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THE THEORY OF ATOMIC SPECTRA
by
E. U. CONDON, PH.D. WAYMAN CROW FEOFB8SOE OP PHYSIOS, WASHINGTON
8T LOUIS, MISSOUEI
XTNIVEBSITY
and
G.H.SHORTLEY,PH.D.
DIKECtOK, WASHINGTON OFEKATION8 BOOZ, ALLEN AFFUKD EBSBABCHi INC,
CAMBRIDGE
AT
THE UNIVERSITY PEESS
1959
PUBLISHED BY TUB SYNDICS OF THE GAMBBIDGK UNIVERSITY PRKSS
Bentley House, 200 Euston Road, London, N.W. I American, Branch: 32 East 57th 8troot Now York 22, N,Y.
JPirtt
printed Reprinted with
corrections
1936
1051 1953 1057 1050
Reprinted
First printed in Great Britain at the University
Reprinted by
offtetlitho
by Bradford db
Dic,kem&gt;
/Vaw, Oambrulge London, W.CLl
To
HENRY NOEBIS RUSSELL
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Preface
...........
CHAPTER I INTRODUCTION
CONTENTS
PAGE
xiii
....
.
. .
.
1
CHAPTER II THE QUANTUM MECHANICAL METHOD
SECTION
12
12
12
Symbolic algebra of states and observable
Representations of states and observables
.
22
.
.
.
.
15
32
Continuous eigenvalues and the Sehrodinger representation
.
20
42
52
6
7
2
The
statistical interpretation
.
.
.
.
.
.
.
24
25
The laws of quantum mechanics
Schrodinger
s
equation
........
26
27
2
Matrix mechanics
Perturbation theory
82
9
2
30
1C
II
2 2
2
R6sum6 of the perturbation theory Remarks on the perturbation theory
Perturbation caused by a single state
34
35
37
12
The
analysis of noncommuting vectors
43
CHAPTER III ANGULAR MOMENTUM
1
3 3 3
...
45
45
46 48
50
2 3
43
5 6
s s
Definition of angular momentum Allowed values of angular momentum The matrices of angular momentum Orbital angular momentum Spin angular momentum
54
56
Vector addition of angular
8
momenta
Selection rule
73
83 93
The matrix of (Ji+J,) Matrix of Tin the jm scheme.
?
on j
...
58
59
61
10
s
Dependence of the matrix of T on m The matrices of /! and /2 where /i +/2=J
....
64
viii
CONTENTS
CHAPTER
SECTION
1 13
III (continued)
Matrix of a vector
P which commutes with J
...
...
. .
PAGJD
67
12 3 13 s
Matrix of PQ
70
71
Sum rules
Transformation amplitudes for vector addition
14 s
73
CHAPTER IV THE THEORY OF RADIATION
14
79
Transition probabilities
Classical electromagnetic theory
79
83
24 34
4*
Expansion of the retarded potential
84
87
The correspondence
principle for emission
54
64
74
The
dipoleradiation field
90
93
97
The quadrupoieradiation field
Spectral lines in natural excitation
84 94
Induced emission and absorption
Dispersion theory. Scattering.
100
t
. . .
Raman effect.
103
10 4
Natural shape of absorption
lines
109
CHAPTER V ONEELECTRON SPECTRA
1
5
...
112
Centralforce problem
112
25
35
Radial functions for hydrogen
114
118 120 125
131
.
The
relativity correction
4
5
5
Spinorbit interaction
5
Sketch of the relativistic theory
Intensities in
6s
75
hydrogen
.
Experimental results for hydrogenic spectra
General structure of the alkali spectra
Intensities in alkali spectra
.
.137
141
8
5
9
s
.147
149
105
Zeeman effect
CONTENTS
ix
CHAPTER
SECTION
16
VI
.
THE CENTRALFIELD APPROXIMATION
.
.
PAGE 158
The Hamiltonian for manyelectron atoms
Equivalence degeneracy
.
.158
160
26
3
6
46
56
6
6
The dynamical equivalence of the The PauH exclusion principle
.
electrons
.
.
.
.
.
.
.
.
.162 .166
.
Conventions concerning quantum numbers. Closed shells Matrix components for S^/(i)
168
169
171
76
86 96
Matrix components for S^gf(i,^) Matrix components of electrostatic interaction
Specialization for closed shells
.
.
.
174
177
1C 6
II 6
One
electron outside closed shells
183
Odd and even states
185
CHAPTER
1
7
VII
187
THE RUSSELLSAUNDERS CASE; ENERGY LEVELS
27 37
The JD/Scoupling scheme Term energies
The Land6
interval rule
.
188
191
193
4
7
Absolute term intervals
195
197
57 67
77
Formulas and experimental comparison
Terms
in the nlx configurations
207
The
triplet
terms of helium
.
210
CHAPTER VIII THE RUSSELLSAUNDERS CASE: EIGENFUNCTIONS
18
213
Vector coupling in antisymmetric states
.
.
.
.213
.
.
28 38
Genealogical characterization of i/Scoupling terms
216
Land6
intervals for terms of coupled groups
.
.
.
.219
.
48
58
Calculation of eigenfunctions
by
direct diagonalization
.
220
226
Calculation
of
eigenfunctions
using
angularmomentum
.
operators
6s
78
Calculation of eigenfunctions from vectorcoupling formulas
228
Separation of the
2
D s of d*
233
.. 412 5 12 6 12 The transformation to jj coupling The transformation between zeroorder states The transformation nlm8m *=? nljm The transformation jjJM^SLJM l . 282 CHAPTER XII TRANSFORMATIONS IN THE THEORY OP COMPLEX SPECTRA 1 12 .277 . . 284 284 285 287 212 3 12 Configurations containing almost closed shells The transformation to LS coupling . . .. eigen. . . 257 257 2 10 3 10 The jjcoupling scheme and the spinorbit interaction The addition of a weak electrostatic interaction .. 287 290 291 .... 236 237 244 249 252 49 59 Multiplet strengths obtained from spectroscopic stability Quadrupole niultiplets CHAPTER X jj COUPLING 1 10 . . 259 262 Eigenfunctions 410 Line strengths 264 CHAPTER XI INTERMEDIATE COUPLING 1 11 .S: CONTENTS CHAPTER IX THE RUSSELLSAUNDERS SECTION CASE: LINE STRENGTHS PAGE 236 P 2 9 Configuration selection rules 39 Line strengths in RussellSaunders multiplets Multiplet strengths in a transition array . . .. . ... 266 2n Matrix of spinorbit interaction for configurations consisting of coupled groups Matrix of spinorbit interaction obtained from the functions 266 270 271 3 11 411 5 11 from LS to jj coupling Line strengths in intermediate coupling The forbidden lines of astrophysical interest Illustrations of the transition . . . . . .
. ... PA GE 295 295 The spinorbit interaction Pure almostclosedshell configurations . . . . 327 327 335 339 344 345 Normal state Normal Hartree of helium Excited levels in helium states of firstrow 348 atoms 351 8 14 s selfconsistent fields 354 358 362 9 14 Survey of consistentfield results Selfconsistent fields for 10 14 oxygen CHAPTER XV CONFIGURATION INTERACTION 1 15 2 Interaction of sd and # in . 376 . XRAYS SECTION 1 13 The electrostatic energy in LS coupling 2 13 3 13 .... ..... 375 .... . . 299 300 301 413 5 13 6 13 7 13 The raregas spectra The The configurations p* s and d*$ 304 306 312 configuration p* pin the rare gases 5 The configuration^ ^ in the rare gases Line strengths 8 13 9 13 316 Xray spectra Line strengths in Xray spectra satellites 316 322 323 10 13 II 13 Xray CHAPTER XIV CENTRAL FIELDS 1 14 The periodic system statistical 2 14 The method of FermiThomas 3 M The WentzelBrillouinKramers approximation 414 514 6 14 7 14 Numerical integration of the radial equation . 365 magnesium 366 367 369 2 15 3 15 Perturbed series Autoionization 415 5 15 Manyelectron jumps of doublet intensities Spinorbit perturbation .CONTENTS XI CHAPTER XIII CONFIGURATIONS CONTAINING ALMOST CLOSED SHELLS...
.... . 1 17 .. 380 Weak fields general case 384 386 416 5 16 6 16 Intensities in the Zeeman pattern: weak fields effect effect : The PaschenBack The PaschenBack Quadrupole lines 388 illustrative examples 390 395 7 16 CHAPTER XVII THE STARK EFFECT. .. .Xll CONTENTS CHAPTER XVI SEOTION 1 16 THE ZEEMAN EFFECT effect . .... . .. PAGE 378 378 The normal Zeeman The : 2 16 316 weakfield case EussellSaunders terms : . . 397 Hydrogen Stark effect at the series limit General theory for nonhydrogenic atoms 398 2 17 3 17 . .. 428 434 435 Index of Subjects Index of Names 439 . 404 409 4 17 5 17 Helium Alkali metals 413 415 CHAPTER XVIII THE NUCLEUS IN ATOMIC SPECTRA 1 18 418 Effect of finite mass 418 2 18 3 18 Local nuclear fields 420 421 . Nuclear spin in oneelectron spectra 418 5 18 The hyperfine structure of twoelectron spectra . 424 426 Zeeman effect of hyperfine structure APPENDIX UNIVERSAL CONSTANTS AND NATURAL ATOMIC UNITS List of Principal Tables . . .
In addition every reader theory will see many places where more experimental information and better or more detailed theoretical calculations are desirable. just like the troublesome sign conven tions in geometrical optics. With this end in view we have aimed to give explicitly an example of the use of each of the general types of calculation involved and an adequate survey of the literature of the more specialized calculations. a great diversity of spectroscopic terminology. Briefly. ijx BussellSaunders coupling. but one choice does have to be made and adhered to throughout a given set of calculations. is at relativistic There exists confusion in the original literature about two matters which we have made every effort In the first it to clear up in this book : recognized that a matrix is not place transformation theory unless the relative phases of the fully useful in the states to which the components refer are in some way specified. we have attempted in every case to make explicit the specification of the phase choice employed. The phase choice is arbitrary. particularly in the theoretical literature. This does not mean that the period of fruitful research in atomic spectra an end. Fundamental questions are still outstanding in regard to the theory of the manyelectron problem and also in regard to the of the interaction of radiation and matter. It is our hope that the book will be useful in stimulating progress along these lines. and find that this gives a nomen clature that : convenient and unambiguous. our usage is the a radiative transition between following a component (of a line) results from two states of an atom. We have attempted to adhere as closely as possible to the original meanings of the nouns which denote energy levels and spectral lines. To facilitate the use of the formulas and tables of the book in other calculations. a line results from the totality of transitions between is two levels . The literature is covered approximately to the summer of 1934 although a few later references have been incorporated.quantitatively explained in terms of the quantummechanical treatment of the nuclearatom model. This interpretation seems to us to be in a fairly closed and highly satisfactory state. All known features of atomic spectra are now at least semi.PREFACE In this monograph we have undertaken a survey of the present status of the problem of interpreting the line spectra due to atoms. since two has been too little matrices cannot be added or multiplied unless these phases are the same in both. a multiplet is the totality of lines . In the second place there occurs.
intensity hope that this new usage will find favour among spectroscopists. . Robertson of Princeton for most of the elegant new treatment of spherical harmonics given in 4 3 to Dr F. Uflf ord work was author greatly facilitated by generous arrangements by the senior at Princeton to relieve him of most of his teaching duties for a term. where he spent the summer of 1933. H.XIV PREFACE connecting the levels of two terms. S. more convenient We We criticized portions of the manuscript. C. U. The greater part of his work on the book was done while he was a Fellow in Princeton University in the years 19311933. S. The present printing is essentially a reprint of the 1935 edition except that a number of errors and misprints have been corrected. In particular we are in debted to Prof. and and to to Mr of Allegheny College for special calculations and B. May 1950 . U. H. E. and a supermultiplet is the totality of nmltiplets connecting the terms of two polyads a transition array is the totality of lines connecting the levels of two configurations. March 1935 We are naturally gratified at the reception that our work has had and regret very much that other duties have prevented our giving it the thorough revision which it needs. BL P. which we theoretical specification of the radiation than either of the Einstein transition probabilities. G. C. and of the Massachusetts Institute of Technology. G. Completion of the Prof. W. We have defined in find to give a 7 4 a quantity. Napier for assistance in preparing the figures. C. Seitz of Princeton . where he spent the year 19331934 as a National Research Fellow. many who have friends with take pleasure in making acknowledgment here of the valued help of whom we have discussed various parts of the theory. Finally we wish to record our great enthusiasm for the beautiful typo once more graphical work of the Cambridge University Press as exemplified in the following pages. E. . called the strength of a line. The junior author is appreciative of courtesies shown by the s colleagues physics faculties of the University of Minnesota.
present. Fig. p. arcs. Newton s experimental arrangement 1 which is taken from Voltaire s Elemens de la Philois shown in Fig. for the spectroscope is extraordinarily sensitive to small impurities and it was difficult to deal with sources pure enough to make certain the correlation of the observed lines to the substances in the source. the technique of spectroscopy as it has developed from Newton s time to the Our principal interest will be the information concerning the nature atom which is obtained from a study of the characteristic radiations emitted by monatomic vapours.And so the true Cause of the Length of that Image was detected to be no other.". I 1. classic Spectroscopy is that branch of physics which is the direct outgrowth of a experiment of Newton s which. some of which are more Refrangible than others. of the After the discovery of sharp dark lines in the solar spectrum and sharp emission lines in spectra of flames. Newton s discovery of dispersion. This task in itself was by no means simple. 1738. The image is not round like the hole in the shutter. As we are here interested in the theory of spectra we shall not concern ourselves with. I sophie de Newton (Amsterdam. than that Light is not similar or Homogenial. . but consists of Difform Rays. ard sparks. but long in the direction perpendicular to the axis of the prism and coloured. This arrangement is the prototype of the modern spectroscope. NEWTON. the physicists of the nineteenth century seized upon spectroscopy as a valuable tool for qualita tive chemical analysis.CHAPTER I INTRODUCTION ". The beam of sunlight enters a hole in the window shutters and traverses the prism. At that stage the experimental problem consisted in correlating the various lines and bands seen in the spectroscope with the chemical nature of the emitting substance. falling on the screen P. 116). led him to the conclusion which we have placed at the head of this chapter. .
In the latter part of the nineteenth century Maxwell developed his electro magnetic wave theory which received experimental confirmation in the experiments of Hertz and Oliver Lodge. but also under some circumstances by molecules and even by single atoms. These are emitted by incandescent solids. where the lines are well separated and generally show no obvious simple arrangement although grouped into small related groups of a few lines. Evidently it is somehow determined by the structure of the atom. so densely packed that in smaller instruments they appear continuous. These differences are now known to degrees of ionization of the same element. Line. For the purposes of the classical kinetic theory of gases it is not necessary to assume anything more about atoms than that they behave something like As a consequence the range of phenomena which that theory embraces is not in a position to tell us more about the structure of hard elastic balls. in many Such cases they are spectra are due to The line spectrum due to a single chemical element in the form of a monatomic vapour shows still another complication. the theory of electric waves was early applied as a theory of light. These are characteristic of the spectra of molecules and arise from the many possible changes in the rotational state of the molecule during the radiation process. It early became clear that the observed spectra are of three general types. atoms than an estimate of their size. having no line structure in the spectroscopes of greatest resolving power. having a special form of line structure in which close groups of many lines occur Continuous. arise from different Evidently the next step is that of trying to understand the structural nature of an atom which enables it to emit its characteristic radiations. It was early learned that quite different spectra are obtained from the same element according to the energetic violence with which it is excited to luminescence. hitherto developed as . which in turn is usually altered by the conditions which render the substance luminescent. Because the velocity of light agreed with the velocity of electric waves. The wave theory of light. individual atoms. In the spectrum of one element we are given a vast amount of data which is measurable with great precision.2 INTRODUCTION Another thing which made for difficulty is the fact that the spectra do not depend simply on the chemical elements present but on their state of chemical combination. that is. Banded. so spectroscopy stood out clearly in the minds of physicists as an important means for studying that structure. In the electric spark more energy is put into the emitting atoms than in the electric arc and generally quite different lines result from the same element for these two modes of excitation. To this period also belongs the beginning of the great task of setting up accurate standards of wavelength.
The wavenumbers of the Balmer series are represented by the formula . The principle received striking confirmation in the same year through Paschen s discovery of an infrared series in hydrogen. A little later the electron was discovered through researches on cathode rays and the chemical theory of ions was developed in connection with the electrolytic dissociation hypothesis.rNTKODUCTION o a theory of elastic vibrations in the universal medium. The best known of these was Bahner s simple formula (1885) for the wave lengths of the visible lines of the hydrogen spectrum. After the work of Balmer comes the important researches of Rydberg and of Kayser and Runge. of matter came into being whose programme called During this period empirical regularities in line spectra were being found. But the custom of thinking in terms of them in the laboratory is probably too firmly entrenched to be shaken off for a long time. except that the lines associated with some differences are millions of times weaker than others so that practically there are important selection rules needed to tell which differences give strong lines. covered that many spectral lines in various These empirical discoveries of spectral regularities reach their culmination in the clear establishment of the Ritz combination principle. that is. branch of physics called the electron theory A for the explanation of the properties of matter in terms of this picture with the aid of the laws of the electromagnetic field. According to this result each atom may be characterized by a set of numbers called terms. Hartley showed (1883) that there are regularities in the spacing of related doublet or triplet lines which are more simply expressed in terms of the reciprocal of the wavelength. Although experimentalists still prefer to express their measurements in terms of wavelengths. The view became current that atoms are structures built out of electrons and positive ions. chiefly those of alkali and alkalineearth metals. This came in 1908 after two decades of important work on the study of spectral series. and this is in accord with modern theoretical views. There is no logical reason today for dealing with wavelengths at all. can be organized into series obeying formulas similar to the formula of Balmer. such that the actual wavenumbers of the spectral lines are given by differences between these terms. and they are seldom mentioned in this book. the ether. who dis atomic spectra. Ritz thought that lines were associated with all possible differences between these terms. This discovery is of the greatest theoretical importance. was re written in terms of the theory of electromagnetic waves. dimensionally like wavenumbers. the wavenumber or number of waves in unit length.
In Ritz s language this means that this particular set of lines arises as 2 2 The differences of the terms cru =R/7i and the particular term cr 2 =R/2 . Rutherford s experiments had given a general picture of a nuclear atom a positively charged massive nucleus surrounded by the negatively charged and much less massive electrons. INTRODUCTION where R 109677 cm1 an empirical coefficient called the Rydberg con stant. . Empirical spectroscopy was organized by means of the Ritz combination principle and the extensive study of spectral series. that the which is now positive electricity in an atom is confined to a small particle called the nucleus of the atom. The theoretical developments had given imperfect and unclear indications of the need of fundamental changes in the electron theory for the process of emission and absorption of radiation. The stage is now set for the great theoretical developments made by Bohr from 1913 onward. even when the is individual terms cannot be represented by for the case with hydrogen. On the experimental side a most important step was the recognition. Spectral lines were associated with the electromagnetic radiation coming from motion of the electrons in an atom. combination principle suggests the existence of lines given more generally by r=R For _ / 1 1\ I. as observed by Zeeman. the lines fall them at the predicted places* Lyman assimilated = corresponding to ra= 1 and n 2. Its applicability is of great generality. 4. Great difficulty attached to the interpretation of the enormous number of spectral lines without the introduction of unreasonable complications in the model. . 71 5. In 1913 Bohr s first work on atomic structure gave a theory of the spectrum of hydrogen which involved several important advances. These developments mark the birth of quantum theory. that there is much more to the matter and radiation than is given by the nineteenth century electromagnetic The electron theory.. It holds in all cases. generally regarded simply as harmonic oscillations about an equilibrium position. Its linear dimensions are not greater than about 10~ 4 those of the whole atom. 3. holding a simple formula as molecular as well as atomic spectra. through experiments on scattering of alpha particles made by Rutherford. on the through the work of Planck on blackbody radiation and Einstein laws of interaction of photoelectric effect. The principle was quickly as found in the ultraviolet three lines an important rule in the analysis of spectra. The first decade of the twentieth century was important as showing. Paschen found m = 3 and = 4. had led to some simple assumptions concerning atomic theory programme structure and had had some notable successes.. \m 2 also nr] in the infrared. 6. particularly in Lorentz s cal culation of the effect of a magnetic field on the spectral lines.4 ..
