
– a specific chemical compound contains atoms in a fixed, compound-specific
mass ratio (see Tab. 1.2).
Tab. 1.2: Key messages of DALTON’S theory (“philosophy”) on atoms.
Atoms Atoms are extremely small particles composing chemical elements.
Atoms of the same element are identical.
Atoms of different elements are different.
Chemical A chemical compound is the combination of characteristic atoms of individual

compounds chemical elements.
A specific chemical compound contains atoms in a fixed, compound-specific

mass ratio.
Chemical A chemical reaction is the combination of atoms or the separation of atoms

reactions forming a chemical compound.
Within these reactions, atoms do not disappear, i.e. are neither destroyed nor
created.
No atom of one chemical element is transformed into an atom of a different

chemical element.
DALTON’S key point was the renaissance of the assumptions made by the Greek
philosophers more than two millennia ago. Chemical elements are made of atoms,
representing the smallest indivisible constituents of matter (Fig. 1.2).
1.2 The inner structure of the atom
1.2.1 The electron and the proton
The identification of electricity and electrolysis were key factors in the development
to make the “classical” atom “transparent”. These two effects appeared to be
completely new to science and stimulated new theories on the atom. FARADAY
(1791–1867) experimentally observed that electric current may disrupt chemical
compounds. STONEY (1826–1911) suggested the existence of “carriers of electric
charges”, and that those carriers were associated with the atom. In 1891 he called
them “electrons”. PLÜCKER (1801–1868) tried to conduct electric current through
vacuum and in 1859 observed cathode rays. THOMSON (1856–1940) systematically
analyzed these rays and realized experimentally that small, electrically-charged
particles – electrons – were emitted from the atoms of the cathode (see Fig. 1.3).
Independent of the type of hot cathode, the electron properties were the same.
1.2 The inner structure of the atom 5
ELEMENTS
Simple
1 2 3 4 5 6 7 8
9 10 11 12 13 14 15 16
I Z C L
17 18 19 20
S P G
Binary
21 22 23 24 25
Ternary
26 27 28 29
Quaternary
30 31 32 33
Quinquenary & Sextenary

34 35
Septenary
36 37
Fig. 1.2: DALTON’S “New System of Chemical Philosophy” describing the elements with individual
symbols and chemical compounds as individual elements interconnected in specific relationships
(stoichiometry), without losing their identity.
This was the experimental evidence of the existence of the electron. THOMSON2
even managed to measure the intensity of the electrons’ deviation in external electric
and magnetic fields. From these observations, he derived the first experimental value
for the charge-to-mass quotient of the electron, which today is q/m = − 1.759⋅108 C/g.
 JJ THOMSON received the Nobel Prize in Physics for this fundamental invention in 1906 “in recog-
nition of the great merits of his theoretical and experimental investigations on the conduction of
electricity by gases”.
partially evacuated
glass tube
– +
HV
(a)
+ –
HV
anode cathode fluorescence

gas discharge screen
(b) vacuum pump
Fig. 1.3: Gas discharge tube experiments. Electric current (HV = high voltage) conducted through
vacuum causes emissions – the electrons (a). Gas discharge of hydrogen gas causes a flux of
“naked” protons towards a fluorescent screen (b).
The most striking point to realize is that the electron itself is a subatomic parti-
cle, thus challenging DEMOCRITUS’S and DALTON’S concept of the atom as the ulti-
mate indivisible species.
Further experiments with similar devices, namely the gas-filled discharge tube,
soon revealed another form of particle emission. In 1886 GOLDSTEIN induced gas dis-
charge and detected positively charged components, which were emitted through a
hole inside the cathode (see Fig. 1.3). Similar to JJ THOMSON’S approach, the degree
of deviation of these positively charged ions of the gas (cations) by external electric
and magnetic fields could be analyzed. On the basis of hydrogen emissions, W
WIEN derived in 1897 a q/m value of + 9.58⋅104 C/g for this cation. He named it “pro-
ton”3 as a tribute to the ancient Greeks; proton means the first, kind of primordial
particle: another subatomic particle.
 Nobel Prize in Physics, 1911, “for his discoveries regarding the laws governing the radiation of
heat”.
Consequently, JJ THOMSON proposed his “plum pudding” model of the atom:

1. The atom is a “substance” (this is new), in which negative charges (electrons)
as well as positive charges (protons) are embedded.
2. Because the atom as a whole is neutral (this was known), the number of elec-
trons must equal the number of protons.
3. Electrons and protons are stochastically distributed inside the atom (like raisins
in an English plum pudding, or like seeds within a watermelon).
1.3 The shell and the nucleus
With the discussion of two types of subatomic particles, a new conceptual level was
reached. However, further insights into the atom’s structure were not possible with
the classic infrastructure of chemical and physical experimental and analytical
methodologies available in the nineteenth century.4 Similar to the impact of the ap-
pearance of electricity on the progress of atomic theory, it was the phenomenon of
radioactivity that opened the door to the experimental studies ahead. (Interestingly,
while radioactivity required significant progress in the understanding of the inner
structure of the atom, radioactivity itself was at the same time a tool to do so.)
In 1896 WC ROENTGEN first measured a new type of radiation originating from
uranium ores, which he was unable to identify and therefore named X-rays.5 Soon
after, M CURIE chemically separated the main elements from uranium ore responsi-
ble for X-ray emission: radium and (later) polonium.6 Samples of radioactive ra-
dium became a popular tool for a variety of seminal experiments – not only at M
and P CURIE’S laboratory in Paris, but also elsewhere. By performing experiments
similar to those conducted for the electron and the proton, it was discovered that
the principle emissions were small, positively charged species.7 The charge was
twice that of the proton and the mass fourfold that of the proton. Since they were
the first radioactive particle emission investigated, they were named “α-particles”
after the first letter of the Greek alphabet – in particular by E RUTHERFORD.
 As we know today, excursions into the atom required subatomic tools and energies much higher
than those provided by classic chemistry and physics.
 (First) Nobel Prize in Physics, 1901, “in recognition of the extraordinary services he has rendered
by the discovery of the remarkable rays subsequently named after him”.
 Nobel Prize in Physics, 1903, “in recognition of the extraordinary services they (i.e. with Pierre
CURIE) have rendered by their joint researches on the radiation phenomena discovered by Professor
Henri BECQUEREL; and Nobel Prize in Chemistry, 1911”, “in recognition of her services to the ad-
vancement of chemistry by the discovery of the elements radium and polonium, by the isolation of
radium and the study of the nature and compounds of this remarkable element”.
 See Chapter 5 for the radioactive transformations originating from uranium, radium etc. and
Chapter 9 for details on α-transformations.
In 1911, RUTHERFORD conducted a simple but key experiment using a radium-

based α-source. He let a beam of emitted α-particles penetrate a thin foil of gold.
These subatomic projectiles, emitted from the radium source with a certain kinetic
energy, reached the gold atoms. While most of the α-particles had enough kinetic
energy to penetrate the foil (and were measured along the line of their origin, albeit
with a somewhat weaker abundance and energy than those released from the ra-
dium source, as we know today), a significant number of α-particles were recorded
at detectors located along all directions possible, indicating reflected or scattered α-
particles (Fig. 1.4).
scattered
α-particles non-scattered
α-particles
gold atom
beam of (representing
α-particles thin Au foil)
α-source
Fig. 1.4: Sketch of the RUTHERFORD experiment, analyzing α-particle8 scattering9 on atoms
of a thin gold foil.
This observation was not in agreement with the THOMPSON model of an atom, which
considered electrons and protons to be distributed homogeneously. In this case, the
α-particles should have been unable to penetrate the gold atom for one of two rea-
sons: the density of the 76 protons and the 76 electrons inside the gold atom, or
because of coulombic repulsion between the 76 protons and the incoming +2 charged
α-particles. Alternatively, if the α-particles could penetrate this substance, it should
have occurred along their line of origin. RUTHERFORD explained the experimental re-
sult by suggesting a new “RUTHERFORD atom model”. It divided the atom into two
 The α-particles emitted from the source originate from the 226Ra itself, but also from other radio-
nuclides involved in 226Ra transformation processes such as 218Po and 214Po.
 Despite penetrating the atom and scattering (elastically or inelastically), another option would
be a nuclear reaction (see Chapter 13). This, however, could not happen in RUTHERFORD’S experi-
ment because of the kinetic energies of the α-particles relative to the high proton number of the
gold nucleus.
principal components – the protons, concentrated inside a nucleus, and the elec-
trons, located within a shell.
RUTHERFORD’S model created a sufficiently empty space between the two sub-
atomic particles known at that time. This space was large enough for two processes:
to permit α-particles entering the gold atom just between the nucleus and the outer
shell to pass through (and reach the detectors behind the gold foil), and at the
same time to reflect and/or scatter incoming α-particles which hit the nucleus (thus
reaching detectors in a 4π geometry positioned around the gold foil).
According to the RUTHERFORD atom model,10 each chemical element is character-
ized by its proton number (Z). For a neutral atom, the number of protons within the
nucleus equals the number of electrons in its shells. Electrons positioned in a shell
were considered to “circulate” around the nucleus. Significant energy was antici-
pated for the speed of this movement in order to withstand the coulomb attraction of
the protons and prevent the electrons from being sucked into the oppositely-charged
nucleus (Fig. 1.5).
(a) (b) (c)
Fig. 1.5: Schematic representation of the successive levels of atomic “philosophy”: (a) The atom as
an indivisible component of matter (Democritus, Dalton). (b) Subatomic structures of electrons and
protons distributed homogeneously inside the atom (Thomson). (c) Electrons and protons
positioned in the shell and nucleus of the atom, respectively (Rutherford). Sizes are not to scale:
the proton mass is about 2000× that of the electron mass, with which size scales accordingly. The
diameter of a spherical nucleus (<10 fm) is about 1000× smaller than the diameter of the whole
atom (ca. 100 pm or 1 Å). Consequently, the “empty” space within the electron shell and the
nucleus is much larger than illustrated. The area of the gold atom is on the order of 10−20m2, that
of the gold nucleus about 10−28m2, making an area of empty space of about 99.999999% of the
atom’s cross-section (see Chapter 2). About 99.99% of the atom’s mass is concentrated within the
little nucleus!
 Nobel Prize in Chemistry, 1908, “for his investigations into the disintegration of the elements,
and the chemistry of radioactive substances”.
1.3.1 New model – new problems
While the new atom model could explain the experimentally observed α-scattering,
it provoked fundamental questions. Three main concerns were:
1. Why should all the protons be “willing” to concentrate tightly together and
stick in the little nucleus – despite the coulomb repulsion of the positively
charged particles?
2. When a chemical element is identified by its number of protons (and the same
number of electrons in the case of a neutral atom) – why may the chemical
properties of one and the same element differ for different chemical compounds
containing the same atom?
3. Why might electrons circulate in the shell? Electrically-charged moving par-
ticles are known through classic electrodynamics to lose energy. Electrons cir-
culating in a shell around the nucleus and within the field of the nucleus must
emit energy. Consequently, they are expected to approach closer and closer to
the nucleus – until they are finally trapped there. The RUTHERFORD atom thus
would be not stable, i.e. could not exist!
In 1913, N BOHR responded to the contradictions between RUTHERFORD’S experimen-