Bohr s early work was the development of a special for the hydrogen atom and the study of rules for the determination of the allowed energy levels. atom and &.gt. (This assumes that the zero of energy is the energy of the lowest state and that before impact the atoms are all in this lowest state. establishes a coordination between the energy E. thereby simplifying the task of determining the energy which are associated with the production of the different lines. E E E .r. . and the terms. so that we shall always write 1 and regard a simply as a measure of the energy in the auxiliary unit. If their numerical values 2 l the frequencies come out formally negative are the frequencies of light which can be absorbed by atoms in the state of This expresses the frequencies as differences of numbers cha l energy &. If The hypothesis suggests atoms are excited to radiate by single electron impacts in which the electrons have known kinetic energy E then the only spectral lines appearing should be those for which the energy of the initial state E^ is less than E.". the series limit. By spectrum bit by levels controlled electron impact it is possible to bring out a bit as the kinetic energy of the impacting electrons is gradually increased. This is rendered precise by the statement that the frequency of the radiation emitted is given by the restricted to a set of discrete values. the atom passes from one energy level to another. The model for this simplest atom consisted of an electron and proton describing orbits about their centre of of The other part dynamical model . its own means of experimental verification. Such experiments have fully confirmed the energy level inter pretation of the spectroscopic terms and have been a valuable tool in experi cm.INTRODUCTION 5 Most general was the idea of stationary states and the interpretation of the Ritz combination principle.) This is the idea under lying the experiments of Franck and Hertz and many others on critical potentials. as in the classical theory. where h is Planck ^s constant. v the frequency of the radiation. or may be Then the postulate is made that the emission or absorption of radiation is connected with a process in which. } mental work.lt. racteristic of the levels. It is postulated that the possible states of atoms and molecules are restricted to certain values of the total energy. These values are determined by the structure of the atom or molecule and may be continuous in some ranges. E the energy of the atom before the radiative process and E 2 its energy afterwards. through the relation The minus sign arises since the conventional way of measuring term values was by counting them as positive when measured from. There is no reason to adhere to this convention.".
but the numerical coefficient comes out correctly. It also failed to basis for the calculation of the relative or absolute intensities of the spectral give satisfactory results when attempts were made to calculate the energy levels of atoms containing more than one electron. Numerous attempts were made to calculate the energy of the lowest state of helium but without securing agreement with the experimental result. The so had to be sought out and of these the allowed ones determined by a rule of quantization which was an outgrowth of Bohr s requirement on the angular momentum for the circular orbits of hydrogen. We shall not trace in detail the work along these lines: for this the reader is referred to Sommerfeld s Atombau und SpeJctrallinien and to called multiply periodic motions Van Vleck s Quantum Principles and Line Spectra. These studies were eminently successful in a semiquantitative way and gave a great impetus to the experimental study and analysis of atomic spectra. This served to give an energy ^=for the circular orbit whose angular momentum n vakesare ^ he 2 is nti. so by this means the empirical Eydberg constant R was for the first time related to universal constants. Naturally this definite accomplishment stimulated other work and in the next few years gseat advances were made in interpretation of finer details of the hydrogen spectrum due to relativistic effects (Sommerfeld) and the effect of an electric field on the hydrogen spectrum (Epstein. in regard to the details of the interaction of the atom with the electromagnetic field. whence the term Not only is the variation as ?r~ in accord with the scheme of terms as given by the LymanBalmerPaschen series in hydrogen. The unsatisfactoriness of the theory came more and more into the foreground in the early part of the 192030 decade after almost ten years in which . The theory was quite incomplete. however. It gave no definite lines. The theory called for a study of the model by means of classical mechanics. Schwarzschild).INTRODUCTION mass according to classical mechanics under their mutual attraction as given by the Coulomb inversesquare law. Evidently Bohr s principles had to be regarded as provisional indications of the direction in which a more satisfactory theory was to be sought. The allowed circular orbits were determined simply by the requirement (an additional postulate of the quantum theory) that the angular momentum of the system be an integral multiple of H = hjSir. Also it gave rise to much Important work in extending the model and the quantum principle to other more complicated atomic and molecular structures.
while v is the timelike component of a fourvector of which is the spacelike part. the associated momentum wave is of the particle is p in magnitude and propagated with a wavenumber a related to p by the equation p = JIG. Very roughly the idea is that just as geometrical optics is adequate for phenomena in which all apertures are large compared with the wavelength of light otherwise diffraction effects . Its successes in such special applications were sufficient to create confidence in the principle. and others. The earlier work is usually quantum theory: it consisted of a few quantum postulates on to the classical kinematics and dynamics. We shall give just a sketch of the origin of the new theory. By quantum mechanics patched we mean the much more unified theory of atomic physics which we owe to de Broglie. This suggestion was made in 1924. Something over a year later it was taken up by Schrodinger and developed in his famous series of papers on wave mechanics. the discovery which has been so extraordinarily fruitful for all parts of atomic physics in the past eight years. Dirac. This emphasizes that the laws of atomic physics must be of such a character that they agree with the classical mechanics and electromagnetic theory in the limit of large quantum numbers. Heisenberg.INTRODUCTION". The most important theoretical development was Bohr s correspondence principle. at first along two quite different lines which were quickly brought referred to as into close relationship. He was led to the formal conclusion that a wave motion is associated with the motion of a particle such that if the direction. In this period much was done in the study of atomic spectra and the formulation of the results in the language of the Bohr theory. It developed rapidly from 1925 onwards. due to Hamilton. between the laws of mechanics and the laws of geometrical optics. This principle was able to make much more definite some of the results of the previous theory in the way of special calculations in particular it gave an approximate method of calculating the relative intensity of spectral lines. This was suggested by the equation E = hv together with the fact that in relativity theory E is the timelike component of a fourvector of which p is the spacelike part. Schrodinger. This was the period just preceding the discovery of the formalism of quantum mechanics. What was much more important than the special applications was the use of the principle as a broad general guide in the attempts to formulate a more complete set of laws for atomic physics* The important problem before theoretical physics was thus the develop ment of a rational system of quantum mechanics. De Broglie built his work on an analogy. 7 physicists were busy making such progress as was possible with the original Bohr theory.
The modern study of multiplets was begun by Catalan. and then to try to alter the formulas so obtained in such a way that the change was negligible for large quantum numbers but was of such a nature that it brought about agreement with experiment for small quantum numbers. Important contributions were made by Pauli. This spin hypothesis quickly many difficult points. In a few months the mathematical equivalence of Schrodinger s wave mechanics and Heisenberg s matrix mechanics was established. The work of Jordan and of Dirac led to a formulation of a single mathematical all system of quantum mechanics. This is the formulation in terms of which current work of importance in quantum physics is expressed today. was regarded by Heisenberg as a single mathematical entity. By treating it and other quantities related to the atom s structure by the mathematical rules of matrix algebra it was found that a definite formulation of the laws of quantum mechanics could be given in accordance with the correspondence principle. and Russell. At the same time Heisenberg took a decisive step in the formulation of matrix mechanics as a definite realization of the correspondence principle programme. for all values of n and m. so that it at once gained acceptance. After the study of series spectra of the alkalilikp metals in terms of the Bohr theory the next important steps were the empirical discovery by Land6 of the laws of the Zeeman effect and the discovery and extensive study of related groups of lines called multiplets in complex spectra. This double array of quantities. The multiplet structure and the problems of the anomalous Zeeman effect called for an essential generaliza tion of the electronorbit model which was supplied in 1925 by Uhlenbeck and Goudsmit by postulating an intrinsic magnetic moment and angular momentum for the electron. It is really remarkable how much of the modern. During this period the study of atomic spectra was being actively pushed on.8 are important INTRODUCTION so also classical mechanics is adequate where the linear dimensions involved are large compared to h/p otherwise effects akin to diffraction are important: these are the special effects which we find in the region of the quantum phenomena of atomic physics. There was developed a vectorcoupling model for complex atoms in which the quantization of the angular momenta of the individual . Heisenberg. theory of line spectra was developed in this way. cleared up In the prequantummechanical period the general method of working on a detailed question in the theory of atomic spectra was to calculate from an assumed model by means of classical mechanics. The initial step was to regard the atom as characterized by &n i 9 ensemble of quantities of the type Pnm e2flTiv ^ in which Pnm gives the amplitude of a classical harmonic oscillator whose intensity of radiation and type of polarization is the same as that of the light of frequency vnm from the actual atom. Hund.
but were obtained in semi empirical ways from consideration of a formulation of the theory that was only true in the limit of large quantum numbers. But that does not mean that the new mechanics is without importance for our understanding of line spectra. Schrodinger and Dirac when applied systematic ally to the study of the nuclear model of the atom is adequate to give an. Moreover. alterations in the theory. This first found a rational place in the theory with the advent of quantum mechanics. Complete as the general picture be lurking somewhere important residual effects. since the results obtained were not part of a closed structure of definite physical principles. Naturally in so short a time it was not possible to make precise and detailed calculations of the system of energy levels of all atoms. so that it is possible to give a unified deductive treatment of atomic spectra in terms of the quantummechanical theory of the nuclear atom. To this period also belongs the discovery of the important exclusion principle of Pauli according to which no two electrons in an atom may have the same set of quantum numbers. especially through the work of Hund in predict ing the general structure of complex spectra and extending the theory of the periodic system of the elements as begun by Bohr. like the advance of the which will necessitate essential perihelion of Mercury in celestial mechanics. Much remains to be done in the way of precise and detailed calculations and it may well be that when these are made it will be found that such an estimate of the power and scope of our present theoretical knowledge is overseems at present. it was of the greatest importance. As an empirical principle. however. This application of quantum mechanics to the atomic model has been the programme of research in the theory of atomic spectra from 1926 onwards. That is the programme of this book. not all the problems of interest could be handled in this way. there may well optimistic. accurate and complete unification of the great amount of empirical data accumulated through analyses of atomic spectra.INTRODUCTION 9 electron orbits and of their vector resultant played a dominant role. In spite of the mathematical com plexities. it became clear in the next five or six years that the quantum mechanics of Heisenberg. Thus it happened that by ingenious use of the correspondence principle a great deal of the modern theory of atomic spectra was worked out without the aid of quantum mechanics. so there were detailed calculations on which to test the quantum mechanical method as well as the task of securing from definite calculations by the new methods those results which had been cleverly guessed with the aid of the correspondence principle. Future development in this field . but enough has been done to give rise to a general conviction that the theory is quite adequate for the interpreta tion of atomic spectra. At present the theory exists in a somewhat closed and complete form.
More elementary. Likewise we make no attempt at a complete account of the formulation of the principles of quantum mechanics. Atombau und Spektrallinien. are SOMMEBFELD (translation by BEOSE). PATJMNG and GOUDSMIT. 1932. Elementary Theory. RTTABK and UBEY. we haTe opened the detailed discussion with a brief account. In this book we make no attempt at following the historical order. Most important among these are BIBAC. At present spectra and there are several systematic accounts of the subject of line their theoretical interpretation. Quantum Mechanics. and hence more suited to a first approach to the subject. Quantum Mechanics. 1934. however. 1930. CONDON and MOBSE. 1929. The Structure of Line Spectra. Advanced General Theory. Springer. The succeeding two chapters are devoted to the presentation of special results from the general theory which are used throughout the book. the detailed develop ment of the theory of atomic spectra begins with Chapter v. 1927. WHITE. An Outline of Wave Mechanics. requiring radical revision of the present theory. MOTT. Viewcg. Mokcules and Quanta. McGrawHill. Atoms. 1930. EEENKEL. This account is intended simply as a review of principles used throughout the rest of the work and as a repository of the theory in convenient form for reference. 1932. McGrawHill. GIBBS. 1935. Liniensgektren und periodisches System der Mlemente. The most important are SOMMEBFELD. In either case the time seems ripe for taking stock of the rapid developments of the past decade in order to prepare ourselves for the completion of the study of line spectra of atoms in the experimental and theoretical studies of the future. We manage to get along without it. Rev. as there are now in existence several works on this subject. All except the last of these are written from the standpoint of the correspondence principle. Line Spectra of the Elements. 278 (1932). Mod. MetBuen. J.10 INTRODUCTION may be merely a story of the filling in of details without essential change in the present views. 1931. Oxford. in the next chapter. Wave Mechanics. Springer. 1934. second edition. Phys. Springer. The reader will have heard that this mathematical discipline is of great import ance for the subject. of the principles of quantum mechanics. We wish finally to make a few remarks concerning the place of the theory of groups in the study of the quantum mechanics of atomic spectra. Cambridge University Press. JSlementare Quantenmechanik. Oxford University Press. 1930. F. VON NEUMANN. When Dirac visited Princeton in 1928 he gave a seminar report on his paper showing the connection of exchange energy with the spin variables of the electron. HITND. 1930. 1930. In order to make this book more useful for independent reading. Wave Mechanics. We have confined our attention to the historical developments to the brief sketch of this introductory chapter. J. BOBN and JOBDAN. McGrawHill. Or it may be that essential difficulties will appear. Oxford. Wave Mechanics. ERENKEL. J. Mathematische Qrundlagen der Qitantmmachanik. McGrawHill. In . Introduction to Atomic Spectra. 4.
Dirac replied. WeyFs protest to Dirac is certainly also applicable to this book. T in der QuantenmechamJc. Methuen.I said I would obtain the results without previous know ledge of group theory. Vieweg. (translation by ROBERTSON). as Weyl said. But so is Dirac s answer. 1931. but. J. This does not mean that is related to the atomic physics that branch of mathematics tool in the we underestimate the value of group theory for nor that we feel that physicists should omit the study of them so new theory. all of Dirac s arguments were really applications of group theory. branch of physics is likely to take most delight in the fact that the theory hitherto rather exemplifies parts of pure mathematics which have been devoid of physical applications. it seems like putting unnecessary simply if to treat the subject by a method which requires this the other hand the pure mathematician studying a new equipment. many new things now that it has been shown to be an important It is simply that the new developments bring with to be learned that it seems inadvisable to add this additional burden to the load. ". T . one of the greatest barriers is that it generally involves new mathe matical techniques with which he is apt to be unfamiliar.INTRODUCTION the discussion following the report. Many things which are done here could be done more Quantum mechanics the theory of groups were part of the ordinary mathematical equipment of physicists. Group Theory der Atomspektren. forces him to a more careful study of boundary value and matrix algebra. To him our plan is not as satisfactory as one obstacles in the way On which shows how the theory of the structure of the atom abstract theory of groups. Springer. But as it is not. WIGNEB. Die 1932. Qruppentheorie und ihre Anwendung auf die Quantenmechanik F. 1931. For those who wish to regard the theory of atomic spectra from the are three books available at present: standpoint of the theory of groups there WEYL and Quantum Mechanic*. Hence if we can minimize the amount of new problems mathematics he must learn in order to penetrate a new field we do him a real service. VAN DEB WAEEBEN. gruppenthe&retische Metlioden . Relativity theory brought the necessity of learning tensor calculus and Riemannian geometry. When a physicist is desirous of learning of new theoretical developments in his subject.". 11 Weyl protested that Dirac had said that he would derive the results without the use of group theory. That incident serves to illustrate our attitude on this point.
Quantum Mechanics (page references are to the second edition). tp s.lt. This will page be followed by a discussion of matrix mechanics.gt. Thus confusion between the symbolic and Schredinger s ^ function will be avoided. Symbolic algebra of states and observables. but we prefer the latter notation because it is more J Dirac uses symmetrical and more easily translated into the Schrodinger in representation. but is vectors in different spaces. reserving ordinary type cj&. For a mathematically more rigorous formulation see VON NEUMANN. a *J&. related subjects. we introduce $. and only real numbers may occur in the interpretation of the theory. a vector in the dual space.* subsequent to represent a state. Mathematische Grundlagm der (faantenmechanik.CHAPTER II THE QUANTUM MECHANICAL METHOD The formulation our purpose is of the laws of quantum mechanics which is most suited to his book. giving references to Dirac.gt.gt. there is no sense in which we can split 4* into a real and an imaginary part.gt. Since tj and $ are [*. The product of a ^ by an ordinary number c is a ty whose components *\&.gt. shall not restrict ourselves to the letter &. but shall at times use different letters for different states. and discussed at length in We and shall review in brief such of this formulation as we shall need.. p.* that due to Dirac.]* system has independent states.lt. the symbolic conjugate imaginary of 4. type for symbolic quantities. are c times those of the original Two states are not considered to be distinct unless the tys which describe them are linearly independent. In any given representation the components are ordinary (in general. f We shall in this chapter use boldfaced and operators in the Schrodinger scheme and for ordinary numbers. chapters we Furthermore. II) is described by a quantity called which is analogous to a unit vector in a space of a great many (in general an infinite number of) dimensions (p. for functions t&. in place of $. Its components are the ordinary com plex conjugates of the corresponding components of *. The state of a system (Dirac. coordinate system. The sum of two ij/s is another fy whose components are the sums of the components of the two of 4&. complex) numbers.* * DIRAC. . In this section the principles of the theory will be set down in terms of the properties of certain abstract symbols in a manner corresponding to the purely symbolic treatment of vector analysis which is independent of any 1. 1S). where a fuller account may be found. 4* has as many components as the &.lt.gt. The distinction between and $ is more fundamental than that between ordinary complex conjugates. &.J if is not a vector in the same space as t&. there is no place in the algebra for the addition of and a $. Since the components of are allowed to be complex. perturbation theory.
gt. r + 8 . of two observables defined by foo^a^oyl*). to the dyadic of Gibbs. that 4*?4*s an(^ $s4 r are complex conjugate numbers. (ai We define the sum. a (w\&. In an experiment we are generally concerned with determining.gt. the particular number which expresses the value of a dynamical at a particular time.or pointerreading. Thus we are dealing not merely with a new set of laws but with an new mathematical canvas on which to represent these laws. denote the result of operation of a on ^ We We need make imaginary to no of provision for the operation is another i*.g. Instead it appears as a quantity of a more complicated sort about to be described. will be repre Any such dynamical variable will be called an observable.gt. Any set of experimental apparatus and operations does not which appear in the theory simply as the source of certain pointerreadings bear a direct functional relationship to other sets of pointerreadings.lt. where a on $. f Linearity of a means that we have and s are any two states and a and b .fa at4&. directly or indirectly.I2 SYMBOLIC ALGEBRA OF STATES AITD OBSERVABLES 13 have a product which is defined as the analogue of the scalar product of two vectors in vector analysis and is therefore an ordinary number.gt. scripts denote different states of a system. respect. The essential the laws of physics has been that we have expected to be able to formulate physics in terms of functional relationships between the pointerreadings and exact given by various sets of observing apparatus.. An observable in the sented and converting it into mathematical theory is a rule for acting on any to a tensor of the second rank. are ordinary numbers. variable. e. In this entirely respect the quantum mechanics is a much more farreaching departure from classical physics than was the theory of relativity. This product will where the sub by convention always be written with the $ first. oij&. We now suppose that any 4* &&d any 4v*K&. (j&.lt. of fy is arbitrary. r}&. feature of classical resulting in a scale.gt. unless otherwise stated we shall take all i]/s to be normalized.lt. by a^. Hence. a on $. where &.gt. r + bfy s = ) aat&. e. 0^ + *%. be written as 61&. . where two observables by The product.&.gt. and that tp^r is real and positive.gt. All of physics has proceeded along such lines hitherto. 22).gt.lt.gt.p fy. for any r and s.gt. in general complex (p. In observing a system experimentally we build an apparatus on a macro scopic scale which interacts with the system by a certain set of operations.. or it is analogous In this another &.* The conjugate ai&. then. + a 2 )4 = a1^ + a 2 is 4&. 24).g. the position or momentum of an electron. in general *&**&. a^. will a&. Since * Dirac does provide for the operation of writing = &. It follows. see equation (2). Quantum mechanics natural science does not do this. and in this theory by a linear operator a (p.
gt. as can be .14 is oil&. denoted by a 1 ". The complex imaginary to i}&. at is called the Hermitian conjugate of oc because its matrix is the Hermitian conjugate of the matrix of a.gt. is defined by the equation (2) where the two states r and 5 are arbitrary (p. because of the Hermitian and antiHerinitian character of their matrices ( 7). where p is a real observable. These are called the allowed. . possible values of a. 4&. by $ r to get $ r k = a$ rfy = a [from r number a.f We shall follow Dirac in calling the which satisfy this equation the eigentys and the states which they denote the eigenstates of the observable a. another j. r will certainly give for the result the number a will be necessarily real. or of a. if for all states r and s.gt. For shown by ( 1 )] Here $ r ai. the possible results of an numbers a for which the equation in ^. That is. at&. observation of are the ordinary an observable a.J/s belonging to the eigenvalue oc . (6) (p. f The whole set of eigenvalues is often called the spectrum of a. The relation between a and a is the same as that between ordinary complex ia ".lt. r is real by (3). The so a is real.e. 29). Similarly. i. is characterized by the fact that the observ able a has the value a.* It can ". and may form a discrete set or a continuous set of eigenvalues numbers.gt. We now make the important physical postulate (p.gt. characteristic. We shall speak of an eigen^ which satisfies this equation for a given a as &.(a (y a ) ).gt.(a )..gt. An observable a is said to be purely imaginary if a = a. (ia)*= observable a is said to be real 1 . The $ r wfy 8 = $ r 8 (wl&. An conjugates. no rule against 1 * a * f adding a and a . 30). a4 = a has solutions 4&. 1 there is 1 &. 29).gt. such an observable may be written as ip. and denote ) it by ). That is.. that a measurement of the observable a with the system in the state a real observable a the multiplying (5) ij&.(a ) we denote by $(a This satisfies the relation * The operators corresponding to real and purely imaginary observables are said to be Hermitian and ant^Henmtian respectively.gt. I 2 ) observable (Hermitian) conjugate to a. THE QUANTUM MECHANICAL METHOD is an ordinary number. proper.(oc = oc 4&. 30) that a state for where a is an ordinary number. 1 be shown from (2) that hence if c^ and a 2 are two real observables the commutator (oc^ a 2 a 1 ) is a observable (p. if oc^ is also real this commutator purely imaginary vanishes.
hence the theorem We now assume that the plete (p. Hence show that the first physical postulate above is a special case of the second. and find the relation between the eigen^ s of a and those of 5aS~x Show .* . and the different 4K a ) s ^^ require another index which takes on the values 1. by writing a = ar 4.ia$ where ar and c^ are real observ4&. we shall never have occasion to determine their characteristic values or functions. since these lack physical significance in quantum mechanics. For a real observable this average value is seen from (3) to be real for any state Moreover.. viz. but observes the various proper values of a with certain probabilities. 33).. $*]* f r aU *s 4&. Representations of states and observables. 1.1 ^ 1) has the same allowed values as a. . Show ). it is seen that a necessary condition for the reality of . Although we shall have occasion to employ nonreal observables as an aid in calculation. 4 is here assumed normalized in the sense of (1). that the observable SaS 1 (where S^SSS". 43).gt. We shall first show that the eigenij/s of a system belonging t0 two different allowed values of a real observable are (unitary) orthogonal in the sense that $(a )4(a". one does not always obtain the same value.gt. 2.gt.. d a for their complete specification. * Note that whenever the combination $(oc )a ^&. this may be replaced by oc a real observable. 2. 2. say d a linearly independent . Now if one makes observations of a on a system in a state i{* which is not an eigenstate of a. tp s belonging to the same eigenvalue a In this case the value a will be said to be d a fold degenerate.. ables.(a ) = 0. of exactly what classes of *I&.lt.) = unless a = a*.&. system in which we This amounts to assuming the whole of a kind of generalized SturmLiouville theory at one step. the eigenij/s of a general f Note that observable do not form an orthogonal set. 3.)$(oc )&. these considerations hold only for real observables. Prove that two real observables commute if and only if their product is real. . that the average of the values of a obtained in this way is the number tpa4 which is characteristic of the state 4* (p. We now make a second physical postulate.gt. 34).* 1 23 and I 2 7b) Therefore (a a".]&. PROBLEMS /(a that the allowed values of any function /(a) expressible as a power series in a are This can be generalized to other functions (p. observe that I 2 7a) (from (p. hence much needs to be filled in here by a study s can be so expanded. (from ). observables. eigentj/s of any real observablef form a com can make a Fourier expansion of an arbitrary fy if a is arises.I2 SYMBOLIC ALGEBRA OF STATES AND OBSEKVABLES 15 There may be several.gt. the vanishing of ai Since the results of physical observation are real for all states we conclude that all physically measurable quantities are real 4&.(yf) . (1) To prove this. 38).gt.gt.