tal findings and the laws of mechanics and electrodynamics by extending classical
physics into quantum physics. He postulated:
1. Electrons are allowed to exclusively exist at defined shells (orbits) around the
nucleus, in which they are not affected by any classical force causing the elec-
tron to release kinetic energy.
2. Transitions of electrons between individual orbital shells are forbidden to pro-
ceed continuously, but in defined intervals (quanta) only.
Although this idea was deduced somehow from the PTOLEMAIC conception of our
planetary system – with electrons circulating around the atomic nucleus like plan-
ets around our sun – this new “BOHR atom model”11 was not in accordance with
classical physics. However, it was able to perfectly explain new experimental obser-
vations obtained for the line spectrum of hydrogen (see Fig. 1.6).
Once the hydrogen atom received energy, e.g. by elevated temperature, a set of
individual photon emissions was observed, lying within the wavelength spectrum
 Nobel Prize in Physics, 1922, “for his services in the investigation of the structure of atoms and
of the radiation emanating from them”. Remarkably, AAGE NIELS BOHR, son of NIELS BOHR, continued
research on atomic nuclei and in particular on the interaction among nucleons causing nuclear dis-
tortion. He shared the Nobel Prize in Physics, 1975, “for the discovery of the connection between
collective motion and particle motion in atomic nuclei and the development of the theory of the
structure of the atomic nucleus based on this connection”.
n LYMAN BALMER PASCHEN BRACKETT PFUND
∞
7
6
(H ) (H ) (H ) (H )
=410.1 nm =434.0 nm =486.1 nm =656.3 nm
Fig. 1.6: Electron transitions of the hydrogen emission spectrum (schematic). Each emission series
(Lyman, Balmer, etc.) corresponds to a different final energy level (n). Notably, emissions in the
BALMER series occur at visible wavelengths, shown below in nm.
accessible to the human eye. However, there was just one electron within the neu-
tral hydrogen atom – but sets of characteristic emissions.
1.3.2 Electron shells and electron binding energy
This observation is explained by allowing the electron to occupy several shells (n)
of distinct energy. The hydrogen electron is assumed to normally exist in the ener-
getically lowest shell (n = 1). When energetically stimulated, it may reach an orbital
shells of higher energy (n = 2, 3, . . . ), i.e. further from the hydrogen nucleus. Imme-
diately, it would fall back to a lower-energy shell.
Once a certain shell is taken as the baseline, the electron is energetically excited
to reach a higher-energy shell, from where it immediately returns. The difference in
energy between a baseline and higher-energy shell is emitted as electromagnetic ra-

diation – light. Each shell represents a certain electron binding energy EB(e). (Electron
binding energies are expressed as − EB(e), meaning that this energy is required to re-
move an electron from any shell n up to dissociation.)
For a given atom where Z is constant, the binding energies of the electrons in
the different shells are proportional to 1/n2. For hydrogen (with Z = 1 and n = 1), the
electron binding energy becomes − 13.6 eV, which is the rationale behind the exper-
imentally-derived RYDBERG constant, RH. The RYDBERG constant represents the pro-
portionality and adds a unit of energy: RH = 13.6 eV.12 The internal relationship in
energy then looks as indicated in Fig. 1.7. Starting with the energy level for n = 1,
any higher energy level is then fractionated due to the EB(e)(n = 1) value 1/4, 1/9,
1/16, 1/25 etc. for EB(e)(n = 2), EB(e)(n = 3), EB(e)(n = 4), EB(e)(n = 5), respectively.
1 Z2
EBðeÞ ðnÞ = − constant · 2
= RH · 2 (1:1)
n n
n= 1 2 3 4
Fig. 1.7: Schematic energy scale of electron binding energy in proportions according to eq. (1.1).
Starting with the energy level for n = 1, any higher energy level is fractionated due to the EB(e)(n = 1)
value as 1/4, 1/9, 1/16, 1/25 etc. for EB(e)(n = 2), EB(e)(n = 3), EB(e)(n = 4), EB(e)(n = 5), respectively.
For different atoms, electron binding energies in individual shells are very much
dependent on the number of protons in the nucleus: the higher Z is, the higher EB(e)
(n) is by ≈(1/n)2. With eq. (1.1), it is straightforward to calculate the electron binding
energy for any electron shell of any atom. For gold (Z = 76), the n = 1 electron bind-
ing energy is − 78 553.6 eV; for shells 2, 3, 4 and 5 it is − 19 638.4 eV, − 8 728.2 eV,
− 4 909.6 eV and − 3 142.1 eV, respectively. The higher Z is and the closer the elec-
tron is to the nucleus, the higher the energy needed to remove it from its shell. For
example, the K-shell electron of gold is bound almost six thousand times stronger
than that of hydrogen.13
 In atomic physics, the energy unit electron volt (eV) is preferred to joule (J): 1 eV = 1.602177⋅10−19
J; 1 J = 1 kg⋅m2 / s2. Alternatively, energy might be translated into mass via E = mc2, and the RYDBERG
constant may be expressed in terms of mass, typically related to the mass of an electron or to the
atomic unit.
 For the following chapters on binding energies of protons and neutrons inside the atom nu-
cleus, it is interesting to note this typical range of electron binding energy, namely less than
100 keV. Typically, chemical reactions proceed at eV scales: 1–7 eV between identical atoms (atom
The transition of an excited electron down to lower-lying shells is well defined

by energy, according to the difference in electron binding energy ΔEB(e) between the
two shells. ΔEB(e) is emitted as electromagnetic radiation of a certain frequency υ
and wavelength λ. In 1888 J RYDBERG generalized a semi-empirical expression of the
wavelength λ (and wavenumber ν̅) of the hydrogen emission lines. In the case of
the BALMER series (n = 2), the reciprocal wavelength is