We shall write the expansion in terms of these states be expanded a".). We observe that a". different states belonging to the degenerate level a Let us choose an observable p which commutes with a. (paap0) (6) Let us now set ourselves the problem of finding the eigenstates of p. we shall choose the a linearly independent .( r". (5) show how we may obtain a Before proceeding further with the algebra of this expansion theory we shall significant choice and characterization of the . which results from the action of the observ This state can be expanded in terms of the complete set P4&. .(oc coefficient as (a r  placing 4* it after the eigenstate: = StKa a r r )(aV ). hence / (oc a". r ).(aVO(aV / j 8a V".r". while If a(3 = pa. a".). Here ) (a and unity if which is zero if a ^ representing the allowed values of a that any state ty may oc = (the Kronecker delta).gt. COTJRANT and HILBEBT.~fold the case in which a has a purely discrete spectrum. p.. states belonging to a normalized and mutually orthogonal This we may do states belonging to oc by a Schmidt process* since any linear combination of Denote these d^ states by 4K a/r ) for r = 1. We then have. the coefficients of i}&. (3) The blank space is reserved for example we write a ". d^. X ). according to these requirements. If the d degenerate.. Hetlioden der MathematiscJien Physik.. from which we draw the j8a / important conclusion that (oc V aV)=:0 unless oc = a".)(oc / on the right of these two equations r ) = 0.) = 8(a .16 Consider first THE QUANTUM MECHANICAL METHOD oc 22 value is da &. Expanding the allowed values equation 4&. r". will also belong to a .) (2) is a function of the discrete set of points satisfied. Denote let (4) represent its expansion we must then deter such a state by j3 ) and mine the coefficients (oc r /3 ).gt.(a". the relations $( r ) t^a* r".) S(r .gt. The assumption is.) = St.) this expansion we adopt the a r notation /  pt&. able p vl*(oc".gt.gt. then.(aV). from (5).(aV) // must be equal. = S a ar 4&.. . aV Consider the state on For *]&. to characterize the $ which is being expanded. ( * See for example.r".r". 34.gt. a".gt.
gt. Higher Algebra. / .r .(/O r". e. (8) Here all the coefficients in a given equation refer to the same eigenvalue of a. If set of states j5 ) which .e. of the form /J y ).e. we may choose a third observable y (independent of a and p in the sense that y is not a function of a and p) which commutes with both a and p.22 REPRESENTATIONS OF STATES AND OBSERVABLES 17 we obtain S a* r* a r *l(*V)(aV/Joe*r r j8a r )(". Since all the eigenstates of p are given by (8).f th Setting this determinant equal to zero gives an equation of which are consistent degree in /T whose roots are the d^ eigenvalues dtf with the conditions assumed.We continue dependent commuting observables until we find no degeneracy in a simul taneous eigenstate of aE of them. we have found a complete we have found a complete set of solutions are simultaneously eigenstates of a and of p. let us set ft) . an eigen state is determined by its direction except for an arbitraiy phase factor e^ f f See.g. BOOKER.gt. we may find a nonvanishing must vanish. i. linear equations for the coefficients ( use the special property (6) of p to the simpler set f ljSla OtaVljS J^jSXotVljSO for all a .y! quantummechanical analogue of the classical number of degrees of freedom.. . Hence we may consider independently the d a equations corresponding to &. ie. 4&. A . Thus a calcium atom with 20 electrons and a fixed nucleus will be found to * set of linear homogeneous equations determines only the ratios of the unknowns. (cc". The number of such observables is the 7 ty(&. 47.r )( r/3 ) = Sj8XaV)(Vj8 a r /5 ) ). (7) TMs set of homogeneous reduces when we Sta r".x". the direction of a vector but not its magnitude. and since of (8). the eigenvalue a These d a equations determine the direction* of that part of which lies in the c a. .gt.gt. We may by a process similar to the is still above find a complete set of eigenstates of y which are simultaneously eigen to introduce in states of a and p. But because of the normalization condition.lt. p. whence S (a * j3 ) = j8 (a r for all a&.dimensional subspace characterized by a Let us find the solutions which lie wholly in this subspace. \ = ot In order that equal to zero unless solution of this type. To each of these roots belongs an eigenstate of $ p lying wholly in the subspace characterized by a To a multiple (d a^fold) root @ will belong d^p linearly independent eigenstates lying in this subit is clear that space. the determinant &.lt. *I&.(a there a degeneracy in these states. i.
gt. say for the complete description of its state. * The normalization condition satisfied by the eigenstates of such a set of observables is given by As a matter of convenience we shall write this product of S s as 8(y^.y^. A set n erms of whose simultaneous eigenstates Yfc * Ya we can describe the state of a system completely.18 THE QUANTUM MECHANICAL METHOD numbers * &.. We can choose a complete set of observables in various ways since any in 8 of the y s w^ &so form a dependent commuting functions 8 1? 8 2 . &.. of 4* with the t&. fc &. (13) The  set of eigenstates is ) (P unit vector of is 4&..(r If the 4&.gt.) coefficients.gt. .[(!". r where ( r )(P ) = $&.gt. 22 require 80 quantum of observables..gt. hence (F A ) and (A   I".gt.. . a set of orthogonal unit vectors.). . A general state 4* has the expansion [cf. We shall denote this set of observables by F for short.. which we shall denote by A. and shall write the as 4(F ). A unitary transformation is a transformation from one set of normalized (unitary) orthogonal states to another such set. . is said to be a complete set. Let us now return to a consideration of the algebra of representations in terms of the eigenstates of such complete sets of observables. yk Yi&. ). y^yj!) r simply S(F. 7j complete set. ).gt.(A t&.lt. The component in the proper sense.r f ). say use the following convenient notation.gt. (3)] The expansion coefficients are given explicitly by multiplying with f $(T (ii) ): OH )=$(r*)4*. given by the scalar product. which is seen to be com we pletely selfconsistent: r (12 ) These equations express the (unitary^) transformation from one system of are known as transformation eigenstates to another. we are expanding is an eigeni* of any set of observables A. For the complex imaginary equation to (10) we shall use the notation (12) $=S( inftr).* general state characterized by th&quantum numbers y[ y^.
Show that the sum of the diagonal elements (the trace) of the matrix of an observable independent of representation. af From the definition 1 2 2 it follows that the elements of the matrix of ).e. 3. (21) and that this sum is just equal to the sum of the characteristic values of the observable by their degeneracies. two different representations is (18) 2.KP) = *(n(naP). i. y say y^. weighted In the Tscheme we can represent the action of a on any fy [cf. and the numbers themselves are called matrix elements or components (cf. In the r scheme the matrix of any one of the s.lt.22 REPRESENTATIONS OF STATES AND OBSERVABLES The observable a is 19 characterized in the T scheme by the set of numbers (14) (Hall". (5)] by* a&. 7 2 ). that is A A ). (15) that (P^nP) = %S rr *. PROBLEMS 1. is diagonal [i. are given by (rVr*)(E&.e. a. which is characteristic of (20) 4. &.) defined [cf. a unitary transformation (19) FT". = ].Jj . The matrix of an observable a which commutes ".gt.gt. Show that the relation between the matrix components of a in two different representations is (A ocA". Since Yi^(P) = we have from (Pnl r is zero unless yi^(P)&.e. (The DiagonalSum Rule) 5.gt. i. Derive the following identity. for which (Pan(raP). and the is cation indicates that this appear in the order opposite to that conventional for multipli not their scalar product but that they form a unit dyad.) P P P P with Yi is diagonal with respect to y i3 This follows at once from (6).lt. (PaP ) Is zero unless yi = yj.r (16) The matrix of a f is the Hermitian conjugate of the matrix of a. Show that the relation between the components of ij* in ). and given explicitly by The square array formed from these numbers as and range over the allowed values of the observables T is called the inairix of a. The matrix of a real observable. is (17) said to be Hermitian.) = S (A P) (Flam (r*A*). ) ( 10)] in the following fashion: (22) * In this notation one obtains a complete analogy between the form of a quantummechanical observable and Gibbs dyadic if one writes a as the operator Here the fact that the t{&.
show that if where K is a constant independent of fcl i and jf. THE QUANTUM MECHANICAL METHOD Show Show that if 22 a anticommutes with y.. then also S (AiM Aj) &.. Continuous eigenvalues and the SchrSdinger representation. on multi wm . the 8 function may be in general treated as an exact symbol when integrated out according to (4). If w 1 is plication of (3) with $(w in the continuous m ). (aY 8 + Ya=0)  (23) that the elements of the matrix of the product ap of two observables are given by (24) (FloflnS (Flam (r lflr*). ( ". (3) where w ranges over the discrete spectrum.. is An eigennj* belonging to a value w lying in the continuous range be normalized according to to $(w )ty(w ) = *(v/ w*) f 9 (1) where 8(#) is an improper even function of a? defined by (2) J which see for a complete discussion of the S function)..lt. ^(A?) derived from these by m n S(rtr!) 8 m n Sl(AtaAi)*.gt. a unitary transformation. .gt. )( w &. =S (The Principle o/ Spectrottcopic Stability) For the states of the preceding problem. Consider a set of derived from these by a unitary transformation: m 4&.(Ai). 3 B continuous. (w".\ ). iKTj). from (1) and the relation (4) ff(x)S(x~a)dx=f(a) * The 8 function as used in connection with continuous spectra is to be regarded as a convenient abbreviated notation which permits simplification in the Handling of more complicated mathe continuous spectrum..20 6. the matrix element (r lar*)=0 unless yj= y*.gt. 7. is certainly the most convenient.(IT) and a set of m states 4&. (25) S 9. over the continuous spec trum of w. Here for all w /fl \ ) = $(uf)fy spectrum this follows. states i^rj). ... ..AiaAi) =* 8&.. w". If a is any observable. This treatment of the one into trouble.. Consider also a set of n states ^(Pj).. show that 4W) ... . 8. Chapter iv. t&.gt..\ ) + (w )dw". and a set ^(Aj). These formulas must be modified in the case of an observable w whose but is wholly or partially spectrum of eigenvalues is not wholly discrete..lt.* The expansion of an arbitrary in terms of the eigen^ s of w will now be of the form (Dirac. although able to lead matically rigorous expressions.
32 (Dirac. &. J&. $=( \x)$(x)dx. THE SCHRODINGER REPBESENTATION r 21 In general.gt. ) (x\ This representation in terms of the eigenij/s of x (the Schrodinger repre sentation) is the most useful of all representations.).. 73). Coordinates will throughout this work be relegated to the position of sub function ) if* when they need be written. since from it is derived the Schrodinger equation which has proved to be a most powerful tool in the where explicit solution of quantummechanical problems.. we can the state J/T. This function (o? (x\ of 4 and will be written as (the Schrodinger Schrodinger representative function). Thus the function (x\T ) which is the Schrodinger representative of fy(T ) will be written as ^x (T ) and called scripts f f the (Schrodinger) eigen*/r belonging to F. and z form a set of commuting observables (complete except for the peculiarity of electron spin which we shall later introduce as a fourth commuting observable a having just two eigenvalues). since no distinction need be made between the operator x and the allowed value x in the Schrodinger scheme. For n particles we have the set #1 i *n yn zn We shall denote this whole set of observables by *i &. Since iff determines equally well speak of a system as being in the state fy or the state t&. and of 8(w for S a a .gt.gt. or $x if we wish to indicate the independent variable explicitly.. (5) S^^J^S^Oa^^S^O x. dz n . a similar replacement of integration over the wn ) continuous spectrum for summation over the discrete..lt.. x for short. . f dx=dxidyi dzt . The most important instance of an observable with a continuous spectrum is the coordinate x. For a single particle in three dimensions x. p.(x*) = 8(tftf).gt.gt. &. &. &.gt. . the space on the line being reserved for the more important quantum numbers. In this notation the expansion (6) becomes * There will be no confusion with the Schrodinger operator x because of the omission of the prime here. which we assume to have a completely continuous range of allowed values. It will be noted that the is called the ) completely determines ty.8&. 4(r ) or the state ^(F). where writing $(tf)i\&.gt. y.gt. (6)t and ( \x) are complex conjugate functions of x. We shall usually denote merely* by x is then written The expansion of an an allowed value of the above set of observables arbitrary fy i& terms of the eigeni/s of )dx.must be made in the preceding discussion in the case of a continuous / spectrum.
22 If a is THE QUANTUM MECHANICAL METHOD an observable. and (7). (10) The proof of this follows from (4).lt. 32 wty is a 4&./r it wft which represents aty* We shall now prove two theorems which show the great similarity in behaviour of 4 and ^ that justifies their being called by the same letter./r(2).lt.lt. (5). (9) If w is an observable which has a continuous range of eigenvalues. we *= This equation defines the operator a in the Schrodinger sense as that func which represents ^ and turns tional operator which acts on the function &.their representatives are equal. and that &. if two 4 s The scalar product of two i&. where /(x) is any algebraic function of the set of observables X 9 is just the function /(x) t^.(r $(r HS rr * . This is easily seen to be the case: /(*)*&.gt../s.gt. have the normalization (theorem II) * This notation assumes that the representative off(x) t{j./&. . shall write as oc&.lt. its eigenstates must be jnormalized according to (1) instead of 1 2 1 and integrals must be substituted for sums in the f expansions in terms of */j(w ). II.lt. Now the eigenstates hence the ift(Y ) 4&.e. In this case we obtain for the normalizing condition u?) in place of (11).gt. This follows from the fact that that the s is the sum of the representatives of the individual of two I.(F) are normalized (2 2 9) according to )4&. Any tjj linear relation &. representative of cfy is c times the representative of are equal.gt. into the function which holds between ty$ holds also between their the representative of the sum representatives.&. This normalization Qfi// x(w ) is accomplished in such a way that the set of eigendifferentials ) (12) if we choose the normalization factor = W t f V AJw (13) . s equals the integral of the is product of their representatives in the sense that if 4(1) tlien represented by i/r(l) 3 ^(2) by &.gt. and will have a Schrodinger representative shall write (8) which we i..gt.
i/j 4 =4 J & w".gt. if K w !i&.gt. and it is in some such way that a mathematically rigorous treatment of the continuous * The set of functions ^(F ) are to be considered as a set of unit vectors in ordinary function space (Hilbert space) in terms of which any arbitrary ift may be expanded.gt. A0* ^asK) dw/ / w.$(? ) (PI ). &. 0) )&.) has the expansion Hence the f vLift(T ) of (8) will have the expansion r )) (is) where from 2 2 15 and theorem II (19) Finally the allowed values equation cciK0 = a becomes the functional equation a&. and w". has the value 1 .written as a sum over Xx( wT values spaced by the interval (this is rigorously true asymptotically as A&. may be expanded in the T scheme according to f r Hence (theorem where* I) $=?&./r(oc &. To see this let us evaluate the integral w". . and will w chosen at the small intervals A have all the properties of a set of eigenfunctions going with discrete eigenvalues.*=^A.gt. J \tJw )$ Now the integral over w".lt. a symbolic x(w ) which would have properties similar to the above. (20) which is is the general form of Schrodinger s equation for any observable.32 CONTINUOUS EIGENVALUES 23 Any 4&. /". in exact analogy.gt. (16) (17) (P ) = $(? )$= r )$da:.) If J I I /W I +AA rici^+A r~ J w".K* ) ) =a &. /C The expansion of a ^ where wr takes on in terms of the eigen^ s of w may then be ".gt.gt.lt. f A. A : wr We could define. The ^ s will then be orthogonal if \iv ~ A.lt.A(oc )&.\ for values of [ / XtA W/ ) Xx( w dx = ". The state a 4* (I". As normalized to unity in the sense of (11). for all values of w which and the value for all other values of w The whole integral then lie between becomes w". spectrum must be given.
.gt. $&. In the state I". (i) s have the values in the state i&. 65).gt. we must modify the above computation to suit the case of is given by a continuous observable. Since /(x) is an arbitrary function of the variables x.(F ). Consider any function /(F) of y ls y 2 . The mean value off(x) in the state If we ^&. what is the probability P(T Yfc on a system answered In the o4* ^kis question ma y be finding the values y 1? y^.gt. Yi&.e. p. I".lt. we obtain from this the physical interpretation of Schrodinger s ?/r function: that $$dx is the prob ability that the system be in the coordinate volume element between x and x+dx. r On the other hand.. 6*. this average value must equal Since the last two expressions are equal for arbitrary functions equate coefficients of each /(I".) to obtain /. from 3 2 9 and 3 2 10. &. an. The statistical interpretation.24 THE QUANTUM MECHANICAL METHOD 32 of the yet we hare defined the operator a only symbolically. is in a state Similarly the probability that the y s have the values (r ) in which the 8 s are known to have the values A [i. make a measurement of the complete set of commuting observables of in the state ijj.The average value obtained is for this function when making measurements on If we Y2&. Y&.jff". This interpretation is seen to be consistent with the normalization of ^ as given by 2 (3 11).   ). r ) r . obvious generalization to the case of a set of commuting 1 2 .gt.1&. following way (Dirac.. we can p(r )=(r Hence the probability that the y 2 . the discovery functions of the co exact functional form of oc for observables that are ordinates and momenta was made by Schrodinger and will be the subject of 4.gt.gt.. On the other hand this mean value = jf(x)P(x)dx.lt. ) * Since f(T /(F) observables of Problem 1.) &. values in now ask the probability P(x)dx that the set x of observables have (to at x.
and the conjugate momenta 3C 15 & 2 . Of course the correspondence principle itself is a broad far partly generalization from experiment. if $o&4^0 ^or a^ 4&. 2. The laws of nature are not. so the for physical quantities all spring known relations between . We have now laid out the mathematical pattern in terms of which the laws of atomic physics are formulated. v V1 L#i&. . 5. The laws of quantum mechanics.3tyJ #i*j w ** x^ u. Analogous to the total energy of the system is a Hamiltonian function H. . [AB. but relations between the operators that stand for various modes of observation. xzn as commuting observables for a Schrodinger representation in3 2 ... real and has no negative eigenvalues.BC]=[A.42 THE STATISTICAL INTERPRETATION 25 1.gt.. The cartesian coordinates x l9 J 13 zl9 .gt. These equations are consistent with K$ and range of allowed values. 3 Pi 9 Pz&. The first both having a continuous equation has been presupposed in using pi x x & 25 . C] =01 .) 1. I". #3JIJ of a system of n particles. is 3. B] for the simple commutator closer analogy to the classical Poisson bracket. To a particular mode of observation with certain apparatus is to be associated a certain operator. the functional relations associated with each set of experimental operations has been carried out thus by appeal to the correspondence principle (as with coordinate and conjugate momentum) and partly by appeal to experiment (as position with electron spin).. then for all 4*.C]. (Dirac uses [A. Show directly that PROBLEMS = S ?(!". between the numerical values given by certain experiments. Show that if a real observable a has no negative eigenvalues. xn y n z n or for convenience .gt. Show that a + p where a and p are any two real observables.. The recognition of what operator is to be as before. ^en a nas no negative eigenvalues.gt.) The commutator of a single of two is given by formulas similar to that for a derivative of a observable with the * We AB for (AB BA)/i& in = product P roduct C]B +A[B. operators from experiment. *? 91): ^ p. C] [A. and conversely that 2 2 . Psn satisfy the following quantumtheoretic laws of nature r i (Dirac. B] shall use the notation [A.B]C+B(A. The remainder of the theory consists of the recognition of the properties of the operators which are to represent various observables. 2) . &. which is the same function of the p s and x s as on the classical theory for the BA.
is PROBLEM Show that the commutator is f( x )PiPiJ(x)**iH . 3 where this dfy/dt indicates a vector whose components are the time derivatives of the components of t* in a fixed representation. That continues to be its importance here. Because of these properties an eigenstate of energy is called a stationary state. ~  . as defined by 3 8: ai}&.f This is proved as follows: Corresponding equations obtain for the Schrodinger function $. In an any observable a is independent Since the probability that the set of observablesT have the values F depends only on the average values of all functions of the y s ( 4 2 ). any function of xl9 x 2&.gt.. and for any particular problem must be determined. by experiment. are of great importance in the quantum theory. the dependence of the state (Dirac. In Schrodinger s notation becomes ^ / (3 ) The time dependence of the eigenstates of energy One has for the eigenstate belonging to H . the exact order of factors and related questions. in the last analysis.26 THE QUANTUM MECHANICAL METHOD 52 analogous dynamical system* The importance of the Hamiltonian in the classical theory lay in the fact that through Hamilton s equations of motion it determined the time variation of the state. t If a does not involve the time explicitly.. 115) j* on the time being given (3) by . this probability independent of the time in such a state. xsn expressible as a power series. p. * . However.gt. which are immaterial in the classical theory.(# ).^dx. and therefore such a state merely changes its phase in time: eigenstate of energy the average value of of the time. 9X (5) where /(#) 6.. Schrodmger s equation. is particularly simple. We shall now discuss the question of the functional form of an observable 2 in the Schrodinger sense.= n^(x)tx.
der Phys. p) of xls is X3n .iM/dx). . Matrix mechanics. 2 (I) Hence the Schrodinger equation becomes (3 20) (2) a standard type of characteristic value differential equation whose characteristic values and functions are to be determined by the use of The original equation given by ). 361 (1926). SCHEODENGEB. conditions. See VON NEUMANN J S book. iifid/dXi). 734 (1926). 79. auxiliary boundary conditionsf on was this equation for the particular case a=J?. as shown by 3 9.. &. the quantum conditions 5 2 I for example . . SCHBODINGEB. t See p. The Schrodinger operator for /(#) Schrodinger s discovery* consisted of the observation that the proper operator for the observable p i is ifidjdxi This is easily shown to satisfy . 9p*n2 merely f(x).p) is = F(x. which gives Schrodinger t This is .62 SCHEOBINGEB is S EQUATION . Ann.. page 53 et seq. We have seen that by the use of Schrodinger s representation in terms of the continuous set of allowed values of the variables x^ formulation of the * we can obtain a theory entirely independent of symbolic 4 s and a s. 7. In .. 79. 27 where a Pi 9 supposed to be an algebraic function F(x./r(oc the energy levels and eigenstates of total energy. and in general the operator for a function g(p) is g( From an extension of these considerations it is seen that the Schrodinger operator for a general algebraic function a = F(x. This discussion is not complete. Ann. der Phys. 143 of DIEAC for a discussion of boundary the governing condition must be that one find a complete orthogonal set of solutions of (2).lt. hence We obtain the operator foipjpi by letting p$ operate Hence the Schrodinger operator for p^pi is ( ifidjdx^ ifid/dx).