1 4 1 1
= − for n = 3, 4, 5, . . . (1:2)
λ B 22 n 2
ν 1
ν= = (1:2a)
c λ
The 1/22 term corresponds to the n = 2 baseline (BALMER); for the other series, this
would become 1/12 (LYMAN), 1/32 (PASCHEN), 1/42 (BRACKETT), etc., with n always corre-
sponding to the higher shell level. The lowest energy emission of the BALMER series
(α-line) thus corresponds to the EB(e)(n = 3) ! EB(e)(n = 2) transition, and according to
eq. (1.2) the wavelength λ of this quantum emission is 656 nm. It represents a photon
lying in the red area of the optical spectrum. The whole BALMER series is within the
visible part of the electromagnetic spectrum.14 Figure 1.8 illustrates the transitions
within the different main electron shells of hydrogen, indicating the individual ΔEB(e)(n)
values for the BALMER series (see also Fig. 1.6).
The energy of the electromagnetic radiation is found using E = m⋅c2 and E = h⋅υ
(frequency υ, wavelength λ, and wavenumber ν̅). The PLANCK constant h was intro-
duced in quantum mechanics to identify the sizes of energy quanta.15 It is basically the
proportionality constant between the energy E of a photon and its frequency υ (E = hυ).
Because frequency is proportional to wavelength by a proportionality factor c (the
speed of light), the PLANCK constant also reflects the correlation E = h⋅c/υ.
ΔE=h·ν (1:3)
1.3.3 Electron shell occupancies
The BOHR atom model not only attributed electrons to specific “allowed” orbital
shells, it also arranged the number of electrons to fit into individual shells. A crude
binding), 3–15 eV for ion binding, 1–8 eV for metal binding and 0.01–0.2 eV for VAN DER WAALS
interactions. The binding energies of nucleons will be within an MeV scale.
 The line spectrum of hydrogen is a “brilliant” tool in astrophysics, for example. Detecting the α-
line and the deviation caused by the DOPPLER effect derives the speed of stars moving in the
universe.
 Units of h are J⋅s or eV⋅s, i.e. 6.626 ⋅ 10−34 J⋅s or 4.135⋅10−15 eV⋅s.
electron electron electron electron shells

bindingg shell transitions
energy number to shell n=2
(symbol) (nm)
0 eV
n=7 (Q)
n=6 (P)
n=5 (O)
n=4 (N)
n=3 (M)
430.0
656.3
486.1
410.1
n= 1 2 3 4 ...
proton
n=2 (L) (= nucleus of
hydrogen atom)
- 13.6 eV n=1 (K)
Fig. 1.8: Electronic transitions of the BALMER series. Four emission wavelengths are shown,
including the α-line at 656.3 nm in red. The binding energy of the “normal” n = 1 electron is
13.6 eV.
viewpoint is to believe that shells close to the nucleus are “smaller” than those more
distant from the nucleus. “Larger” shells can accept more electrons. Figure 1.9 illus-
trates the filling of electrons into the first three shells of an atom. Shell n = 1 is consid-
ered “closed” when it contains 2 electrons, shell n = 2 accepts a maximum of 8
electrons, shell n = 3 accepts 18, etc.
1.3.4 Electron shell structure and the Periodic Table of Elements
Over the centuries, a variety of individual chemical elements have been identified.
Their physical and chemical properties were measured according to the analytical
technologies available. This created a huge dataset of element-specific chemical
and physical parameters. It appeared that some elements behaved chemically quite
similarly and could thus be considered group-wise. Chemists like MENDELEEV (in
1896) realized that there should be a system to classify and group the elements ac-
cordingly. An initial criterion was to line up the elements following their increasing
mass, starting with the lightest one, hydrogen, with number Z = 1. The other crite-
rion was to consider the chemical similarities of some elements and to put them
into different groups.
ELECTRON
MAIN
SHELL
NUMBER
n=4
n=3
n=2
n=1
ELECTRON
ORBITAL
SHELL
NUMBER
l=1
l=0
NUCLEUS
Fig. 1.9: An atom of the element calcium in its neutral atomic state containing 20 protons and 20
electrons. All electrons are distributed within the various main shells n according to the maximum
shell occupancy numbers and electron binding energies (qualitatively).
These thoughts led to the concept of a “Periodic Table of Elements” (PTE)

(see Fig. 1.10). With the later identification of the atom’s electronic structure
(electrons arranged in different shells of the atom), it becomes obvious that the
earlier semi-empiric structure of the PTE was perfectly explained by properties of
the atomic electrons of the various chemical elements. The seven horizontal “pe-
riods” reflect the number of main electron shells (n = 1 to 7). The filling of each
period from left to right corresponds to the number of electrons allowed in each
main shell. Theoretically, there is a maximum of two electrons for the first pe-
riod, eight for the second period, 18 for the third, 32 for the fourth, etc.
Fig. 1.10: Periodic Table of Elements (PTE). The seven horizontal “periods” reflect the main electron
shells, with n = 1–7. The 18 vertical columns form “groups” of elements with similar chemical
properties (because of similar outer electron shell occupancies). Groups 1, 2, and 13–18 are the
“main” groups.16 The value below each element’s name is its molecular weight in g/mol.
1.3.5 Ionization energies
If the excited electron reaches a sufficiently high energy level to escape from the
nucleus’ attraction, this energy value is the ionization energy Ei(e). In the case of the
hydrogen atom, this value is 13.6 eV. (see Tab. 1.3).
Tab. 1.3: Binding and ionization energies of the hydrogen electron.
n       ... ∞
EB(e) (eV) −. −. −. −. −. −. ... 

E ! n  . . . . . ... .
 Color-coded substructures of periods mirror the subshells s, p, d and f, with maximum occupan-
cies of 2, 6, 10 and 14 electrons, respectively. This can be explained by quantum number systemat-
ics, see below.
Fig. 1.10 (continued)
Ionization energy is defined as the energy required for an atom to release an

outer-shell electron. Its value is different for each chemical element because it re-
lates to Z and the outer electron shell energy. There are first and second ionization
energies. First ionization energy refers to the first electron released from the neutral
atom. Second ionization energy refers to another electron emitted in a subsequent
step from the + 1 ion of the element. Ionization energy shows a systematic trend
within the periods and groups of the PTE (see Fig. 1.11): within a group, ionization
energy decreases with increasing proton number; within a period, ionization energy
increases.
1.4 Quantum mechanics
Within the BOHR atom model, not only does each electron have a characteristic en-
ergy as defined by its shell, but each shell was also postulated to accept a specific
number of electrons. Moreover, although multiple electrons can occupy the same
main shell, each electron of an atom is still considered to be unique. Of the 76 elec-
trons located in various shells of the gold atom, all are different in at least one
parameter!
2400
He
2200
Ne
2000
1800
Average Ionization Energy (kJ/mol)
1600 Ar
1400 Kr
H Cl Xe
1200
P Rn
1000
S
800 Si
Mg
600
Al
400 Li Na
K Rb
Cs
200
0
10 20 30 40 50 60 70 80 90
Atomic Number
Fig. 1.11: First ionization energy of the first six periods of chemical elements. Within a group (e.g.
the noble gases, red line), ionization energies decrease with increasing proton number: He (Z = 2)
! Ne (Z = 10) ! Ar (Z = 18) ! Kr (Z = 36) ! Xe (Z = 54) ! Rn (Z = 86). Within a period, ionization
energies increase; e.g. for the n = 3 (L) period (blue line): Na (Z = 11) ! Mg (Z = 12) ! Al (Z = 13) !
Si (Z = 14) ! P (Z = 15) ! S (Z = 16) ! Cl (Z = 17) ! Ar (Z = 18).
1.4.1 Quantum numbers
The nomenclature applied is “quantum numbers”. It bridges the energy levels of the
BOHR atom model with quantum mechanics introduced by SCHRÖDINGER et al. and molec-
ular orbital theory proposed by HUND and MULLIKEN. Accordingly, there is a set of four
quantum numbers which characterize each electron, like a fingerprint. Three (n, l, m)
are dedicated to the orbital parameters of the electron’s existence in terms of energy and
orbital angular momentum, and the fourth one (s) to the intrinsic spin of the electron.
The principal (or main) quantum number is n. It defines the different main
shell the electrons exist. It quantifies the maximum number of electrons to fit into
each main shell. The energy of these shells, however, depends on the individual
atom. There are basically seven principal quantum numbers with n = 1, 2, 3, 4, 5, 6,
7, also symbolized by Latin capital letters K, L, M, N, O, P, Q. Artificial elements of
Z > 118 will start filling electrons in the n = 8 shell.
Shells may be structured into subshells. All shells except the K-shell (n = 1)
involve multiple subshells. The subshells are indicated by the orbital quantum
number l.
The value of the electron’s orbital angular momentum reflects individual orbits
of electrons within a given main shell. Thus, many electrons may “circulate” within
one and the same main shell, but do not overlap, as they populate individual or-
bital spaces.
The orbital angular momentum correlates with the principal quantum number.
The higher the principal quantum number n, the more subshells may be populated
within that shell. The maximum number of subshells is l = n − 1, i.e. 0 ≤ l ≤ (n − 1).
Consequently, there is l = 0 for n = 1 (because n − 1 = 0). In contrast, there are four
subshells for n = 4, namely l = 0, l = 1, l = 2, l = 3. Those orbital orbitals are denoted
as s, p, d, and f.17
Quantum mechanics not only introduced specific energetically “allowed” orbi-
tals for the circulating electrons, it also characterized electrons in more detail. The
key point was to consider electrons not as localizable particles like planets, which
can be correlated at any point in time to a specific position. Instead, their existence
in space and time was proposed to follow probabilities only, defining states of high
and low probability. Because only discrete values may exist in quantum mechanics
(as indicated by the PLANCK constant,18,19), the “real” orbital angular momentum L
is identified through the relation
2
h
L2 = (1:4)
lðl + 1Þ
h
h = (1:4a)
2π
Figure 1.12 illustrates the different features of electrons with different principal and
angular quantum numbers existing in space along an x-y coordinate system.20
All s-electrons (l = 0 orbitals) exist in sphere-shaped orbitals around the nu-
cleus. The distribution within that sphere is homogeneous, i.e. there is a certain
probability for the s-electron to be in the center of the coordinate system.21 Because
 This quantum physical idea can predict “real chemistry”, i.e. the chemical behavior of ele-
ments. The PTE shows a specific block of “p-elements” containing elements with the outer electrons
located in the p-shell of the main shells n > 1; these are the main PTE groups III through VIII. There
are also “d-elements” and “f-elements”, i.e. the lanthanides and actinides. Again, experimental evi-
dence is beautifully correlated with theoretical concepts on the atom’s electronic structure.
 The symbol ħ stands for the “reduced” PLANCK constant, where ħ = h/2π. The reduced PLANCK
constant is preferred in cases where radial dependencies are relevant, such as angular frequency,
solid angle, etc. (see Fig. 1.20).
 Nobel Prize in Physics to PLANCK, 1918, “in recognition of the services he rendered to the ad-
vancement of Physics by his discovery of energy quanta”.
 This is mathematically derived for the simplest case – the one electron system of hydrogen.
 One of the main features to understand nuclear transformations is the principal difference be-
tween probabilities of existence of electrons of s orbital quantum number compared to other orbital
quantum numbers. As depicted in Fig. 1.12, s orbital electrons do have a probability (although
3s 3p 3d
2s 2p
1s
Fig. 1.12: Two-dimensional illustration of the orbital distribution of s, p, and d electrons for n = 1–3,
imaged as densities around the atom’s nucleus. For l = 1 (1s, 2s, 3s, etc. electrons), the density
distributions are spherical. The sphere’s radius increases slightly with n, following the relationship
in Fig. 1.7 and according to eq. (1.1). The change in size is more dramatic as Z increases, when
electrons become more and more attracted to the nucleus. For instance, the 1s-electron gets closer
to the nucleus if the chemical element has a larger proton number and electrons are filled in 2s
(i.e. starting from lithium) or 3s (i.e. starting from sodium) orbitals. The same is true for p-orbitals
of n = 2 and n = 3 shells (2p, 3p), etc.
the electron binding energy differs between shells (see Tab. 1.3), the radial distance
between each orbital and the center of the coordinate system increases with n. For
example, the s-electrons of the n = 2 shell (L) are further from the nucleus than n = 1
(K) electrons.
extremely small) to exist close to the center of the Cartesian coordinate system (i.e. the nucleus);
shells with different orbital quantum numbers do not. Despite the extremely large dimensions of
electron shells compared to the atomic nucleus, s shell electrons are “allowed” to exist close to and
even within the atomic nucleus. Of course, these probabilities drop dramatically when increasing
the principal quantum number from n = 1 to n > 1. At minimum, each atom will have K-shell s-
electrons, and important nuclear transformations of radioactive nuclides (such as the electron cap-
ture branch of the β process or secondary processes like inner conversion) rely on this feature of s
orbital electrons (see Chapters 8 and 11).
From l > 0 onward, the electron density distribution is no longer spherical. The
orbital distribution of p-electrons (l = 1) is dumbbell shaped and the d-electrons (l = 2)
exist in orbitals of other shapes (see Fig. 1.12). Thus, a three-dimensional system is
needed. Figure 1.13 illustrates the different electron features of p-orbital electrons ex-
isting in space along an x-y-z coordinate system.22 The general profile is dumbbell
shaped. The two symmetrical orbitals on the left and the right represent so-called
bonding or nonbonding parts. Within a Cartesian system, there are three different op-
tions for a dumbbell: a p-electron of identical characteristics may either occupy space
along the x-axis, the y-axis, or the z-axis (px, py, pz). In the center of the coordinate
system, i.e. at x = y = z = 0, the probability to exist is zero.
z z z
x x x
y px py pz
y
Fig. 1.13: The three-dimensional dumbbell-shaped orbitals of p-electrons along x-y-z axes of a
Cartesian coordinate system.23
For l = 0, there was one s orbital. For l = 1, there was one p, but with three individual
profiles: px, py, pz. The number of those subshells increases with increasing values of
l. Mathematically, it is expressed by − l, −(l − 1), . . ., 0, . . ., +(l − 1), + l (see Tab. 1.4).
For l = 2, for example, there are 5 possible states, namely − 2, − 1, 0, + 1 and + 2.
Each given l-orbital thus contains a set of electrons described by a new parame-
ter: their magnetic quantum number m. It may be thought of as if electrons within a
certain subshell may form groups of “clouds”. In fact, it reflects the projection of
the orbital angular momentum of the electron within a magnetic field, referred to as
an axis of the polar coordination system. (Negatively charged electrons moving
around a positively charged center are influenced by an electromagnetic field.) The
final orbital angular momentum thus becomes Lz = ħml.
 This again is mathematically derived for the simplest case – the one-electron system of
hydrogen.
 This organization of orbital distribution of the 3p-electron states is not an abstract concept. It is
reflected in real chemistry, where the px, py, pz states make a huge difference in terms of forming
chemical bonds and thus forming chemical compounds.
Tab. 1.4: The four quantum numbers making each electron of an atom unique.
Quantum number Symbol Values Names Example
Main (principal) n n≥ , ,  . . . K, L, M, . . . n=
Orbital angular l  ≤ l ≤ (n − ) , . . ., n −  s, p, d, . . . l = , ,  . . .
Magnetic m −l ≤ m ≤ + l −l, . . ., , . . . + l for p: m = − , − , , , 