557 (1925). If a is real. Chapter vi. i. 34. 2. Born. for example.28 THE QUANTUM MECHANICAL METHOD the same manner the theory can be formulated in a way in which we deal only with the matrices representing states and observables in terms of the discrete set of allowed values of a complete set of observables T. BOKN.7 = 1.. In this form we see clearly that we cannot add a 4? and a ip. 35. 22. fur Phys. HEISENBERG. BdoHEE.e. (cf. . This corre sponds to the original matrix mechanics of Heisenberg. ibid.* in the expansion represent $ (or iff) by the array of coefficients (F ) in terms of the ^(F ) [or ^(T )] written as a matrix of one column. by (PaP) (PaP) (PaP) (PaP) (PaP) . t The product of a matrix &? with m rows and k columns and a matrix 3S with n columns and k rows is defined as the matrix of m rows and n columns obtained as follows : * where all the S s are over . 2 2 20).. 879 (1925). . BORN and JOKDAN. in order that *jy^ niay be an ordinary number (a matrix of one row and one column).) labels the is the column.) becomes is (1) by the usual rule of matrix multiplicationf (cf. 858 (1925). Introduction to Higher Algebra.. the first index F in (Par". Zeits. ibid. and Jordan. That is. For example. and JORDAN. fc. where by convention second index T". the product $(A )*KA". 33.. 4* and 4K^ ) ar represented respectively by  We (P ) ) and When a $ represented this way. . and that we must form their product in the order tjujj The observable a is represented by (PalP) (PaP) (PaP) its matrix as defined in (PocP) . a $ must be represented by a matrix of one row. which means 2 2 17) that the diagonal elements are real and that the corre sponding elements on opposite sides of the diagonal are complex conjugates... HEISENBBEQ. For a discussion of matrix algebra see. this matrix row and the Hermitian.
.72 It is MATRIX MECHANICS 29 and uses the laws now readily seen that all of the preceding equations remain true when one substitutes for ^ s and a s their respective matrices of matrix algebra. i.e. While the coefficients (F A ) may be arranged into single rows or columns there is a sense in which the whole square to represent the matrix of 4*(A )&. give the allowed values of a. hence this calculation is known as the diagonalization of the matrix of a.. the equations (2) furnish d^ linearly independent sets of transformation coefficients (F ocV) for r these coefficients . The roots of (3). i.. condition (1): S(aVF)(FaV)==Srr (4) These transformation coefficients determine the eigenij/s of a. For a d a/fold root.. they determine those linear combinations of the eigen4 s off in terms of which the matrix of a is diagonal. An approximation to its solution in the case in which certain of the nondiagonal elements may be neglected will be considered in the next section. 2 (cf. The allowedvalues equation becomes a (PaP) (PaP) a a . 2 7 et seq.(2a) linear equations Carrying out the matrix multiplication. (3) This determinant.gt. which is called the secular equation..e. though usually of infinite order. (2b) The condition that determinant of the this set shall have a nontrivial solution is that the coefficients vanish. The values of must be chosen in accordance with the orthonormalization = 1.) / we obtain the set of simultaneous S[(F ar )a 8 r^](Fa ) = / / for all I". will often be such that the only nonvanishing elements lie in subsquares along the diagonal. d^. so that the infinite determinant will factor into an infinite product of finite determinants each of which can be treated by ordinary algebraic methods. that a (r ar 2 3 ) =o.. and A may conveniently be considered as the array of (FA ) s for all matrix which transforms the eigen^ s of T into the eigenij/s of A. Let us write (F A (F A S 2 2 ) F 2 ) (5) .
8. which we shall write as A  ). number.. . it will be desirable to choose the members of this set in a way significant to the a given * This is is the equation which is usually written in the form t In this discussion the ^ s and a s may be either in the symbolic or Schrodinger scheme.) ..  A". as in )ll 2 2 .30 THE QUANTUM MECHANICAL METHOD (r 72 The matrix on the right. which is easily seen to be the matrix (A r ) is also its reciprocal. ing observables in the F scheme and we wish to find the transformation to (A I  (F". i.. where I is the unit matrix.xVa we find (F a j8 $ )!! by the multiplica tion of (r oc&. say the observable If /3 we know = a + eF. and .lt.lt. p. 2.gt. by (7) by (3).e.  (7)* Al = (A Dll II (r jal nil of commut Suppose now that we are given the matrices of a set a.x. the scheme in which these are simultaneously diagonal. /J a )\\. . Perturbation theory. This enables us to obtain the matrix of 7 in the a /? t ) .. Let us denote the mutually distinct proper values of a by a 1 a 2 . . If now there is a dn fold degeneracy in the value a n we shall need another index to . denote these states by ^(an*). is (1) where e is supposed to be a small &. /} s scheme. n T= . Since eF may be considered as a as the perturba * perturbation on this approximation method known tion theory. is a unitary matrix in the usual sense: it has the property that its Hermitian conjugate. by (1). &. jA ) Now if (r A represents the transformation from the T scheme to the scheme to the E scheme and (A E ) the transformation from the A scheme. the diagonalization of which gives states 8 4* (a etc. We diagonalize a r ) With this matrix. . .x we transform the matrix of p to the states ip(a ft s ) scheme. . T scheme directly to the E scheme ( is (rqEOHi(n A 0!h!( A 1 E )l. distinguish the different states going with this same proper value. We may ^r s for determined only to within a unitary transformation. we can develop formally a successive approximation method for finding those of an observable which differs but slightly from a. 2 2 18) by 6) A scheme is 2 2 19) oc  by the multiplication of three matrices. (4) to obtain the unitary matrix (r .. ll(rA )iHi(A nii=i . . See 4 for an example of this procedure carried through in detail. dn Since the set ol . the allowed values and statesf of some observable oc. Using (6) (&. the transformation from the given (of. where Z== 1. Since p commutes with a this matrix will be diagonal with respect to a hence we can find a set of (a r ) . The transformation of the matrix of a from the r scheme to the accomplished (cf..lt.
..JB{?  .82 PERTURBATION THEORY 77 1  31 problem in hand. Let us then choose ^(oc ) in such a way that all matrix wZ nZ components of the type (a Fa ) are zero unless l~l This is possible since the transformation which diagonalizes that part of the matrix of V . dn 72 see that the advantage of our particular choice of ^(a ^) lies in the fact that where .lt.. (ic0. It is this special case. which refers to the level a for any given set of ^(oc^ s will transform this set of s to one satisfying the above requirement. for all L n $^ = a (3) We shall suppose the eigenfunctions which belong to these values to be also 3 of the form nZ np shall {^ } is a linear combination of the $o(K ) for^p= 1. This we may do the coefficient of each power of e in the equation by equating to zero /^(n = W( when this [a is (5a) expanded in the form J8* + F . 71 \ Floe *) with a given n are shall consider all different as I runs over the range . d n nl (&.2. Now it may be. We shall call these d values nl from oc . .. P *. The observable j8.] = 0. We we may take ^ {^} = ^(a ^).. /3 n fi . .. .. This gives us the set of equations: (6a) (8b) ^ nl f * ( 6c ) nr nJ If we express ^ K{^ ] in terms of the ^(a ).x... suppose that each of them may be expressed as a power series in e of the form (2) ^=^+ # + where clearly expressible as a power series in 10*+.] [^ {j3*} + W^} + e* h{?*) +. which differs but little from a. Our problem is now to determine 7 powers of in (2) and (4) formally the coefficients of the various in terms of the matrix components of F and the known properties of the observable a. when we have chosen the states in this way. . and which differ but little nd and shall 712 n for small e. that the com i/f 71 ponents I.... using the notation = S^(a^ ){awT ^}.. We shall return to the more general case later.1.. will have dn proper 71 values which coincide with a in the limit = 0...*W  . practically the only case of importance in applications.) (7) .. which we now. .
this is to within a phase the only nonvanishing set of solutions of (10) which satisfies the condition (Sa).{0?]a** 7{^ {K^ a where wT } = {anT K^}. *)[(^". if all \ &. id)  (8a) *  attr } {a 0". {a^ 0^8(Z.x".^) (10) J Mjr for each value din and I a set of d^ equations* for the {a 0 }.$f {a^ ) l  7 ^ . {nr lorti nT ){a r (a".. S ^(a^ n". S ^(&. r for to zero the coefficient of in now shows us n. "..* 1 2^  j8 {r i^ _ +S ril jgjfi ". nor are the {oc^ l/c* 17} coefficients in a unitary transformation.) F 0{ n/ tt 0 }] = 0. ^n (9) (13) The third ec[uation (6c) becomes. It tells us that if we take = a*. (9) to zero in this expression gives is [(a^Fia0ft ]{^ iO^} = 0.l".8(n. braces because the ^K{^nl} do not form a set of orthonormal states.lt.  Fa wT  1^}] = 0.*}] (8b) Sj. when expanded in terms of the 0(an ". we would have obtained at this point a set of equa tions determining the ^r(anZ ) as we have chosen them. + S (a Equating the This coefficients of 9Jj(a. They 3l r are satisfied by taking jSj Ha^FIa*). when expanded in terms of the ^(ocu/r ). (rl.0 [( . _ 1 (80) equation (6a) is just the allowedvalues equation for the and gives us no new information. ^ r ){"..r). This would lead to a further complication of notation which it seems desirable to avoid. had used an arbitrary system of ^(a n ) s. as we have already observed. first The observable a. w*) nl jSjf {a".32 THE QUANTUM MECHANICAL METHOD 82 we can have introduced the curly solve these equations in succession. The condition that the 0(j8* ) We form an orthonormal set independent of gives us the following conditions on these transformation coefficients: = 8(T. j8y With these facts. the second equation (6b) becomes.. (11) (12) This makes For a given the (anl V\ are different.lt. (U) * These equations have the above simple form because of the way we have chosen our t//(oL nl ). ). If we .x^) Equating 0(oc** ) n". {anr jOnZ } will be zero unless ra = w. *  0^} ! n^Z".
procedure since to set r anzi pzi_ Q^ The most convenient n 7) tion with a phase factor. gives us the value of {a one pleases. n 3=n fflS rc/j (g V\ rt n.lt. n r to zero for n". (8a) has been satisfied by the choice (11). and so on ".x^ 1"._ Q^ or that the real part of (a * l ^} is zero.lt. (15) coefficient of nr i/f(a ) (Z". With this choice an imaginary multiple of t/r 2 is reduced to ?/r we may obtain any solution from such a particular one by multiplica we see that the arbitrariness in which we shall also set equal to .n r \2 nl} ing each approximation in terms of the previous zero. But if 0( j8 7t/ ) is a solution of the same phase for = as 2 = given by (4). we have. and so on. but do not take care of normalization.x ".lt. if f(e) k^ 4. imaginary part being arbitrarily set a collection of formulas./r(j3 ).lt.e. The value of {x.lt. 71 ization relation (8c) for n l ^nl determines the real part of {a ^^}. nl ifj(p .lt. but these equations for n l considered to secure normalization.82 PERTURBATION THEORY coefficient of nl ifj(a. setting the coefficient of w *r n/ This procedure may be continued as long as 2 }. is obtained as above. of O] which occasions the is nl \l nl }. ) if/(0) = 0.A 2 c + O is . /f(&. \ni\ynii 7 / _j_ anf \m\ i . {a determine aset of orthogonal states. . See the next section for ./r(a ^ contains an arbitrary imaginary multiple of arbitrariness of {&. may choose the imaginary part of n w/ This is connected with the arbitrariness in phase of l } arbitrarily. and it is clear that recursion formulas may be obtained express one. 33 Equating the ) to zero gives nl . the .J8* + S (a*] F a (fyfill 0{a \ nT  1^} = 0.jSjf from which Equating the {&.x We nz j/r(j8 ) n &.l aJ a ( \lft ril V V\nnl\ ). Equations (5) and hence }. The coefficient of ^(oc^) in the expansion of the fourth nr rtr The normal equation (6d) gives $ The coefficient of ^(a ) gives {a 2^}. for the higher approximations. This shows that n &. ^ Z) to zero gives have now determined ^{/J^} completely except for the coefficient which is not determined by equations (6).^n in (14) ) equal Finally.*} . (6) nZ l nZ  We This means that equations (8) will be automatically satisfied for n l ^nl nl must be expressly (orthogonality condition). .z \JjQ [i. (8b) tells us that n &. {&. e^&. zero.lt.lt.
dn in such a way degenerate. indices. (13) is 82 If the (an? Fa^) for a given no longer the Such a problem should he handled by writing three indices on the states ^(ot^ where (a^F a7* ) is independent of j.. we do it so that )&. and so on. Write (2) + . j". R6sume oi the perturbation theory. We know the characteristic functions and values for an observable a and are interested in those of an observable /3 = + oc 7.34 correct solution.. (1) Denote the distinct eigenvalues of a by a1 a2 . If (18) for j=*f still has a degeneracy. have to use four 9.. If we are to choose the set of states for a given n and I with significance. . the expression n g* (*** I F l ^Tf)(^Tf V an/r I \ ) nr? a*a ff (18) which is written down from (15). n {* jtT lf \^ + ^^ (3) Then I = 2 nT (a = 2 (a^lFla^Oia^ Idcl) 111 } S F which refers * One can determine this set of states by diagonalizing that part of the matrix of to any set of d n orthogonal states belonging to a".* such that the dn values of (oc^l V\&nl ) are The following applies only to n s all different. and let ocn be dn fold = 1... . we {W ^ . The formulas for the coefficients in ^/M) will now should complicated than before... vanishes unless =j In this case we shall = #(***) and that will be given by (18) for find that we have # be much more j*=j. THE QUANTUM MECHANICAL METHOD n are not all distinct... 2. .gt. Choose the dn eigenstates 0(oc*0 (Z * ) that (a^lFjoc 71* ) vanishes unless Z = Z .
we have a diagonal matrix of which we know the characteristic values and functions and which is nondegenerate by hypothesis. and let us suppose r w* nl that the difference between two diagonal elements of the type (ocm P ocnl ) and ) (i. But our perturbation theory is expected to converge rapidly only for small perturbations a small perturbation being one which causes shifts in the eigenvalues small compared to the original distance between eigenvalues. and the much simplified formulas to which those of 9 2 reduce when the system is nondegenerate are applicable. Then the /c in 9 2 is of the order of magnitude &. Let a. Let us represent by T a of the order of magnitude of an element of the perturbation matrix V.RESUME OF THE PERTURBATION THEORY 35 {a nl l nz }=0 10. The rest of the matrix of eV may now be considered as the perturbation.x  Fa difference j3f j8? such as occurs in the denominators of 9 24 and 9 2 5) is also of order V. a number  (&.* Now if we take as the un perturbed levels those for which the degeneracy is removed by the diagonal * This statement is based on the 7 following rough considerations.x f while the K ^ term in (an/I nr )8 ) is of the order of magnitude Since the displacements caused by the perturbation are of the order of eF and the original distance 32 .lt.an between two adjacent degenerate 2 th term levels of a.lt. Remarks on the perturbation theory.e. nn be a number of the order of magnitude of the difference n . If we add to the matrix of oc the diagonal elements 7 (a^leFja ^) of the perturbation matrix. It may not at first sight seem clear why we have set down these com plicated formulas for the perturbation of a degenerate system when we might by a simple device have reduced the degenerate system to one which is nondegenerate.
A124. as we have done in the last sections.gt.7\ ~&.n / w 7 l *I7\ nfl \ * \ / which contains in the denominator the distance between the firstorder eigenvalues instead of that between the zeroorder eigenvalues. and is probably as accurate as the former. between levels is of the order a wn we see that we cannot expect the theory to converge rapidly unless these displacements are small compared to this distance. Roy. let us consider in detail a simple finite case for which we can obtain an exact solution. we have no reason to suppose that the nondiagonal elements will have an effect small compared to the effect of the diagonal elements.lt. \ / n]\ T/l 7&. A122.e. From the formulas no 9 2 4 and 9 2 5 we find that to terms _ 90e 2 180e3 3690 4 . adding the differences to the diagonal elements of the perturbation.gt. Let us take the matrices of a and F to be (5) [where we have already chosen the states ^(a 11 ) and t/r(oc 12 ) in such a way that n 12 (0c (Foc )=:0] and consider the characteristic values and states of the observable in e 4 = a 4.36 THE QUANTUM MECHANICAL METHOD 1C 2 elements of the perturbation.] * In fact.* It should be remarked that if we do use the device suggested above we obtain for the coefficient of e 2 in p71* *** ~r&. The question of the convergence of the perturbation theory has been considered by WILSON Proc.eF. i. In particular the magnitude of the elements {a (* } connecting two states which originally belonged to the same unperturbed level is strongly affected. If the differences p? jgj* are of smaller order of magnitude than F. Hence if we wish small compared to the distance between unperturbed rapid convergence we shall probably need to consider the set of states going with an unperturbed level as a unit and the perturbation as a whole. . For calcula tions just to the second order this formula will at times be convenient. [This means that (1) and (2) can be correct only for small *. levels. if two or more unperturbed levels lie very close. type should be small compared to unity for rapid convergence. To obtain a slight acquaintance with the perturbation theory.gt. Soc. For infinite matrices no such definite results were ob tained. He shows that for finite matrices the theory con verges for all values of the parameter e. 589. If this one might take as a guide the requirement that an expression of the good provided is not true. it is advisable to consider them as one degenerate level in the perturbation scheme. (1) and (2) are too small. The above criterion is &. 176 (1929). m m the differences in first order shifts are of the same size as the shifts themselves.
In the second order these 2 2 by that at with strengths 90e and lOe which soon 0. 11.1 to 401 order in e. THEORY } 37 while to terms in 3 . &. 3 } 3e.A( ) &. &. The situation is states are repelled .0. &.558 3 } (7) 2 411085 .lt. 3. the 0. To the first order the level at 10 splits into 2 states of eigenvalues 10 and 10h5. */r(oc ).lt.gt. or in the form 10 4. The curves marked oo give the 0. 1 2 and 2 2 .lt. 2. Phys.5 3*  2 + + o5 3 +45 + 5 2 c } 3 U75e 3}.* Fig. t BEILLOTJIK. i^(a ^(/J ) 12 The approximation becoming.gt. and values obtained by a direct diagonalization of the matrix oc + cF. and 3 a order and as given by the exact calculation. &. It is of interest to see what one can say rigorously about this * repulsive* effect of perturbations. A crossing of the true levels results in a crossing of the two states for e will be shown in II 2 to be impossible. 0. The fact that the second values for being better than those for is better than the third or fourth must be regarded for e approximation 12 are over as accidental. 43. I 2 for values of e from 0.5755 The eigenvalues to terms of the (6) are plotted in Fig. divided by the firstorder distance between the levels.gt.lt. 379 (1932). de Physique. Joux. Where two curves are not separated in Figs . 2.6 *. The eigenfunctions $(p u ) and ). which for 11 u and ^(a 12 ). The crossing of the levels in this approximation contributes somewhat to this inaccuracy. The secondorder perturbation theory for this case has little accuracyfor a displacement of over one percent. e&.lt. Perturbation caused It is by a single state. 4th as follows. . Bev. and vice versa.gt. 70 per cent. to these functions is seen to be no better for c &. of magnitude equal to the absolute square of the matrix element joining these two levels divided by the unperturbed distance 2 between the levels. 1. their ordinates differ at most by 0*0 1 unit. and one state at 0. 830 (1933).&. 2 a shows the coefficients in the corresponding states to 1. MACDONALD.1905 2 .  seen that in general the secondorder perturbation theory may be levels resulting from the interpreted as a repulsion between each pair of firstorder theory. rapidly change character for 92 per cent. In the zero* 11 approximation there is a doubly degenerate level at 10.10 2 REMARKS ON THE e PERTURBATION". The third and fourth approximations include the third and fourth terms in the powerseries expansion of the true eigenvalues (marked oo). 3. &. at = 01. than for e &.lt.