px, py, pz
Spin s ↓, ↑ -½, +½ s = −½, +½
Finally, there is a quantum number reflecting the angular spin momentum, s, of

an electron. Like the earth’s movement around its axis lasts one day (see Fig. 1.14),
one may understand the electron’s spin angular momentum as a spinning process
around an axis of the electron’s sphere.
EARTH
Earth spinning
SUN around its axis
(spin angular momentum)
Earth moving in space

around the Sun
(orbital angular momentum)
Fig. 1.14: Conception of the two different angular moments of the planet earth circulating around
the sun. The earth’s movement in space, taking one year, would mirror the orbital angular
momentum of an electron around an atom’s nucleus – reflected by the quantum number
l. Similarly, the earth’s own movement around its axis, lasting one day, may help to understand the
spin angular momentum of the electron – denoted by the spin quantum number s.
However, the momentum is either in one direction or the other – there are no further
options. The corresponding spin quantum number s thus is either +½ or −½.24 It re-
flects an intrinsic parameter of the electron. For example, for a given set of n, l, m
 Note that there is actually no “positive” or “negative” direction of the angular spin.
there are always two options for an electron, which differ in angular spin of +½ or
−½. This is denoted as HUND‘S rule. The value of this spin quantum number s is:
S2 = h2 · sðs + 1Þ (1:5)
Now each electron is fully identified by (n, l, m, +½) and (n, m, l, −½). Each subor-
bital, defined by (n, l, m), can contain a maximum of two electrons of opposite spin,
and the general notation for how magnetic quantum number and spin are linked
is ms = ±½. Finally, each electron is supposed to be unique. This is known as the
PAULI exclusion principle:25 in any quantum mechanical system (such as electrons
in the atom’s shell, nucleons in the atom’s nucleus), two particles of identical quan-
tum parameters should not exist.
1.4.2 Electron configurations
Finally, electron configurations are named according to a set of quantum numbers,

expressed by a number (main shell / main quantum number) followed by a Latin let-
ter (subshell / orbital quantum number) and a final number as the superscript (indi-
cating the number of electrons per subshell). In many cases, only the composition of
the last (outer) shell (or subshell) is indicated, assuming that all the lower (inner)
shells are filled completely. For instance, 1s1 indicates the first main electron shell
(n = 1), its s-orbital character (l = 0), and that this orbit contains one electron only.
Chemically speaking, this is the electron configuration of a neutral hydrogen atom. In
comparison, 3p2 says that there are two electrons located in the third principal electron
shell (n = 3) and that both are of p-orbital character (l = 1). For a neutral element with
all the lower-energetic shells and subshells filled completely, i.e. 1s2 < 2s2 < 2p6 < 3s2,
this element is silicon comprising altogether 12 electrons (and 12 protons).
1.4.3 Orbital occupancies vs. electron binding energies
Figure 1.15 illustrates how electrons fill the individual orbitals for the element cal-
cium. The complete composition of this element of Z = 20 according to quantum
number logic would 1s2 < 2s2 < 2p6 < 3s2 < 3p6 < 3d2. However, this order is followed
only for the first 18 electrons. The two outer electrons, i.e. electron numbers 19 and
20, prefer to occupy the 4s2 orbital instead of the 3d orbital! The explanation lies in
the energy of the individual shells and subshells. It is a matter of fact that the 4s2
“comes first”, i.e. shows a lower value of EB(e) relative to the binding energy of the
 The Nobel Prize in Physics, 1945, was awarded to W PAULI “for the discovery of the Exclusion
Principle, also called the Pauli Principle”.
4d 4d 4d 4d 4d empty
shells
4px 4py 4pz p orbital

(l = 1)
3d 3d 3d 3d 3d
4s
s
orbital
3px 3py 3pz (l = 0)
3s
2px 2py 2pz
2s
Energy
1s
Fig. 1.15: Electron shells arranged according to the system of the four quantum numbers are filled
by electrons according to the electron binding energy of each subshell. (left) Electron orbitals
defined by quantum numbers and arranged with increasing electron binding energy. (right) The 20
electrons of the chemical element calcium filled into main shells (circles), subshells not indicated.
The chemistry of calcium is defined by its outer electrons, which are the two 4s electrons instead
of 3d electrons.
3d2 subshell electrons.26 This effect becomes more pronounced the closer the outer
electron shells are in electron binding energy. Furthermore, because differences be-
tween individual subshells of higher main quantum number become smaller and
smaller (see Fig. 1.7), the effect of overlapping subshell orbitals becomes more and
more pronounced.
 This order of electron subshell occupancies is reflected in the structure of the PTE, i.e. it per-
fectly correlates the experimentally observed systematics of chemical elements with electron struc-
ture parameters. Interestingly, the same will be discussed in the following chapters, where the
overlap of nucleon shell structures will explain the stability of the nuclei of atoms.
The individual probabilities of electrons to exist in various shells, but in partic-

ular in the last, outer shell, are largely responsible for the chemical behavior of a
given element and for the type of chemical bonding between two or more atoms in
a chemical compound.
1.5 Mathematical explanations of the BOHR atom model
BOHR’S atom model postulates that electrons are located in various shells. This
statement satisfies experimental evidence, such as line spectrum of hydrogen and
positioning of chemical elements within the PTE. However, mathematical verifica-
tion of the model’s postulate was delivered only later. SCHRÖDINGER27 developed the
corresponding mathematics to calculate parameters such as the electron energy of
the simplest model, the one electron of atomic hydrogen. The concept is to quantify
electron parameters in terms of particles existing within a potential well.28
The key intention is to deduce fundamental parameters of the electron (and
other particles), such as energy (potential and kinetic), velocity, and position. The
mathematics itself in detail is beyond the scope of this book. The basic idea is to
treat the electron as a wave, and to derive its wavefunction Ψ. Finally, the quantum
mechanical parameters are correlated to the basic physics of the electron, such as
the radius r of a certain electron shell, and its energy described as E = f(r).
1.5.1 Potential well
A potential well considers a particle (here, an electron29) inside a well (or box), and
defines a region defined by a (local) minimum of potential energy. In nature, a lake
filling a valley surrounded by mountains represents a three-dimensional potential
well.30 For mathematical treatments, one-dimensional model systems are consid-
ered. The well localizes a “free” particle within the two walls of (infinite) high po-
tential energy along an x-axis. Inside the box, the potential energy U is zero, while
outside it is infinitely large.31 The two walls are characterized by positions 0 and L
 Nobel Prize in Physics, 1933, “for the discovery of new productive forms of atomic theory”.
 It is introduced here because it is also relevant to the quantification of nucleons within a poten-
tial well. It is thus applicable to particles of the atom’s nucleus, for e.g. understanding the nucleon
shell occupancies (see Chapter 2), and introducing the tunneling effect (see Chapter 9).
 . . . could also be a gas molecule, an electron, or a nucleon.
 The simplest model implies a single, negatively charged “free” electron existing in a box (“par-
ticle in a box”) within the electrostatic attraction caused by the positively charged nucleus with a
potential energy V > 0. This is a potential well, which does not, however, completely describe the
whole truth of electron(s) within a real atom.
 There are slightly modified considerations for a potential well.
(see Fig. 1.16). Within the well, i.e. between positions 0 and L, the particle moves
with constant velocity and is reflected from each wall without losing energy. It can
leave (or escape the well) only if it becomes energetically excited.
U=
U=
U (x)
O L
x
Fig. 1.16: Electron potential well. An electron inside a well (a box) exists within a specific region
defined by a (local) minimum of potential energy. The well localizes the “free” electron within two
walls of (infinitely) high potential energy along an x-axis of distance. Inside the well, the potential
energy U is zero, while outside it is infinitely large. The electron moves with constant velocity
between the two borders (walls), characterized by positions 0 and L.
In quantum physics, the electron is treated as a wavefunction with wavelength λ.