38
THE QUANTUM MECHANICAL METHOD
._
I
i
I
.A0
\08
M
:C4
.02
M
.04
.06
09
.10

2 Fig. I
.
Successive approximations to the eigenvalues of a +
V of (5) as functions of c.
II 2
PEBTURBATION CAUSED BY A SINGLE STATE
39
X"
/
0.6 L
2 for the eigenstates of Fig. 2 . Transformation coefficients in several approximations a 4 eF of (5) as functions of c.
40
a certain set
THE QUANTUM MECHAOTCAL METHOD
1
H
2
Suppose that we have diagonalized that portion of a matrix referring to
^(J.
,
),
$(A
2
),
...,
$(A
n
)
A
1
,
A*,
...,
A
n
and that we wish to know the
*I*(X)
of states, obtaining eigenvalues effect on this set of levels of
the inclusion of another state
in our diagonalization.
That is, what can
we say in general about the eigenvalues
A
1
...
of the matrix
aj
02
A*
...
...
An
(1)
&lt;z
n
where we let (A*\ be different from
matrix
entirely.
\
X) = o^
;
(X\
\
X) = X ?
We shall suppose all the
oc
s
to
zero, since a state with
a=0 may
be removed from the
If the state going with the eigenvalue A of this matrix be
we have, from
(1),
the equations
(of.
7 2 2),
0,
0.
(j=l,2,...,n)
(2a)
=l
(2b)
Substituting the values of (4*[X) from (2a) in (2b) gives the equation in
A,
which is equivalent to the secular equation obtained by setting the deter minant of (2) equal to zero. The roots of this equation give the allowed
values of
A.
i is such a (3), which is seen to become infinite at X = A shown by the heavy curves of Fig. 3 2 for the special case noted. The individual summands which are added to give this curve are indicated by the light rectangular hyperbolas. With these same values of the A a and cc s, the value of X may be chosen at will. With the particular
The
left side
of
)
function of A as
= = 13, the right side of (3) is represented, as a function of A, by the leftmost straight line of unit slope. The abscissas of the encircled points of intersection of this line with the heavy curve give the five allowed values of A. The allowed values for two other positions of the perturbing level are also shown: one for a position = (2) = 23 within the group of levels A i9 and one for a position = JT(3) =36 above the whole group of A s. It is clear from this picture that the (nf 1) proper values of the matrix (1)
choice
X X
X
X Z
,
X
He, if we
A\
assume that 1 A* .. A n one below A\ one between A 1 and one between A* and A*, ..., one between A n~l and^ n and one above A n
&lt;
A
&lt;
.
&lt;
,
.
II 2
PERTURBATION CAUSED BY A SINGLE STATE
is
41
This
independent of the value of
X and of the a
A
s,
provided none of the
a
s
vanish.*
It is interesting to speak of this in the following way. The perturbation and a set of levels A\ ..., n which He entirely above it between a level
X
pushes each level of the set up, but not above the, original position of the next itself is correspondingly pushed down. The perturbation higher level, while and the set A\ ..., A n pushes up each level of the set between any level
X X
2 Fig. 3
J. 3
2 l= 15, ^. == 20, Graphical determination of the roots of (^l^In this example, A 4 4 = 35; [^1 = 5, a 2 = 5, ou = 2, a4 = 2. The roots are indicated for a, = three different values of X: ^&gt;=ii^ 2 &gt;=23,r
.
= 25,
1
I
X&
I 
1
I
1
1

which
X (but not above the original position of the next higher below X (but not below set which level); the original position of the next lower level); while X itself is pushed up or
lies
above
pushes down each level of the
to
lies
down according
whether the
sum
v
* If two of the
l
a *l 2
*r=2*
A* =A J, there
is
A
B
are equal, say
also a root at A*.
42
THE QUANTUM MECHANICAL METHOD
above X. Hence with regard
II 2
calculated for those levels below
those levels
X is greater or less than this sum calculated for to the displacement of X one may
correct direction of say that the secondorder perturbation theory gives the motion even when it does not give an accurate value of the amount. There is, of course, no rigorous meaning to the correlation in the pre
levels ceding paragraph of the eigenvalues of (1) with the unperturbed 5 A\ A 2 , ..., A n X. However, when all the perturbations are small, the states belonging to these eigenvalues will be very closely
,
The curves of Fig.
3 2 are seen to represent, after a fashion, the potential
to along the Aaxis of the plot dne to infinite lines of doublets perpendicular 2 2 2 1 the paper at points A\ A* y and A^ of linear moment f lo^l fioc 2 f oc3
A
,
,
[
,

,
One obtains an eigenvalue when  X. The dipoles to the left of an eigenvalue raise ever this potential equals A
and f oc4
2

in the direction of increasing
A.
the potential and hence tend to push the eigenvalue up while those to the down. right lower the potential and tend to push the eigenvalue
At any given eigenvalue the relative amounts contributed to the potential
by the
different strings of doublets are rather closely related to the relative contributions of the corresponding states to the eigenstate in question. These relative contributions to the eigenstate are shown by (2a)
(4)
to be proportional to the quantity
jQ/
_ ^ instead of to the quantity
&gt;
*
*"
.
1
ft
which measures the contribution to the potential. One sees in Kg. I 2 an illustration of the forces which keep an eigenvalue from passing the next unperturbed level in the fact that /J11 could not exceed
the first order value of/?12 even though
,
j8
tried
very hard to push it past this
position.
be mentioned that equation (3) is often very easily solved for the values of A, especially for values which lie close to one of numerically the .4 s so that one term on the left side of the equation is very sensitive to
It should
small changes in A whereas the other terms are relatively insensitive. In this u 12 way the roots j8 and /? of the problem in 10 2 were easily obtained to six
significant figures
the root
In such a case
as that of
/? being then given by the diagonal sum rule. 10 2 the roots must be obtained very accurately to
give moderate accuracy in the transformation coefficients because of the occurrence of A^ A in (4).
12 2
THE ANALYSIS OF NOKCOMMUTIKG VECTORS
The
analysis of
43
12.
noncommuting
vectors.
In quantum mechanics, the components of the vectors of physical in
terest
become linear position, momentum, and angular momentum operators in place of pure numbers. The manipulation of such noncommuting vectors is facilitated by a set of formulas modified from those
of the usual vector analysis. If and are two vector observables
,
A A X9 A y
it is
B (A=sA ai+Ayj+ A z k, where A g are scalar observables),* the commutators connecting the and components of A and B transform like the components of a dyadic; hence
convenient to write
[A,B} = [A x ,BJii+[A x ,By]y + ....
(1)
i.e.
Two vectors mil be said to commute when this dyadic
is
vanishes,
when each
component of one commutes with each component of the other. This dyadic
not the dyadic
9
AB
BA, but is related to it as follows:
[A Bl = AB(BA)
where
posed) dyadic.! Hence in general
= ABBA(BxA)x%
[B,
9
(2)
$ is the unit dyadic ii+jj+ kk and
A]
*
indicates the conjugate (trans \A, B], but from (2) we see that
.
[B,^]=[J,B] C
With these
(3)
momentum vector
conventions, for a single particle having position vector r the set of commutators 5 2 i may be written as
j&gt;,
and
[r,r]
= 0,
[J&gt;,]
= 0,
[r,j&gt;]=tor]=&
(4)
In a similar fashion, the commutators of a scalar observable components of a vector observable A form the vector
X with the
(5)
{X,A}~{A X]~[X,A x}i+{X&gt;A y}j+[X,A z}k.
y
(This is the vector XA AX.) A scalar will be said to commute with a when this vector vanishes. The following generalizations of 5 2 2 will be found very useful
[
vector
AB, C] = A[B, C]  [C, J]B, [^xB,C]=^x[B C]~([C,^]xJ8) c
J
(6)
,
(7a)
[C,
A x B] = [C, A] x B A x [B, C\)
(
,
(7b)
(8)
[Z,JB].
* In this section
we
letters for vectors in the
shall use lightfaced letters for ordinary observables, reserving boldfaced Gibbs sense.
a complete discussion of the ordinary f See GIBBSWILSON, Vector Analysis, Chapter v, for the theory of dyadics. It shotdd be pointed out that in combining non commutative vectors, order of the factors must be preserved; thus
,
etc.
44
THE QUANTUM MECHANICAL METHOD
vectors
all associative
12 2
With noncommuting
and
distributive properties
of ordinary vector analysis are preserved; other elementary operations
must
be performed in accordance with the formulas
(9a)
]x
,
(9b)
where s and
scalar
x
indicate the scalar
crosses respectively
and vector obtained by inserting dots and between the two vectors of each dyad in a dyadic the
as defined
and vector of the dyadic
by Gibbs;
(10)
A*BxC=AxBC,
[B,A]C
4[C,B],
(Ha)
(lib)
(12a)
(AxB)xC=BACABC[B,A]C
=JCBJBCJ[C,B].
The
(12b) del
application of these formulas to the ordinary vector operator (V) has been discussed by Shortley and KimbalL*
*
SHQRTLEY and KIMBAJLL, Proc. Nat. Acad.
Sci. 20,
82 (1934).
CHAPTER
III
ANGULAR MOMENTUM
Because of the symmetry of the atomic model, the dynamical variables analogous to the components of angular momentum in classical dynamics The properties of play a fundamental role in the theory of atomic spectra.
these observables, and of the electron spin, which we shall develop in this of atomic spectra. chapter, have constant application throughout the theory
NOTE. In this chapter and henceforth we shall no longer distinguish by a difference in type face between quantities of a symbolic nature and quantities in the Schrodinger representation. While this explicit distinction has been found very useful in the exposition of the theory, because of the two schemes no confusion will be complete symmetry which has been shown to exist between the entailed by using the same type for each in what follows. In this way, boldfaced type is released for its customary role, that of indicating a vector quantity in the restricted threedimensional Gibbs
1.
Definition of angular
classical
is
momentum.
its
In
mechanics
if
the position vector of a particle relative to an
origin
is
r and
its linear
momentum is p,
angular
momentum about
(I)
defined to be
L = rx p.
We
in quantum tentatively define the angular momentum of a particle mechanics as a vector given by this same formula in terms of the position and momentum vector observables.
From the basic commutation rules (12 24) we find that the vector L does not commute with itself, i.e. that the three observables Lx L y) Ls do not commute with each other. Instead we find, from a double application of
,
12 2 7, that
=r x
[p r]
9
xp (r x [p
9
r] x p) c
since twice the antisymmetric part of the dyadic r x (p x $)
this
is (r
x p) x g,
(2)
becomes
[,]=arises: if
(r
x p) x
3 =  ML x &
commutation rule as would this be equivalent the definition of an angularmomentum vector, to the definition by means of (1) ? It turns out that (2) is more general than extra generality that is needed to fit electron (1), and that this is just the So we shall suppose (1) to hold for a special kind of spin into the picture.
The question now
we were
to regard this
46
angular
general
ANGTTLAB
MOMENTUM
orbital
I3
momentum which we shall call angular momentum defined by
E
angular
momentum. The
or in terms of components
by
letter
wiU be denoted hereafter by J while the
3
I will be reserved for orbital
angular momentum.
2.
Allowed values
of
angular
momentum.
,
We proceed now to investigate the properties of the observables Jx Jyy Jz which are consequences of 1 3 3. The squared resultant angular momentum (1) J2 = J + J2 + J2
,
is
shown by application of 12 2 6 to commute with the vector / and hence with all three components Jx ,Jy and Jz As a consequence there exist 2 simultaneous eigenstates for J and any one component, say Jz We can 2 find the allowed values J and Jz by the following procedure. Let $(y J* J z ) 2 be an eigenstate of/ Jz and a set* F of observables which make up together with J2 and J, a complete set of independent commuting observables for
readily
,
. .
,
the system in question. We shall require that F commute not only with Jz and J2 , but also with Jx and Jy for a reason to be given presently. Then
,
From
these relations it follows that
___
Since
Jx and Jy are real observables, we see from this that Jg ^ V/2/
\
\
}
,
since
2 the allowed values of (J^+Jy) and of JT are essentially positive Problem 3). Now using the commutation rules 1 3 3, we find that
(cf.
42
,
Jz (Jx iJy = (Jx iJy
)
)
(Jz
).
f
(4)
2/ Jz ) gives Operating with the two sides of this equation on ^(y 2/ = ( j; *) ( J* ijy) *(rJ* JJijy ) ^(r/
J"
W*
W
(
5)
But this equation that unless
it is
is
of the form of the allowedvalues equation
(
and asserts
(6)
^ g ^ jv j/
it
}
an eigenstate of Jz belonging to the eigenvalue Jz ft. It is vanishes, 2 also an eigenstate of/ 2 belonging to the eigenvalue J and of T belonging to 2 the eigenvalues y since JF and F commute with Jx and Jy (This is the reason
.
denote complete sets of commuting observables ; n ve used capital Greek our individual observables will in heresffcer w shall use these letters to fill out complete sets variably be Eomaa letters of special significance. For convenience we shall denote a set of eigen or F*. values of r by y or y in place of the previous
* In Cliapter
letters to
I"
.. This integer we shall. where j is restricted to the ^=J. This restricts the allowed values of to the numbers j (j f 1) S 2 With any one of these values the set of allowed values of /. j. (m=j. 2j. (jl)H. . times H. J2 . = m#. write as values 0....". f.(J*? +%J% from which. j. . . and from (8) 2 &. accord with the traditional notation... since 2 2 &. /..2). . .lt...^=^&. j 1. Similarly. 2. .. Jy and J enter the commutation rules allowed values of Jx and Jy are the same as those of Jz solution of the allowedvalues problem. . JK. .gt. or zero. where m3 takes on the values j. Hence this series must have a lowest member JF 2 J\ and a highest member JF 2 J\ From (6) we see that the corresponding states must satisfy the relations .. (8a ) gives (8b) From these since J\ equations (8) we find that ^ J\ by hypothesis. &. this shows that J\ = J\ Now the difference must be a positive integer. contrary to hypothesis..  For these allowed values of Jz we shall use the notation mfi.23 ALLOWED VALUES OP ANGULAR MOMENTUM ) . ~j) (11) Since J^.. () (10) . the This completes the . forming simultaneous y 2 eigenstates is determined by JK. (7) But we have already seen that the values of Jz which may occur in simul taneous eigenstates with J z are bounded. 1. symmetrically. for otherwise the left sides of these equations would be eigenstates belonging ) to J\ first of these equations leads to ft and J\ f fi. ifr(yj J Q Z) * by hypothesis. writing .. Operation by ( Jx + iJv on the = IT . J2 (Jo)2 + jo = operation by (J x iJy ) on the second equation J3 (Ji)2%Ji = .J z s +n. .. j. j = j (j + 1) #*.gt.lt.1.. 47 F commute with Jx and Jr Hence starting with a 2 Jz we in general find a given pair of allowed simultaneous eigenvalues J for the requirement that whole series of allowed simultaneous eigenvalues ... For convenience we shall often omit the subscript^. J. (9) as 0".. in Jl~Jz . ..... J . J 2 . Hence .A(r/ Jl) o .
That equation (Jx tells us that (1) $(yjml)~N where 1 2 2.j =j.48 3. mean by that set of states connected by the relation m) (j m + l)$(yjm I). The matrices ANGULAR MOMENTUM of angular momentum. This is the arbitrary phase which occurs in any $ because two states are not distinct unless they are linearly in dependent. the nonvanishing components of Jy are found to have the values (yjm+l\Jy \yjm)= %ift/(jm)(j + m+l) m + 1). using ]. J x&.gt. Such an indeterminacy of phase can have no effect on any of the results of physical significance. we must have. 33 Further development of the method used in the preceding section enables us to find the matrix components of Jx and J y in the representation in which 2 J* and Jz are diagonal. (o) . (2) an arbitrary real number. iJy ) $(yj m) N y] (Jx iJy ) $(yj m) i (Jx =N If this is N K*[j(j+l)m(ml)]. We shall. to equal unity. . For this reason it is permissible for con venience to make an explicit choice of phase. in gi5 N where 8 is = = 0. Since (Jx iJ^f = (Jx + iJ y we find. vanishing elements have the values is seen from (3) m ~m 1. (1). iJy )$(rJm). The first step of the ^r s 3 occurring in 2 5. therefore. N is the factor normalized in the sense that necessary to normalize $(yjml) when $(yjm) is of 1 2 1. to be zero unless y = y . (3) which is obtained from (1) and (2) by setting 8 We may now immediately obtain the matrix The general element of the matrix of components of Jx and Jy . The non Similarly. It will he convenient to denote the value of J by is the normalization giving the value ofj and of Jz by giving m.
Formulas (4) and (5) may by the use of vector notation* be combined into the one formula + 1). from (3) j^ y Similarly K (Jx iJy ) m)(jm+l)(yjml\K\y jml).if 49 (6) The relation f (y j m\Jy \yjm ) e~* (yj m \ Jx yj m \ r ) connecting the components of Jy with those of Jx will be found useful. y These two expressions are equal by assumption..lt.iJy we see that (11) using the expansion (9)./f(o? m) = S xG8? m) (pjm\ajm). Now. entirely independent of m.J] = 0) ) (8) m such that the coefficient ( j + m) j m+ 1 does not vanish. jK". We may at this point show. but by the following argument we can show it to be (yjm __ (jm J". This theorem is of importance in cases where the Hamiltonian commutes with various angular momenta (see I 7 ). on comparing we have the result coefficients (yjm\K\y jm) = (yjml\K\y for all values of f jml) ( (X. Then lajml). (7) l\J\yjm) = (i + ij) %fiV(j + m) here represents the eigenvalues of a set of observables which commute y Let us consider in the y j m scheme the matrix of such an observable. that the unitary trans formation between two schemes of eigenstates belonging to jm is entirely independent of m. m = m. Let &. . This matrix will of course be diagonal with say respect to j and m.. On comparing this with (10). We write 7 K$(y jm)^ijj(yjm) (yjm\K\y jm). /? (9) is We need not here sum over j iff 7 and m in x because %(/J / in ) orthogonal to (a j m) unless j 1 = j.33 THE MATRICES OF ANGULAR MOMENTUM . in a similar fashion. with which commutes with J. l). (10) But from (3) we have l) = (Jx .
. Introducing spherical polar coordinates r.^ (5) seen to be normalized in the sense = S(m X).Jv Jx =iKJ z . Show that if j =  the matrix representing the component of angular tion specified by direction cosines ?.50 Hence AKGULAB MOMENTUM this transformation is entirely 33 independent of m. = m A(&. z (6) . PROBLEMS 1. How does the eigen^r for the value + Jft in the along the direction (I. 2. Jx Jy Jz when j = 1 and .gt. m. (m^ an integer) (3) (4) t) &. m. { m ) .gt. Find the matrix for Jx+J^ and verify that its allowed values are those of JT 2 Jf. Orbital angular momentum. n w=J) and 0*=J.&. 9. . 72 that the allowed values of 3.gt. this Prove by direct application of the allowedvalues equation matrix are + Jft. verify that JxJy . Find the eigeni/r s for the states in which J = J and the component of angular momentum J&.m.e. 6. n)? 4.J# in the direction ( . i. Write out the matrices for 5. The Schrodinger wave function must be a singlevalued function of position. 4. sentation and learn Let us now consider orbital angular momentum in the Schrodinger repre some of the properties of the ^r functions which will be useful in later work.Z.(%).*\ r & r U We shall write where is $(* m t) L^mfi. ( 2) v\Y which has the solution z VZTT where A(&Lz ) is independent of the coordinate 9. we / find that Lz = The Schrodinger equation 3 g v g ##\ dy 2/o= *dx} *fe~ (1) v 89 is for this observable L ji&.J).J(mz ) = ~~ VTT e".x. in writing the transformation coefficients joining two such systems of states we shall ordinarily omit the m^ writing merely (jSjjoy). n is momentum in the direc n l^im l+im where the rows and columns are labelled by (j=J. TW n) compare with that for . n} has the values direction (?.lt. For this reason. &. so z must be an integral multiple of ft: T* * t ^ \ . .lt. .