The waves are reflected at the walls of the well. In order not to annihilate waves
after reflection due to interference, particles may exist only if the wavelength fits
within the well length L (or vice versa). The simple mathematical expression is Lwell
= n ⋅ λ/2, indicating that L should be an integer multiple of half of the wavelength.
Only in this situation are the waves reflected in a way that reproduces the initial
wave again (see Fig. 1.17).
Consequently, electrons are only allowed to exist in specific states (defined by n)
where their energies are multiples of n. The “allowed” energies of the wave (i.e., the
electron with mass m) are, according to eq. (1.6), proportional to the square of
n. Each value of n corresponds to a wavenumber according to eq. (1.7):
n2 h 2 n2 h2
En = · = · , with n = 1, 2, 3, . . . (1:6)
2L2 m 2L2 4m
πn
ν= (1:7)
L
n=1 =½
n=2 =1
n=3 = 3/2
Fig. 1.17: Waves being reflected at the walls of a potential well. A wave may propagate “forever”
only if half its wavelength λ is an integer multiple n of the well length L: Lwell = f(n ½λ).
1.5.2 Harmonic oscillator
According to NEWTON‘S laws of classical mechanics, a classical harmonic oscillator

describes a particle oscillating back and forth along a spring (see Fig. 1.18). There is
a stable mass point of equilibrium with a corresponding potential, depending on a
spring constant k and a restoring force F. The harmonic potential is U ≈ x2. Both the
position and energy of the particle are exactly known.
1
UðxÞ = k · x2 (1:8)
2
δ UðxÞ
FðxÞ = − = −k·x (1:9)
δx
This is different in quantum mechanics. The position of an electron is not precisely

determinable; the same is true for the absolute value of an electron’s energy at a
specific position. In contrast, a probability function is derived for the position of the
electron (see Fig. 1.18).
exact position
impossible to
determine
position
potential
probability of
energy level electron
CLASSICAL OSCILLATOR QUANTUM MECHANICAL OSCILLATOR
Fig. 1.18: The harmonic oscillator in classical physics and in quantum mechanics.
1.5.3 SCHRÖDINGER equation
The (time-dependent) SCHRÖDINGER equation defines wavefunctions Ψ and yields

probabilities of finding (the residence) of a particle, which are expressed as Ψ 2. To
solve these wavefunctions, two operators32 are used: Ê (energy operator), which is
relevant to the total energy of the wavefunction, and Ĥ (HAMILTONIAN operator),
which represents the specifics of the object under consideration and the fields influ-
encing the objects.
^ = EΨ
HΨ ^ (1:10)
^ = − 1 h ∇2 + U
H (1:11)
2m
^ = ih δ
E (1:12)
δt
1 h 2
− ∇ Ψ ðx, y, zÞ + Uðx, y, zÞΨ ðx, y, zÞ = EΨ ðx, y, zÞ (1:13a)
2m
The HAMILTONIAN operator in its general form is expressed in eq. (1.11), and com-
bines terms for both kinetic energy ½ħ∇2 and potential energy U. For the kinetic
energy, the reduced PLANCK constant ħ and the mass of the particle are considered.
Further, the nabla operator ∇ is involved,33 which represents the derivatives for all
coordinates in space. Time is not considered here.
 In mathematics, operators are procedures which apply to a whole function.

 The nabla ∇ is a vector differential operator, similar to the LAPLACE operator (or Laplacian) Δ,
used to calculate how the average value of a function f over spheres deviates from f(r) as the radius
of the sphere grows. ∇2 = Δ.
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 H consists of a single proton.

– What makes a nucleus stable (or unstable)?

The intention of this textbook is to illuminate the concepts of radioactive transfor-

Mainz, December 2013

Vichuquen, December 2021 | Berlin, May 2022

Preface for the 2nd edition VII

1 The atom’s structure I: Electrons and shells 1

2 The atom’s structure II: Nucleons and nucleus 37

3 Nucleons: Binding energy and shell structure 59

4 From stable to unstable nuclides 95

5 From stable to unstable nuclides: Mathematics 105

6 Processes of transformations: Overview 145

7 β-Transformations I: Elementary particles 177

8 β-Transformations II: β−-process, β+-process and electron capture 199

10 Spontaneous fission 277

11 Secondary transformations 307

12 Post-processes of primary and secondary transformations 343

13 Nuclear reactions 373

1.1 The philosophy of atoms

1.1.1 The beginning: Just philosophy

FIRE EARTH AIR WATER ETHER

tetrahedron hexahedron octahedron icosahedron dodecahedron

1.1.2 2000 Years later: Experimental evidence

Conservation of mass (LAVOISIER): The overall mass represented by all reaction

Law of definite proportions (PROUST): Species undergoing a chemical reaction com-

mass  × ( ×  g) +  × ( ×  g) = × ( ×  + ) g = (:) g

mass ratio H:O = :

mol  ×  mol of H  ×  mol of O × ( mol of H +  mol of O)

molar ratio H:O = :

atoms  × .⋅ +

total  × .⋅+ =  × .⋅+

These chemical observations allowed DALTON (1766–1844) to develop a “modern”

Tab. 1.2: Key messages of DALTON’S theory (“philosophy”) on atoms.

Atoms Atoms are extremely small particles composing chemical elements.

Atoms of the same element are identical.

Atoms of different elements are different.

Chemical A chemical compound is the combination of characteristic atoms of individual

A specific chemical compound contains atoms in a fixed, compound-specific

Chemical A chemical reaction is the combination of atoms or the separation of atoms

No atom of one chemical element is transformed into an atom of a different

1.2 The inner structure of the atom

1.2.1 The electron and the proton

Quinquenary & Sextenary