J&.lt. @ s of different I and the will be orthogonal since ^r(yZm^) is orthogonal to *fj(yl mj) for l^l l r . since the .(Z) known from (5).p s (9) does not depend on m and we may l finally write (12) ^(yZm. (9) ^ z l ^^ m t where B(y lmt ) is independent of & and 9.lt. since for a given value of the associated values of m^ are 1.) = J%Z)0(Zm. . s will be normalized for any ml has been normalized. and hence also excludes fractional values of the number Z. where quantum orbital angular 2 = Z(Z41)# 2 .. find the B(yll) will recur for each m t .I&. * ( 10) The coefficient of sin fl has here been chosen in such a normalized in the sense way that Q(ll) be J The phase has been taken as ( 1 I) for convenience in later work. this gives us the differential equation 30 (II) rrom which 0(Z Z) = . on the coordinates 8 and Hence the factor B(ylmt of ) mj) for all l the factor . . same and insofar as a state ^ s belonging to Z and m l is concerned. .43 ORBITAL AlsTaiTLAB MOMENTUM 51 The requirement (3) rules out fractional values for tlae z component of momentum.). m &. Since $ I. However.)O(ro.gt.1) ( sinz e. I. by repeated applications act only and (8). these Since (10) @ s for the same Z but different l will not in general be orthogonal. (7) Z.gt. 3 Now having In particular. m s take care of this orthogonality. let us find the dependence on 8 of the Schrodinger representative 2 and 9 In terms of polar ^(yZwj) of a simultaneous eigenstate of F. we have from 3 33 Since is &. I . m &.lt. I Now coordinates the operators for L Lx and Ly are given by . may readily be calculated by transformation from We shall write = (y m^ &(l %) m[} as Cartesian coordinates. since (8) ^(yll) = B(yll)Q(ll)^(l) of 3 3 3 (11) *fj(y I we may. the function B(y 1) 42 in (12) is quite arbitrary.
by *&. a tL y )*e^/W^ Using these relations and the known form of 0(Z Z). this particular expression for it being known Rodrigues formula. iteration. the explicit forms of the @s are 0(1 Q)=Vfcos0 9(2 0) =V(2cos*0 0(3 0)=V(2cos 3 . 1. the result being Hence 0(Zm) = (l) 0(?m).lt.sin2 0) 0(2 . (13) From (8) we have i from which. 2. choice of phases m (18) The natural curious occurrence of the factor which we have made here leads to a rather 1 only for positive odd values of m. We can also use (14) to find expressions for (lm) in terms of the deri vatives of the Legendre polynomials. we find the general formula and in particular The polynomial polynomial z in cos# which follows the irrational factor is the Legendre as P (cos0). 3. If we had approached the problem through the usual form of the theory of * For Z=Q.52 Now we find to obtain these _ (i2 t ASTGTJLAK MOMENTUM 43 s explicitly.3cos08inz 0) = + V^cosflsinfl 3 2 0(3 1) = +Vfi(4cos 0sin0 sin 0) 1) 0(2 2) 0(3 =Vif = 2) fl in2 . _ By 3 repeated applications of 3 3 ).
and where the JS?Zm will of course depend parametrically on the angles which relate k to j. = cos&cos0 + sin0sin# / / cos(9 9".(coso&. * This question of phase choice has caused some confusion with regard to the relative phases of the matrix components of angular momentum and of electrostatic interaction. Since this is an eigen?/r of L 2 belonging to I.lt. may be derived P. 9". .gt.43 ORBITAL ANGULAR MOMENTUM l) 53 spherical harmonics the natural tendency normalizing factors with omission of the ( would have been to choose the m in these formulas. 9".) of spherical harmonics of (9. (231 where 6 and 9 express the direction of r as referred to a coordinate system with pole along k (see Pig.jV(Z + m) (lm + l) (l m.gt. 167 (1932). . Rev.) as follows: = Q (l 0) &. 42. (#". . We quote here for reference three other relations which may be obtained as special cases of results derived by matrix methods in 9 3 : (21) Of great importance in subsequent calculations is the relation known as the sphericalharmonic addition theorem.* we find the relations From the form of the operators  (8) 3 together with 3 3 Go m cote 0(Z m) =  Z mf 1) .D (0). 9) and o&.) The formula is (22) S where This relation coso&.1). 9) and (0*. (20) which are useful in some calculations.gt.. A. which expresses the Legendre in terms polynomials of the angle between the directions (9. Phys.). I 3 ). it may be co0 r K expanded in terms of the eigenfunctions referred to k as pole: (ZO)0 (0):= S (24) ~ ". . 9". See the discussion by UITOBB and SHOETLEY. Now ZyO ^O) ^)^. where Lz is the com ponent of angular momentum in the direction k But from vector analysis 6".
gt. = J ^^ . 953 (1925).(m) I 3 it is clear 9 ). metric function of #9 and Interchanging #9 and 9".gt. possesses an essential part of the hypothesis is that the electron also moment whose component is + e#/2ju. then J?te Now P. This is known as the hypothesis of electron spin. 13. Naturwiss.) proves the theorem (22). Nature. we 9". . AHGtTLAK MOMENTUM + 0(1 ml)*(ml) iV(Z+m)(Zm+l) Equating the coefficient of (lm)Q&. that Pj(coso&.) = 5^= S0(Z m) *(m) &". But from Fig. We have then 0(0". 9".) see from (24) that !?.lt.) 0". f UELENTBECK and GOXTDSMIT. from (24). (26) = g(6. Hence since = 1. Spin angular momentum. P.c in a intrinsic An magnetic gues 264 (1926). &.. 9 equal only if This can be true only if g is constant and hence unity everywhere. On comparing this with where /is (20).(l) in the special case 0". must be a sym in (25) gives ).54 Hence. we see that if we choose Eu to be arbitrary. PROBLEM Show from (1) and (8) that an expression which 5. ( 25 ) where ^(0.gt.(m) siR6".9&.Ei m] = 0.(lm) $". 1 . and then setting cos0= 1. = 0.(eoso.1 m * This follows immediately upon expanding the Z derivative of (cos0 1) (cos0+ 1} in Rodriformula by Leibnitz theorem for the differentiation of a product. 117. to zero gives the recurrence relation = 0.= !."..9*) = !. 9) for aU pairs of directions. This But (25) and (26) are g(9".&*". is essentially the angular part of the Laplace operator. In 1925 Uhlenbeck and Goudsmitf discovered that great simplifications could be made in the formal description of atomic spectra by assuming that electrons possess an intrinsic angular momentum whose component in any direction is restricted to the values %H.* (16) shows that/(0.
601 (1927).Sa. hence S has always the . the set *. xn.) = set With the introduction of the spin. The view that the magnetic opposite signs are natural enough on the simple moment originates in the classical electrodynamic effect of a rotating of magnetic moment to negative charge distribution. the ratio has twice the value angular momentum (the magnetomechanical ratio) for the orbital motion of the which is given by the classical theory and holds electron. it is convenient for the special case of introduce a notation different from the previous s ^ \ &. t DJGRAC. is Pauli* has shown that a quantummechanical description of the spin that the spin as an adequate for most purposes can be obtained by treating 3 . However. m * PAULI. we always have . but we shall the spin Pauli. 2 value of proper value  ( + 1) & If we write the proper the proper values of Sg as m/i.gt. (Any component of the spin angular ) then becomes the function (x y z St serve as well. Zeits. 2 3 and 3 but in angularmomentum observable of the type considered with j restricted to the value .53 direction in SPIN which the ANGULAR MOMENTUM component of angular momentum 55 is p. fiir Phys. Chapter . Ss of the spin are restricted to p.gt.f&. in We postulate The proper values of the dependent of the orbital angular momentum L. Further developments by Dirac f have shown to be intimately associated with relativistic effects. but to these must momentum would observable. usually treat spin in the simpler way introduced by then for the electron a spin angular momentum S. z is no longer a complete be added a fourth of observables for a single electron.. 43.) The Schrodinger ^ Here we have introduced the letter or for SJfi as which we shall write thus to when used in the sense of a Schrodinger coordinate. . y. S 2 as s (# h 1) ft* and From 334 and 33 5 we find for the components of S the Pauli spin matrices (1) In vector notation these matrices* are given by (oci. Quantum Mechanics. say S. 2 z component.
(yji J 2 ^i^ 2 ) (1) which jx and mx are the quantum numbers labelling eigenstates of J and Jtel Jz and m 2 eigenstates of J\ and J to and y eigenstates of a set of observables F which commute with J and J2 We wish now to investigate the in .lt. . momentum two commuting angularcommute when each com (Two ponent of one commutes with each component of the other.r. which are to be correlated with our \jsxyzl an * * Roy. 3 3 write out in the form (4 component of spin in the direction whose direction cosines are . 53 The coordinate a of course.r=!/ [ fXV2a $xyza dxdydz. i. (5) PROBLEM the results of Problem 3.\ ^s/ wi \ &(VYI yw V that this set is complete is obvious. density at this point with spin The direct product of two eigenfunctions now implies.r. 227 (1927)] discovered equations which are equivalent to those s formulation however does not bring out the physical . A116. Yector addition of angular momenta. $. We may then write any function iff as and represent this by the matrix rxyz if I / A r \ The by result of operation of S on $ is then given by the multiplication of (I a .) Then the states of the system can be represented 2 Consider a system in which vectors. Soc. j *r. values . 6. m / s ). restricted to the An eigenstate of Sg with quantum number m8 depends on the coordinate 8(&. question of the addition of these two vectors to obtain states character ized by proper values of the sum and the z component of the sum. JL and J are vectors are said to in terms of the scheme ^&. y. a through the factor ANGTJLAB MOMENTUM is.^l gives the probability for finding the electron at xyz with spin + \ l^^^I 2 the probability density (4 ). the most general ifj for which the m.lt. n] has the value + Jft. z: ^  S &. summation over a as well as integration over x.e.* is When \. Darwin significance of the two functions. DARWIX obtained by use of PauB matrices.f form an orthonormal set of functions 5\/ of a in /^^ the sense that + ". / that \ is.V /m ". If we can * 3 By the use of two [Proc. W \GH7YIS J ) == / f \ f 0(0". 7 ) expressed in this form.r7/z\^/ ^s) AM \ /O\ \ ) The factors 8(&.lt. in the Schro dinger scheme. J) and 8(cr.gt. when the dyadic [JF19 jy vanishes.56 Schrodinger expansions. From ) (I. . ^r functions.
this value of m. then. One of these # 2.lt. m a = J 2 Hence there must be two . However. j l} and J 2 ^u^ are common to the two modes of representation. we realize that not only the quantum numbers y. t/ r of independent commuting observables. An eigenstate of this set we shall denote by Consider now the subspace characterized by the eigenvalues y. j l and w =j 2 2 . We introduce.gt. . and since it contains as many observables as the above. above are eigenstates of the 2z complete set r l F ya ?Ji&. s &./ corresponding to the three values of (m1} m 2 ): This means that we must have in addition to the values j=*j_ j^j^+jzl also the value j=Ji+j 2 2.~i The question which immediately (2/x + 1) arises is the following: What are the (2/ 2 + 1) values of j. Hence namely therefore the largest j occurring must also m =j l m 2 = j 2 . jl9 and j 2 From 2 3 11 we see that this subspace is (2^f 1) (2J 2 + 1) dimensional.gt. if either^ oxj2 were . From the fact that Jz = Jlz + J^ tum .1. _ JlJ JV 2=J2&.gt. 57 process. we can add any number by repeating the These considerations are of fundamental importance for the theory of atomic spectra.1 and m l = jt .gt.63 learn to VECTOR ADDITION OF ANatTLAB MOMENTA add two vectors.gt. But the set FJUIJ .^ 2 is seen to be also a set of independent commuting observables.&. the vector resultant of our two angular momenta. ^o the quantum number m. i/r s with .gt. s the other must belong to a j =j belonging to 771=^+^2 we know to be that going with^=j1 fj 2 +J 2 . 2 .1.gt. it follows that m = m + m 2 Now since /is an angular momen . it should also be complete.gt. 3 in this subsatisfying the commutation rules 1 3. In general there will be three s &. corre sponding to the number of ways of independently assigning l and m./&.J2 l &.lt. The space must do so accompanied by largest the m which occurs in a is m =j + j when m and largest m occurring in a $ must be j^+Jz cj&.2 to . The rs states tf&. for they give us the basis of the rigorous quantummechanical tran scription of the older vectorcoupling characterizations of the energy states of atoms. with m =j +j% 1. be j l +j z There are two .J25 e/ r l3&. m which characterize the query is s of this subspace? The method of answering this apparent when .gt. m them T s: m lJlyJl _i  A *&. any j which occurs the corresponding 2j + I values of m.
That with these fa go the proper number (2^ f easily verified. It will be convenient for future reference to calculate the matrix elements of JP in the scheme If we write JT2 in the form (1) it follows immediately from 2 3 2 and 3 3 3 that 1 lm (2) The matrix components we seek definition 2 2 14. m=m l f m 2. where the allowed values ofj are given by (4).lt.lt. .f&. the least value jl +j2 n of j is obtained when js n= j8 where je is the smaller of j^ and j2 This gives n = 2js and the least value of j as {fa J2 \.58 ANGULAR MOMENTUM 63 we should not have had all three of the states (3). in the last analysis. 2 only on &. . . 2 .gt. the de generacy of each m must be proper to account for the occurrence of the values . if ". The matrix of (Ji+J2 ) 2 . 1)(2J 2 + 1) of values of m is we have two commuting angular momenta whose 2 2 the squared squared magnitudes are JiO*i+*)^ an(i J^O a + l)^ of the vector sum of the two angular momenta can take on the magnitude To summarize. ^J . .gt. \ they refer to quite indepen dent particles. These values are just those given by the empirical rule used in discussing atomic spectra by the vectorcoupling method. and consequently would have obtained no new value of j. or to quite independent coordinates of the same particle for example to two different electrons or to the spin and orbital motion of the same electron. starting with the parallel case differing which gives the resultant (j^ + J 2 ) and taking all possible values from this by integers down to \jl j2 for the antiparallel case. (5) where J^ operates only on 7. In general. are these coefficients of according to the These components are seen to be diagonal with respect to as required by the fact that J2 commutes with J z &. that we can split any angular if Two momenta will commute only eigenfunction of the type (1) into a sum of the type &.t(pj 2 m a ). This means.khen values J ( j 4 1) 2 . One can represent the result pictorially by thinking of vectors of lengths j\ and j2 added vectorially. From this point on.
.J]= rx& 12 2 . This commutation rule applies to a large class of vectors: itself (a) Any angular momentum satisfies it with respect to (b) (3) 3 (cf. each of the addends satisfies this commutation rule with respect If Jr =Jri+j2 + ? to JT.Tv]=ftTx .. values }. by saying that T satisfies this commutation rule with respect to J. the coordinate r and the commutation rule with respect any to /. scheme. I3 Hence any vector formed by addition and cross multiplication from vectors which satisfy this commutation rule will also satisfy it.&. where each addend commutes with all the other addends. From 12 2 9 we find that jr=rj. This means that the com ponents of T have the following commutators with respect to the com ponents of J: We shall indicate this relation (2) [J2 . where a has the value 2 and S2 the value ^ ( + 1) % 2 The components are seen to have the 4.Tz ]=o [/.. St the spin moment.gt. .. 1 3).rj=r tf [J.. (3) where 8. also satisfy it. Both r and p satisfy this commutation rule with respect to X.) of vectors which satisfy this rule with respect (e) Any linear combination (d) Hence if J=zL l JrL 2 +. p] by means of (c) 12 2 7a. (L t is the orbital moment of the i th electron. where J is any satisfies angular momentum. Selection rule on j.. will be fruitful to in We shall return to the question of the transformation amplitudes for vector Before discussing that question matrix methods the properties in the j vestigate by addition in 14 3 it m scheme. . this follows from a simple calculation of [r xp.73 I (1 59 + /2 2 We shall need particularly the matrix of L*S= S L. of the matrix of a vector T which the com (1) mutation rule in the notation of ^ T] = [T. momentum p of electron satisfy this to shows that the cross product of any hence of any number of vectors) which satisfy this rule will two vectors (and J will also satisfy to that of (/) A calculation similar it. m= of Matrix T in the j m . r] and [r x p.1) THE MATRIX OF (/! ) ft . + Sl + S2+.
The second vanishes only when j j= 1. on/ j necessary for the nonvanishing of a matrix component connecting the states j and /. This is L/MV2YHO.? = 0.TJ )} 2 2 using 12 lla to expand Jx 2 . (4) We independent of whether 1\ commutes with 2 or not. must have * a nonvanishing matrix component we . Since7rconunutes with 7 [by (4)]. (5) Take the matrix component of this equation referring to the states a j m and a / m where/ ^j. T3 in a representation in which J with JT are diagonal. .7L7. iH(J z T.2ifi{ . i.+ 1) .4&J(J T).". (6) instance of this is the square of such a vector.7]7= (/rx 3. j Js 0.e.gt.1.2s[y ( j x r[J [J rj] = . shall now consider the problem of obtaining the matrices of Tx . rj.2j (j + l)f (/ + 1) + j * (j + 1) 2 left is 2 ] (cy m TV f m 2 ) The bracket on the while 2 j UU+ 1) / (/ + 1)] (j = (jf? (j +f + 2 I) 2 ) . The first cannot since f =j and. .Ty 2 . . T]] = Z ) Hence y4r _ 27^7^+ TJ*=2W(J*T+ TJ . /. . Hence for . Aa important special 1. : [/. 158). 7&. This we may do by a method outlined by Dirac (p. . we find that L/ 2 . + 1) +/ 0". But IP. Hence must In order to obtain a nonvanishing matrix component one of the brackets vanish. .). a condition .[r.ZifiJ x(JxTifiT).60 Another important ANGULAR MOMENTUM fact 83 which follows immediately from 12 2 6 is that the scalar product of any two vectors* which satisfy this commutation rule with respect to J will commute with Jx Jy Jz and hence with J* .rx 37) Prom tMs we have 2 2 = .. + 1)1 = C? +/ + 1) + (j j . Js and a set A of observables which commute We shall first obtain a selection rule on j. 2 Using the relation 12 6.zvrjo. this component will vanish for the last term in the equation.. T .. (/x T". From the rest we obtain: 2 0".
we have of the matrix of 3". the only nonvanishing components of Tz are those ( for which m = m. j + 1 is necessarily all that leads to non. We For the matrix of It will ^T ~^ ^ 3". say that joining the states a j m j(j+l)1P(*jm\T\v?jm ) = (KJm\J\KJm )(*j since J T is diagonal with respect to j and m and since m (7) J is diagonal with respect to a 9. These Tx and Ty by using the relations 2Tx relations obtain because Tx and Ty are assumed to be real observables. f lb) We denote now obtain the dependence Jx iJy by /. ^ * The m j^m^ range j&zm^s j. by hypothesis.ffewce (ajm t e^". This Is of course a in thej type necessary. r / / / e ".vanishing matrix com $ Although the range is true for the full ponents. 158. of the Dependence matrix of T on m. in place of Tx and T y individually. not a sufficient.83 MATRIX OF T IN THE j m SCHEME. we can very easily obtain a selection rule on m.]a ) and .T 9 iTA = \J.rx The matrix oi/ is known. / oc /m / ) = m = ml.. Ekmentare Quantenmeehamk. it is important to note that this equation. = 9 TA^ Take the a J m. Tx or &e only nonvanishing matrix component of Tv are those for (la) which Since m = ml. the we can obtain those of observable x iTy since from the matrix of + 3?~ and ZiTy^^f. on m. If we [/. = unless w = mf 1.^7. p. Tz commutes with Jz shall .^ = Hence \J. a / m matrix component: ^(xjm\r\* 3 m )(*jm\r\* or (mm +l)(ajra^a /m )==0. The method of the derivation of the selection rule on 29 of BORN and JOBDAN.&. condition for a non. We shall later wish to take some sums over m and shall sum over this latter . SELECTION RULE ON j 61 of a vector of the scheme are those for which (6) is satisfied. may obtain a relation which will be useful later by taking a matrix The only nonvanishing matrix elements of any component T m We component of equation and a j m : (5) diagonal in j.* be convenient to consider. have \J. From 3 3 3 the only nonvanishing components are rest of the section follows is essentially as in DIBAC. Then j m (ajm[ 9 r W ?m W unless .^=fojy . range.vanishing component. J9 3T . as well as all the following.gt.
m+l) m)(!j m\/\* r j m+l) (j j = 0.62 rules of the equation ANGTJLAB. (4) = (aj m. We have that is.w) tf. becomes Multiply by f V(j+ m+l)/(Jmf 1) and rewrite: (qjml^lay+lm+I) ^(aj ml\r\* j+l_m) = _ V (j+f+2)(j+m+l) V0*+m+l)(j + m) .  y CX ~". from (2) 3 fm).~ / 1 j Again each ratio is independent of m and hence is Theii If f=j+1.  we find.wi) \ yaj \ and rewrite as \ OC /_!.^ ". (3) set equal to (a j: T\a! j (5) 1). MOMENTUM satisfies 93 Take the most general matrix component which This is \a! r the selection j or.j\T\a! j) 9 We by the this quantity being dependence on m independent of m.^^ Hence ). (6) We shall now determine the dependence of the matrix of Tz on m. J?: .^. jl m+l) = (a^Tja jl)^. 27^ . If/ = j. 1.. we have tf j = 0. for (ocj If j =ji } m\ST a j m+ 1) = (aji T:K j)V(jm)(j + m + (3) becomes l).1 Multiply through by V(J wi)/(Jf. Hence of the elements of diagonal in j: 3".1). 1) (3) and since this holds for any value of m we see from the form of the relation shall denote this ratio that each ratio must be independent of m.w. (y.
we see that 1. (aj:T:a jf) = (a jir:a . table of the nonvanishing Collecting all our results. We have from (Ib) the f jfl) determine the matrix of can m = m. t (8) Tz is real. (11) .j\T\u! r %V(j + m)(jm+l) (i ij) j)mk j1) $V(j + m)(j + ml) (i ij) (ajmj T\a?j m = 1) (a j: T\* m 2 *.(aj: T:aL or Also. This fact rt For instance.). one obtains in an analogous way from (7) T 2 7 / (9) (10) real we see by comparison of this with (9) that matrix (ajjTja /) as we have defined it is Hermitian. *(*3\T\* 3+^^ (ajm ra j m 1 1) = = (aLJ\T\!j) (v. The other components of ff* are found in a similar way. Then 2% (&j .gt. since 7 f j) / r / (ajm2 &.9s DEPENDENCE OF THE MATRIX OF f ON are m 63 Now the only nonvanishing matrix elements of /^ Since we know T directly from the matrices of ^/ and HT we selection rule (7). =j we have from (7): or / =J+ 1 Since 2^ is (ajmI 2 a jlm)==Vfm (aj:3 :a jl). jm)=m(ocj:T :oc / j). we have the following matrix components of T . from (5) we have enables us at once to obtain the matrix of J Hence 7 the .
obtain the complete matrices of J^ and J%. Z s and 5 5 s of the individual electrons. The matrices of Jl and JFa where J + J2 = J. Zeits.. . the matrix (aj:J:a /) = 8^8 aa. we see that in going from the scheme ocjra to like jj(ajj3j)H. 743 (1931). 10.) 3 diagonal in y.gt. we shall not will be ^ and j 2 carry the label y.gt. if they commute remarks hold in particular for J Jy and Ja9 for which x&.lt. just a scheme jSjra. its total spin momentum and 2 = angular momentum of an atom . 10 and 11 follow GUTTOTGER and PAULI. (1) gives Using this and the corresponding element of J2 is (2a) obtained by in terchanging subscripts 1 * and 2. some of the y s would naturally represent the m &. Consider the representation is the total where the observables T commute with x 2 J. . (If 7Ji J2 J = S. 67. These /) is diagonal in j. J^ 3 : or. x its total orbital momentum. 3 so that in this case the formulas (11) agree with 3 7. 3 From the above formulas and from 3 11. / J . For brevity we shall later drop also the labels j l s 9 ! 1 gives us the dependence of these matrices on m. from 9s ! 1 j(3 But or + l )&(M*3\ Jti3iM) = (:Ji323^ Jl = (J JiJ relation. Hence we see that in every independent respect IKccjjTja j behaves like the matrix of a real observable. with A it is diagonal in a. ANGULAB MOMENTUM if TX9 Ty and Tz commute 9* with. hence we need now determine only the (j\ j 2 jl j2 j ) and (jx j2 j: J2 :jx j 2 /). the matrix \\(*j\T\&. For the case/ =j these follow easily from 83 7 which becomes for the z component ofjt 5 ^s. .* If J is the sum of two commuting angular momenta JI and JF2 we can . . J 2 . j the matrix of an observable: )\\ is transformed by act Here we have used the notation in 3 3 that this element )!! is the proof (A?cy) s (j8jmajm) justified by of m. fur Pliya. J / Then the matrices ofJi and /2 and J2 Since they will not depend on y.64 From (ccjiTia its definition.x. J .
103 THE MATRICES OF Jx AND /2 WHERE Ji+J* = J .10 Jil (2a) Now. from (2a). JJ= tft/lv t( ^ or (JixiJiv) JizJiz (^ix to 9 3 10 3 Take tOnefajijm. we obtain the relation ioviui)m^ We get another relation in a similar fashion by taking the j x j j m 2 . with the abbreviation ^ JiO\+ 1 )JaO*+ 1 SB! )&. 65 use the The components not diagonal relation in j are more complicated. from Hence.jlv . and with the abbreviation . We [Jlx _.l\Ji\})^(j =* or ( 31 Jil ft/ (3 m)(j i OVJJ)*. using 9 4 (omitting the labels j ls j 2 ) : JiljlWm* (3. ( 3) j J2 j m component of the identity Jl= ttJ This becomes or.gt. 3iJz3 mJf component of this equation.
. this + formula becomes (2V) It is to be noted that P is a function only of and j +jt while Q is a function only of j x and j j. I &. Hence if (j\JJ 1) the nondiagonal elements of J^ are all positive. we have = .O l ~J2) 2 O i  . We former and (4) for lOViL/l)I a and lOI/Jjfl)} 2 For the we obtain NOW hence Iff : j IU: J11. In adding J^ andJ2 we choose the relative phases of states of different j so that the nondiagonal elements of J^ are positive. We shall carry both signs as a matter of convenience in the sections immediately following. and hence negative.(j\Ji\j. shall always use (2b) with the upper sign.Jilj elements of J^ are all real and positive.+ 1 Ay) by substitution of j 4. of J^ negative * With the abbreviations P(j) =y ~ }\ +j2 ) (j (i +jt +j2 + 1) QU) =0\ +J 2 i) which ve shall use in the nert section. reverse We ~h) ( (2b)* ={?} ^Ae tsame expression.gt. . uantity may be obtained from (5) have now arrived at the point where we should choose the relative phases of the states of different j.1). ".i for J. Since the matrix of + 2 must be diagonal with respect to j. However. tllis q. This we do conveniently if we take i) ^ be real and positive for all j. elsewhere we.66 ANGULAR MOMENTUM can solve (3) 103 . This means that the nondiagonal (fi. J 4 + ( J* ~^ + 2 (Ji + J2 + *) 2f . those of are all We J= J J An alternative J& choice of phase would reverse these signs the roles of J^ and JF2 therefore write . In the following pages we must be consistent in choosing everywhere either the top or bottom sign wherever the symbols { } and { + } occur. 8 Since OViJj + *)i 2 =iO".
gt. Because F components of P (/./&. 2  latter relation we see that P must satisfy . zero.J Because of this 11. &.j&.gt. = S.) The matrix of P will necessarily be diagonal in fa.e. [ & jVitfi fl + Ofo".lt.1. or may be Li9 the orbital momentum of the i electron. (If /j. so for convenience we may omit the label for the moment the y / which will occur in all matrix fa We shall also omit in y).10 TB[E MATRICES OF /x AND J3J WHERE Ji+ J2 =J . P may be eSr* the total electric th moment. 67 this point we phases of the states At S may &. or r$ or th pi9 the coordinate or momentum of the i electron. 3 dependence of P on m is given by 9 1 1 we ence on j in the yfa fa j m scheme./=J+ 1 (from 9 6 and 9 10): W or Since the matrix of tM) J is j". =j+l. These phases are completely specified by the above choice of relative for the state of largest j and phases and the following specification m (namely j=m = fa +fa) of : P which commutes with jFla We shall now consider the matrix of a vector P which commutes with J but which satisfies 8 3 1 with respect to J. the coefficients of m and of unity must each vanish. Matrix a vector .gt. etc.. 8 s ! with respect to 2 also. The shall proceed to find its depend J . where /= Ji H.(yji3* J2 J m ) of 632 rotative to the states mm i z) of 6 1. 1 0*) 0*2 jVi&J) O t JiJl/2 J+ ) Here we obtain a^ Since this relation is independent of m. i.+ I ^iyi J + !)] (Jt Ji^Ji J + J ) 52 .(yJi also conveniently make a definite choice of the &. (fJ^^^ = (J*J^ W known. . and JT2 are necessarily diagonal 1 or 3 1 with selection rulej 2 fa= satisfies 8 respect to J2 we have the .lt. Consider the yfafaj m] y A Ja/ m+1 component of the equation (JtoiJ^P^PttfteMiJ3 3 First for f=j. this furnishes a recursion formula for Now consider the case / = j.
(5).gt. [. .1 ) = ~ 0*P&) O l jVilJi Jl)( 2 ) becomes. J first of these from the second gives 0". on substitution from 103 2b . j.) = U*flP\J*J)&.1 ) If we can determine (j z j\P\j2 j+l) from (2). or &&P& For the case ^2=^2 ! 3 by taking the complex conjugate of (5). from (4).P=j a lj . we have (7 ) J.O ^Vib . using .l(JJ\Ji\hJ) (3 + 1) .1 (j.OW+ 1 i& J + !) or.68 ANGULAB MOMENTUM first Subtraction of the second of these from the gives 3\3\P\h3) = 0.Henee where the last factor is 3 given by 10 2b. j". (3) will give us (hJ\P\jJ).(j. and (4). =j the two M& JSubtraction of the 1) . We see that these ratios must be independent ofj.jV^JW+OUil^ii^J. 1 (3) In the same way we obtain from equations (1) for the case j =j. from 103 2a Similarly. (j2 j\P\JzJl). For the case j2 =jz (2) gives us . jilPI/Ji) . + 2)] ii^U. as implied by the notation (M^lh). ! From (3) we obtain.
fa Q(j] are essentially positive quantities takes on negative values in certain instances. the formulas 10 2 are special is itself of the type P.JT2 P which commutes with Jls where J =/ : . and the double signs inverted. 3 we find that the dependence onjofQ is opposite choice of signs in 10 2b. (3) and (4) give us ?) are essentially the complex conjugates of these quan tities. ^ } (8) When we seek the corresponding components for a vector Q which com mutes with /2 since the only essential distinction between J^ and Jz is the .11 s MATRIX OF A VECTOR P WHICH COMMUTES WITH/! us (j 2 69 THs gives j\P\j^l JH). Using for conciseness the abbreviations* ) (3 + Ji +h + 1 ) &. Since JTa given by (8) with j^ andj% interchanged 3 of the type Q. since Ijj. and ^ cases of * (8). we find the following complete table the matrix of a vector of formulas for the dependence on j of 4. Knowing this.gt. We note tfcat P(j) and .
1635 (1931). ^ the matrix elements will be independent also of the value of jx This will be true in all cases which we shall experience. In particular if /2 = Pf P we 103 2. . Matrix of PQ. made of the In this case . respect to J enables us to repeat in factor. if not always. be of such a character that when a resolution of the type 63 5 states in question the vector wiH operate only on 2 not on &. the matrix of the scalar product of a vector P which commutes with J^ and a vector which commutes with J2 both of which satisfy the commutation rules 8 3 1 with respect to J. many 12. Since P satisfies the commutation rule 83 1 with respect to JF2 and . Bev. for example^ have from the first formula of 93 11: . in the yjifajm scheme. is .lt. PQ * JOHNSON. a vector having the properties of P will usually. of the matrix of t a l 2 l l . We shall . 3 =sm ^ in which we know from 103 6 that these two matrix components are equal. This matrix will of course be in j^ and m and by 3 3 8 the elements will be entirely independent diagonal of m Further. Knowing that the factor (yJ2\P\y j*) of (8) Jim the same properties with respect to the vector J2 as the 7 (ajITja 3 /) of 9 11 has with. 38. From 8 3 4 we see that this will be product Q . That these factors actually are equal is shown very simply by a calculation of (yJiJ^^m^Pl^ j^j^m^m^) from 3 li and of (yjj J 2 jmjPiy A j 2 j m ) from 93 11 and (8) for the case &.70 The question AKGULAB MOMENTUM of obtaining further information 11 s about the factors now arises.lt. Phys. We shall find by the formulas J2 = J2 f J . commutes with J^ we can express directly from 9 3 i 1 the dependence on m 2 P in the yJ j m m scheme. . hence we shall here treat these elements as independent ofj l . many cases the considerations of .* It will be convenient at this point to obtain.P\ y JiJ$) = (yj&Ply fz) for which in accordance with 9 3 1 1 we use exactly the same notation as we have adopted for the factors occurring in (8). (9) There occur here on the right the factors (yJiJjf. or if 10 3 or II 3 with respect to this can determine this factor completely and P commutes with J^ formulas of the type (8) are again applicable to determine the dependence of the matrix of P on J2 and the present discussion may be repeated. applications for such calculations.
A.j) OWi J .?m (yjij 2 jwlPiy". 1) 0".gt. There are certain sums of scalar products and absolute squares of matrix elements of T and P which will be of interest to us in connection with intensities of spectral radiation.1 . + +A ^* + 1) (A +ja +j) (h +5* . As in the previous formulas we may interchange P and Q j1 and j2 if we invert the double signs.Js (A + js 4 v* y". (* ? m*\T\* j m =$ ) 1 8mm.J m ) S (rs^lfh] (y* Ale!/ A!^!/ J4 i) y* (y* Alfll/ Jil)VOi (yj i A j \P*Q\y ji+l Ai j m) = J2 (yA!Py*Ai) (y*Ji!!yVi+i)Vc/+A A . _ j. (i) where (2) .) ( /!2V j) S( j. The elements of P*Q are easily shown from 9 3 11 to be given by the expression  S ". are those obtained by taking the Sum rules. jiQjy + S(yjlj 2 j:^y^ y When the formulas we obtain = 11 3 8 giving the iS Cy JaifV J2 (y^ iiCI/ Ji) ) U + 1) ~h Wi + 1) .1) O +A jJ The only other nonvanishing elements y complex conjugates of the last four above. j) j o*+ (1) dependence on j are substituted here 3 1)&. (2) . JI^I/Ji j.jj^^^ A j.gt.gt.lt.1) 0&. (Compare the second and third elements.) 13.&. From 9 3 I1 we easily find (the calculation is similar to that used in 3 obtaining 12 1) that 2 m* * (ajmTaT&. j ).A A+ 1) +A A +2). j) (/ ji j.12 s MATRIX OF PQ 71 diagonal with respect to j and m. j+l) (/Ji/2 J+11CI//1/2 J) + 1) (*f + 8) j 2 jjpj/ ji j. j.(ayiS !* j".
(3) For the case of the vector over the j values of the F of II 3 . The straightforward evaluation of these quan l. S 5* m".72 In particular. then mf ANGTJLAB MOMENTUM 13 3 the These sums are independent of the m value of the state ocj m occurring on left. andJ2 substitution from 11 3 8 is algebraically very complicated. may be performed at once (4)=S. p.Smm . final state. They are not symmetric in j and /. .J2. 49. . should like to go on and obtaining the values of we sum (1) (4) tities 1. ?ni S mm t ^ ^ S (y Ji J 2 j m y^ J 2 mi m a ) J mi T (y Vi rVJi JD (y A^ Py A The sum over fin". to give a factor 2 l. 7 4 be It will be convenient to obtain now a relation which will in interpreted as indicating that the total radiation from and unpolarized. This by unfriendly complication may be avoided by a transformation to the scheme as follows: = (4) JT $mm . Using the relation an atom is isotropic m we readily find from 3 Sm j 9 11 that 2 TO j 771 = S m 2 = (ajmra /ml)p (2j + l)(^jT:a /) S(j 3 j ). * t lootnote. but become symmetric if multiplied by (2j + 1) to accomplish the summation over m.
$(jm) 9 for m 7^ m m 2 Hence.gt.m2 any eigenstate of Jz with another eigenvalue./&. 2 ) is orthogonal to 1 4 an eigenstate of Js =Jlz + J^ with eigenvalue m^ 4. m value.. one does not need in this discussion to write the yji j z explicitly. (I) the coefficients (mL m^ j m) will contain a factor (?% 2 m). 73 last From the discussion at sum is given by (1) as we know that the value of the The factor remaining is then which unity since the values of these transformation coefficients are independent of y. but of the j value of the state occurring on Transformation amplitudes for vector addition. obtain a set of though..13 3 SUM RULES the end of 11 s . Finally then. give us a set of states $(j m) with the particular 3 3 and 10 3 to use. We can. +m is to diagonalize the matrix obtained in 7 3 of 2 J".g.iP!y #) S(J. in the relation ift(jm) ( = &. (4) becomes is and in particular j S Kw i J jl P Ir A J2 j m m over the values j 2 ) = j a (y.lt. by using the formulas of . in terms of the eigenstates (6 3 1) As indicated. One way to obtain a transformation between these two schemes . More over. 3 3 and 10 3 themselves. in the m^m^ scheme. however. e. These sums are inde pendent not only of the left. ) (5 ) Here/ the is summed l9 and j\ 1. To complete the discussion of the addition of two angularmomentum vectors we need to know how to express the eigenstates (6 3 2) 14. This method does not. since it is (?% m . hence none of the matrix phases we have agreed in elements we have calculated would be valid in such a scheme. since they do not occur as summation indices in the transformation.(?% m 2) (n^rn^jm).
m) ( j f m j ( jl This becomes.m O J^y )] (Wj.m) (J 4.m) j. . we a ir laf ) obtain from a ^application of 3 3 3: itf0 or.1). namely (el 10 6) and m there is only one non vamsMng Knowing the j state $(jm).1 m) when we know the states $(jm) and ^(j+1 w). With the initial condition (2).1 m) = ])% . 3 3 gives us the state fa 3 $(jm.1: JJ j) (w^ m a j.iJ *(J iJly + (Jto iJ 2y ). m 2 j m) (  j  ). I03 . equating coefficients o 2  j w) (3) fV(j2 Hm 2 hl)(j 2 m 2 ) (w^ma+llJm)* This is the desired recursion relation.e.74 ANGULAR MOMENTUM 14 s recursion formulas which completely determine the transformation coeffi cients with the proper phases. on expanding and equating coefficients of ^(m^m^ as before. (4) where the (/i/jyl are given by 2. all the coefficients (m^m^jm) for the given 3 3 3 in the and m. V (j . the two recursion formulas (3) and (4) determine completely all transformation coefficients for the addition of a given jj and j z A general formula for the transformation coefficients is very difficult to obtain from these relations. This relation gives us the state ^( j. i. Expand mi m 2 scheme: SIT I Jl j S 77ll77%2 4 Since / . The general solution has however . For the state $(Ji+hJi+Js) of highest j S coefficient. 9s From value of j. and 10s we obtain the recursion formula which steps down the 9a ll From we find that ".
#0 h ma m . Repeated application of (3) gives then the top row.gt. e Assume the basic states a mb ma) and $(jb ja mb ma ) to be identical (cf 63 5) The states $(ja jb j m) and $(jb ja j m) must be essentially equal. (6) In Tables I to 43 are given the values forJ2 =f. but that they will have different e nondiagonal phases is seen from the fact that for the ^(JaJbJ^) linear combination of the states a b) f &.(j * WIGNEE.f&. Ji) (&. we obtain a way of evaluating these transformation coefficients. the summation in which reduces to one term for this case.gt. 2.gt. this sum becomes very complicated. &.gt.lt.(jf)j ^ . 1. however. .lt.( &. %)&.gt.gt. Hence. the factorial of a negative number being meaningless.. which are sufficient for most cases in atomic spectra: one seldom wishes to add two angular momenta the lesser of which is greater than two. a jb we associate jb with Jx ja with J2 we obtain a state $( jb ja jm) as a certain . these states must change their relative phase However.lt. 206. When. is But by making tables f. p.j&. For the top row. This formula is so complex that the calculation of coefficients by its use as tedious as the direct use of the recursion formulas. Formulas determine immediately tlte element the upper left corner. especially of (4) for the passage from one row to the next.f In the addition of two angular momenta ja and jb we shall wish to know the effect of the reversal of the association of ja and jb with the and j2 of the above formulas. f.. ^ J^ will be positive while for the ^(JbJaJ^ these elements will be negative (cf. we have Oi m i 1 h J ) = S (J &. If we associate ja with j I jb with j 2 we obtain a state $(ja jb j m) as a certain linear combination of the states a b ). . 10 3 ).(j ^ m m . 3 0(ji Ji wii) = A ah 0).14 3 TBANSFOKMATIOK AMPLITUDES FOB VECTOR ADDITION 75 been given by Wigner* by the use of grouptheoretical methods as the following expression: (j + A + Ja + ! Oi ) ! In this summation K takes on all integral values consistent with the factorial notation. which show the result of adding any j\ to convenient ^ = 0. For the trivial case j 2 = 0.gt..lt. . i. . from this (4) determines directly the other rows. The most convenient method of com putation combines the use of (5) and of the recursion formulas. Gmppentheorie. for j^ja+jb the two states are equal since for a jbjajb)&.f&. for successive values of j. t These tables may be calculated (2) and (3) m . a +jb they both equal elements of the matrix of m~j &. The bottom row is obtained very simply from (5). and 2. from the recursion formulas alone or from (5) alone. ie.
w + 1) f  /3( Jj + m + f )(/i OT + )( A m +f ) i .W 4. t Calculated bv F. From Wismer.m + f) Jli 0\3*i 5 y ! +fX/i .lt.lt. MOMENTUM O i 14s i w x rn^ji %j m) TABLE 2 3 . yiffl*X.^)( J\ TOT + )( Jj .7! + 3) y : v Jl+t .f } (2^ + 1X2^ + 3 2.i +m  % A .i)( Ji + TO + iX Jl + V Jli /3( Jl + MI . .: .*)0*i .76 TABLE I3. 5712=  1 V ] (2jl + l)(2j1 + 2) y&. V^i TABLES 3 \ + TO . __! ^ X 2^ r2f 2^(2^ V .m ./i+*Xj i+f) 2/i(2JilX2A + l) 7712= v 1)( /3Q".W (2^1X2^+1X2^ Jlf v * ^^ v/^ 2^(2^1X2^ Seitz. . v / ( v V v/ &.i+W".
143 TRANSFORMATION AMPLITUDES FOE VECTOR ADDITION 77 c5 .
the probability that the z component of spin nave the value +J is cos 2 (0/2) and that it have the value . For the case j =1 . Compute eos 2 (#/2) and sin2 ($/2) for this angle and compare with the square of the coefficients in the first row of Table P. This is an example of the difference between quantummechanical formulas and those given by classical methods. Zeits. consistently with the correspondence 4 principle ( 4 ).] (a) the spin is parallel to I as a vector (6) According to the vectorcoupling picture when/ =Z + and when j has the component m the angle it makes with the z axis is cosd~m/(Z + }).J) as suggested by the vectorcoupling picture. [PAUU. Show that if the spin of the electron is known to have the value + in a direction making the angle 6 with the 2 axis. m ) (?) PROBLEM Investigate the relation of the preceding formulas to the classical vectorcoupling picture. b\3a Jb j ) =(  l) y + ^0 6 ja . 43. fur Phys.J is sin*(0/2). * This agrees with the relation O o J6 m a given by Wigner.J one has still to use coa9=m/(l + }) instead of m/(l . although. the two agree for large values of I. 601 (1927).78 Hence the AKGTTLAB states in question MOMENTUM satisfy the relation* a )b 3 M 3 3 the states for other values of m are given directly in terms of this by 3 must 3.
CHAPTER whole subject of IV THE THEORY OF RADIATION ". 1888. Such a theory of quantum electrodynamics cannot be said to exist in definitive form today. * EINSTEIN. of making a spontaneous transition with emission of radiation to each level B of lower energy. Einstein then ascribes to it a certain pro bability per unit time.". Likewise it is possible at present to develop the theory of radiation along general lines with considerable assurance that such alterations as are later brought by a alterations in the Hamiltonian many revision of the theory of the electromagnetic field will not affect our conclusions. Zeits. . in a level of argument more than the minimum energy. In this apparatus between states. but it also recognized that these laws require some kind of quantumtheoretical modification. The light sent out in the process has the wavenumber (EA Es )/hc according to Bohr s rule. : spectra divides itself rather sharply into two parts the theory of the energy levels and the corresponding states.* The independent of special views concerning the electrodynamics of the transition. chapter well is we That radiation s present the general theory underlying the radiative process. Emission of light takes place when there is a transition of an atom from a state of higher to a state of lower energy a quantum jump. But the general structure of the theory of the energy levels can hardly be affected since it possesses so points of close contact with the experimental data. Phys. 121 (1917). A(A. OLIVER LODGE. Phil. Likewise absorption takes place by an upward transition that is caused by the action of the fields of the radiation on the atom. 1. We start the consideration of these processes by a somewhat phenomenological method due is to Einstein. 18. Mag. August. When it is developed it will probably produce which will change the details of the theory of atomic energy levels as we present it.The electrical radiation seems working itself out splendidly. to be embraced in a general theory of quantum electro dynamics. is to be treated according to the general scheme of Max electromagnetic theory is unquestioned by physicists today.. JJ). and the theory of the radiative process whereby the spectral lines arise transitions The theory of atomic through The preceding chapters have provided us with most of the needed for an attack on the first part of the problem. that is. main Transition probabilities. Let an atom be in an excited level A.
(4. by Bohr s rule. The argument now uses the principle of detailed balancing. The quantity r(A) (2) by y^ = B A mean life of the level A. by the (4) N(A)=g(A)erW. The supposed to be isotropic and unpolarized and to have spectral energy p(a) du in unit volume in the wavenumber range da at a. according to which in statistical equilibrium the rates of each elementary process and its inverse are equal. the radiation density given by Planck formula. where g(A) (b) is the statistical weight of the level is A s . then the field produces transitions from at the rate A to C by absorption where a is the wave number corresponding to the transition. By As purely statistical considerations we can find relations between the and B s. If C is an energy level higher than A (where A is now not necessarily an excited level). B) is called the for if the only processes occurring are those of spontaneous emission N(A)^N from which it (A)e { ^A\ (3) follows that r(A) is the mean time which an atom remains coefficients repre in the excited leveL Einstein also ascribes to the atom two probability field in senting the effectiveness of the radiation radiation field is causing transitions. ^ The coefficients A and B are fundamental measures of the interaction of the atom with the radiation field and have the same values whether there is thermal equilibrium or not. for we know that in thermal equilibrium different levels are given (a) the relative numbers of atoms in MaxwellBoltzmann law. This . due to spontaneous emission processes (1) where the summation defined is over all states of lower energy. The two kinds of emission are regarded together as one elementary process and the one kind of absorption as its inverse. Also the radiation stimulates or induces emission processes from C to A at a rate given by N C) B(Gy A)p(a).80 Then if THE THEOBY OF RADIATION the I4 number of atoms In the level A is N(A).
953 (1910). see also FERMI. 33. the two Hamiltonians commute with one another and so each commutes with their sum. (If we regard two separate systems as one system.) The emission process consists of a change in the system whereby energy leaves the matter and raises the quantum number of one of the field s degrees of freedom by one.r) p(&. it is possible to make fairly precise statements concerning the amount of energy in the field and the matter.lt.lt.A). Phil. Rev. f JEANS. Chapter xvi. Mod. Chapter xi. 4. (8) theory. field and matter.at or is shown to be Srra 2 da per unit volume.C) P (a) = N(C)[A(C. 87 (1932). Phys. 1427 (1910). The absorption process is a change in which one of the field s degrees of freedom has its quantum number diminished by one. The matrix component is taken in a representation in which the states of the two to use is the one parts are labelled by quantum numbers. Because of the rather weak coupling between the two parts. Without going into details ternal changes in unit time is ponent of the interaction energy between the field that the probability of these in proportional to the square of the matrix com we can say and the matter. Dynamical Theory of Oases. Ann.A) + B(C. therefore eigenvalues of each are constants of the amount of energy in the motion. f DEBYE.r)lBirkco*. the energy going into the matter. 9 i ( } Using the latter relation the total rate of the emission processes can be written in the form N(C)A(C. which way of writing it is shown by the Dirac radiation a quantum mechanical outgrowth of the method of Ray leigh and Jeansf and DebyeJ for handling the statistical mechanics of the radiation field. (6) Tn order that the last three equations be consistent we must have g(A)B(A.C)=g(C)B(C A) A(C A) = Birhca*B(C. therefore n(a) is the mean number of quanta per degree of freedom for the field coordinates belonging to waves of wave number or. Hence in equilibrium we have N(A)B(A. cs 6 . this is only approximately true. the component the initial state and whose final indices specify the final state. Quantum Mechanics.I4 TRANSITION PROBABILITIES 81 seemed strange until Dime s radiation theory* showed that the two kinds of emission were really related to the same process. The number of degrees of freedom of the field asso ciated with waves in the wavenumber range do.A)[n(a) + ll That this is a significant is where = n(&. the size of quantum associated with each such degree of freedom is kcu. The whole transition probability will be very small unless the whose initial indices specify * DERAC.A) P ()]. In the Dirac theory the electromagnetic field and the emitting or absorb ing matter are treated as a single dynamical system. der Phys. 20. But if a small inter action is present. Mag.
* They find that the relative probability of emission in the range da at a. and decrease in n corresponds to absorption. The actual emission in the statistical ensemble will there fore be proportional to \n(a) f 1] as in (8).gt. so far as the change in any fieldwave s quantum number is concerned. !) As increase in n corresponds to increase in field energy. Zeits. is o TT ~7T7/T2&. so emission by of energy to this degree of freedom can occur even in the absence of passage radiation (^ = 0) in it. 2 I f ) (cr/&. the quantummechanical analogue of the fact in classical theory that a radiating oscillator has its amplitude atom s change in energy is in a single process damped out by the loss of energy by radiation. the lack of symmetry is just what we need to get the spontaneous emission as is proportional to n+l. . The interaction of the field with the matter is a linear function of the wave amplitudes.7 where u = yrv + TTrJ 4xTC\r(A) r(C)J I 1 / I 1 \ ( ^ 10 ) / * WEISSKOPF and WIGNEE. fiir Phys. ffiv. contain as a factor (n q\ri).82 initial THE THEORY OF BABIATION and final states of I4 the whole system have the same (or almost the same) energy. where n is an integer. given in the hope that it will make clear the way in which the two apparently different kinds of emission are really two parts of a single process. All others are zero. We conclude this outline with the remark that quanta in it is not quite true that the only transitions occurring are those in which the just opposite to that of the field. 54 (1930). (n = _ 72. where n and n are the initial and final quantum numbers of the degree of freedom in question and q is the numerical value of its amplitude. . we may take for the matrix components of q the wellknown values = (Vn. But (ngn l)j 2 is proportional to n. or emission by the matter. Since the field coordinates are dynamically like harmonic oscillators. This is just a sketch of the theory. so the matrix components. s rule. This gives rise to the natural breadth of spectral lines. Hence the possible field energies associated with each wave are hv (n f ). 63. so absorption well as the induced: j(7igj% + l)J 2 by passage of energy from this wave to the matter is simply proportional to the amount of energy already present in that wave in excess of the zero point energy. This point has been by Weisskopf and Wigner. Thus the wavetrain emitted is finite and not monochromatic when expressed as a sum of monochromatic waves with a Fourier integral.lt. where a is now measured from studied in detail the wavenumber given by Bohr . Each of the coordinates for a wave of wavenumber a is dynamically = equivalent to a harmonic oscillator of the frequency v ccr. where n(d) is the mean number of all of the degrees of freedom of the right frequency.
the electric field S and the magnetic field ^. c ot SB 4fljr. ^ g c dt which expresses the conservation of electric substance. In these we have a scalar field p which is the electric charge density in electrostatic units and a vector field I which is the electric current density in electromagnetic units. The Coulomb law in electrostatics. (d) The Ampere law for the magnetic field due to electric currents. These have the property that if they are made to satisfy the equations 0) 62 .T . to gether with Maxwell s displacementcurrent hypothesis. 2. (2b) (2c) ^. There are various auxiliary fields which may be conveniently employed in dealing with these equations. We Maxwell regard radiation as a spatial flow of energy governed essentially by s equations. This line width has no practical importance for ordinary spectroscopy as it &. is smaller than the width of image produced in spectroscopic instruments owing to their finite resolving power. Classical electromagnetic theory. Faraday s law of electromagnetic induction.lt. Related to p and I are two vector fields.I 4 TKANSITION PROBABILITIES tells 83 the distribution of energy over the line and relates the halfwidth. These fields are connected by an equation of continuity. (2d) These equations express respectively the fundamental laws: (a) (6) (c) Nonexistence of a magnetic stuff analogous to electric charge. the most important of which are the scalar and vector potentials cp and A. which are characterized by MaxwelPs equations (2a) 0. This O to the harmonic mean of the mean lives of the initial and final levels.
In the theory of the differential equations (3). This is a usual procedure in dealing 9 will satisfy with electromagnetic waves at points far from their source. Expansion of the retarded potential. as in the case of a rotating unsymmetrical charge distribu . Example 4. / pikR (1) &. In terms of p (7) where 3. (5) t =t the distance between the volume element dxdydz and the point r x y z This is known as the retardedpotential solution because each volume element contributes to the potential according to the value of the charge and J8 is f . An exactly similar f f formula gives A in terms of J. derived from them by the formulas IM Maxwell s equations. Jc = 2?rv/c = 27rcr. R/c. To develop the classical theory of radiation in a form suitable for use in the quantum theory we need to expand this retarded potential formula under the assumptions that p and J vary harmonically with the time. In the expression &". .?(x y z t )~ eW^JpLifo we may use the expansion* * BATEMAN. density there at a time earlier than the instant t by the time it takes light to travel from the volume element to the point x y z . i. Hence we write where I is in general a bivector [a vector of the form and I the equation of continuity becomes div/+$fep = 0.lt. 388. Partial Differential Equations.e. It is to be noticed that if p s one may set = and derive S and 3tf simply from A. (Jp f iiy] . tion. p. we take p(xyzt) as the real part of the expression p(xyz)e^ivi Here p(xyz) may be complex. . In the theory of atomic spectra p and J are essentially zero outside a sphere 1 of radius small compared to This suggests an appropriate development of the retardedpotential formula according to powers of k.84 THE THEORY OF EABIATIO3ST 24 and ^. it is shown that the solution for the scalar potential can be written as * y in which z 1 i )  J P&y^dxdydz.
we find for the amplitude of the A th diverging wave At this point we introduce the classification of terms by powers of Jcr.\ 9/ O^_i_Q\ * KT l*&. Substituting (2) in (1). moments of the charge distribution. . the second gives what is called (electric) dipole radiation.r 1 i l . The first measures the transport of energy.i^Aroj we ( find for the leading terms in the scalar potential tftrivi i} P == ^~ A corresponding expression holds for A on replacing p by I. and A and are Bessel functions: z . 91 =jprrdv. we readily find that . the third gives (electric) quadrupole radiation. w the angle ^ ( $ ) This shows us that the potential given by diverging spherical waves. We define the dipole and quadrupole moments of p by the equations P= fprdv. the second that of angular momentum.(^Ar l. instead of by the integer A. (7) Using the values of the Legendre polynomials...34 EXPANSION OF THE BETARDED POTENTIAL f 85 is where r and r are the radii to the points x y z and x y between them. the higher terms correspond to local fields near the oscillating charge shall r distribution. o. It has not been necessary thus far in spectroscopy to consider higher terms. Since ^ /9}j_l\l a. since (1) corresponds to a system of We be interested only in the two leading terms in Z. are expressed in terms of the successive Here the terms The first term vanishes. We shall be interested only in the first three terms.lt.\(kr ).
where M=ljrxldv the magnetic (8) moment of the electric current distribution. and rQ is a unit vector in the direction r Let us make the corresponding reductions for the vector potential. we find Jpcfo = 0. Putting g= 1. therefore represents part of the electricquadrupole radiation field in the whole of the magneticdipole radiation field.86 THE THEORY OF RADIATION . 34 where 3t s is written for the invariant sum of the diagonal terms in 91. J(Ir + rl)dv = % which enable us to express the vector potential in terms of the moments of the charge distribution.xM. fldv we find the relations = ikP. the second 9 term here is proportional to the quadrupole r can be written as r. Because of the occurrence of k in these formulas we need only the first two terms in A to have terms to the order &2 in the result: f /* J /^V + ^M_ / \ f I \ The first term gives the part of the vector potential associated with the dipole radiation. A The second term and To summarize. The second consists of two parts: = The first ir^ moment. vector or dyadic function of position that is finite everywhere that p and I are not zero. First we note that from the equation of continuity and the fact that p and J vanish everywhere outside a finite sphere we may write =z f where g is any scalar. for convenience in later work. Putting g r and rr. as = already asserted. . we have here. the scalar and vector potentials up to the second power of k in the moments of the charge distribution are 9= ^ Since the coordinates of the volume elements of the charge and current distribution no longer appear.
integers) (3) the other hand. (&=l. E system expressible in terms of a set of constants of the motion..2. the quantum frequency associated with the transition set of quantum numbers by Bohr s frequency condition is Developing this in a power series in the r s. the other terms represent is a linear function of corrections... The correspondence principle for emission. The most fruitful idea in passing from the atomic theory to the quantum mechanics was the correspondence principle of Bohr. we have ^ The the first dE quantum term is just the classical frequency.. fc Tne classical frequencies of the fc _O m . In classical mechanics the energy of such a scopic frequencies of is .34 EXPANSION OF THE RETARDED POTENTIAL letters to 87 used unprimed tials denote the position and time for which the poten are computed. Bohr s . J = %&.. so that the combination frequencies which occur in a Fourier expansion of the motion are of the form Er^ = %rkwr k k vJh On from the (rk . From the principles pf quantization developed for con limit of transitions ditionally periodic dynamical systems it followed that in the asymptotic between states of large quantum numbers the spectro Bohr approached equality with actual frequencies of the mechanical motion. the higher terms s. In the special case in which E that of a system of harmonic oscillators. J 5 which is great idea was that this approximate connection probably holds not only for the frequencies. motion are given by the formula . %.. but for other features of the spectrum as well. Jl3 J2 strict Jn3 known as action variables. Before calculating the radiation field associated with the potentials of the preceding section let us investigate their connection with the problem of emission in the earlier quantum theory..n.aninteger) (1) .. The quantum conditions re these J s to values that are integral multiples of h. 4. vanish so that the correspondence is exact.
.88 THE THEORY OF RADIATION 44 According to the frequency relation we have a definite term in the Fourier analysis of the motion....). the spontaneoustransition probability for the transition in It is this which is postulated to be question. asymptotically equal to the classical rate of radiation. That is.. is * A HEISENBEEG.%.. ^ indicates the real part of the expression in The expected rate of radiation in quantum theory is ^A^ + where T!. .. Likewise the polarization of the radiation is postu lated to be that of the classical radiation due to the corresponding Fourier component. the combination term with multiples rla r2 . (6) where each r runs over all positive and negative integers..gt... . Zeits. Although the radiation process in quantum theory 1 occurs in jumps.. .. .IPJnj + Ti. namely (n . Thus Fourier for the electricdipole radiation the procedure is to develop the components of P for motion in the state specified by %..gt..]e ^. w 2 .] it was = [%.. whereas the classical radiation process is essentially con tinuous. (% ) &. namely.)&.. [*!. nn in a series. rl3 2 .. Tn . Exploitation of this analogy corre sponds to the first step in the formulation of quantum mechanics as done by Heisenberg. correlated with a definite .. quantum transition... ..]. (7) is the analogue of the Hermitian condition for matrix components... for example.. .).. the correspondence principle. fur Phys. 33. .. (8) where v^Tir^EfdJ^ and braces. 879 (1925).* Since P(t) is real. which by the Fourier components of P whose frequency corresponds to the quantum frequency in the sense of (5).)^(w be such that the expected rate of radiation for a particular transition will have a similar asymptotic correlation with the corresponding Fourier com ponent of the motion. therefore... Bohr postulated that statistically the transition probabilities will + Tl9 . there is an classical rate of radiation asymptotic connection between the rate of radiation of this frequency and the classical rate of radiation due to the dipole moment. The notation for the coefficient is chpsen to suggest its analogy with the corresponding matrix component in quantum mechanics. the rate of radiation of energy By is related to the by quantum jumps in the transition (% f TX ..JP^KT!.
44 THE CORRESPONDENCE PRINCIPLE FOR EMISSION 89 For large quantum numbers and small r s the value of this classical rate of radiation does not depend much on whether we use the Fourier com ponents of the motion of the initial state or the final state. For a complete account of detailed accomplishments of this kind see and Line Spectra* Van Vleck. Moreover. Therefore we postulate that the radiation as to angular intensity distribution and polarization. If certain of these were absent in the initial and final state. It is really surprising how many developments were made with the correspondence principle in its original form. ) our aim here to develop quantum mechanics inductively from the corre spondence principle. Bohr never offered the correspondence principle as more than an intuitive view that it is in this direction that we should seek for a more complete quantum theory it was in this direction that Heisenberg found it. possibilities one might even consider basing the Fourier analysis on some intermediate motion. Its importance in leading to the discovery of quantum mechanics cannot be overemphasized. the same as that given by the classical theory for a charge distribution whose moments are where (a\ 6) is the matrix component of the kind of electric or magnetic moment under consideration. naturally. one felt very confident in the prediction that the associated quantum jumps had zero probability. . 1926. and in a certain class of inter mediate states as well. But for smaller quantum numbers these two sets of Fourier amplitudes may be greatly different and the correspondence principle does not say which should be used . . * National Research Council Bulletin No. by Heisenberg s replacement of the Fourier components by the corresponding matrix components. In addition to these two . It is not .times the classical rate of radiation of this charge distribution. . the spontaneoustransition pro bability is to be taken as =. say one with quantum when considering this jump. We shall use field accompanying a spon taneous transition from a state a of higher energy to a state b of lower energy is. it no longer occupies a prominent place in the details of our subject. 54. . Quantum Principles The lack of symmetry between initial and final states which characterizes the above discussion was remedied. after that discovery. the principle in this form. and the verscharfung of the corre spondence principle accomplished. Washington. The selection rules were obtained by arguments concerning the absence of certain Fourier components. Rather we wish merely to sketch its place in the theory of atomic spectra. All suchschemes numbers (% f J^ n 2 f r2 are equally good asymptotically.
the radiation is linearly polarized with the electric vector in the plane determined and P. the dipole moment is of the form Pk 9 directed along the zaxis. In the theory of atomic spectra P is nearly always given by formulas like For transitions in which Am = 0. (4) 9 3 11.}P\^rQ . The dipoleradiation field. where ii+jj+ kk. We haye preferred to put the theory of emission on the correspondenceis principle basis merely to avoid the lengthy calculations needed to derive the results by quantummechanical methods. The postulates are justified in Dime 5. Using 2 44 we find. P. (2) ?r $ is the unit dyadic Since is S and ^ are given by the real parts of (1). In this case. in any direction of observation. Let us investigate the field associated with the terms in 34 9 which depend on the dipole moment. s radiation theory. The flow of energy is given by the Poynting vector. and the radiation field is that of a simple linear oscillator. Therefore at large distances the flow of energy is r. on retaining only the r~ l and r~ 2 terms.90 THE THEOBY OF RADIATION shall 44 For an atom the various moments which we need are expressed in terms of the coordinates of the electrons by the formulas It the matrix components of these quantities which are to be used in calculating the radiation.r. The intensity at an angle 9 with the zaxis is by r (5) . the time average radiation __ given by _ (3) where S and Jf are as in ( 1).
We shall denote by 6 and the unit vectors at each point in the direction &.f usually more convenient to shift the phase so and so coincide with the principal axes of the that they are perpendicular 1^ ^ and choose S so that the real and ellipse. We may now .4 . (9) s endpoint describes an ellipse turning from ffi into counterclockwise on looking at the plane normal to r as you would be faced if the light TQ in the direction opposite to r (that is.lt.54 THE DIPOLEBADIATIOK FIELD is 91 so the entire rate of radiation through a large sphere in all directions *. Am the zaxis (7) and the whole radiation in all directions is the same as (6). such that the real . Before calculating the polarization in the case Am= + 1. where $=z$r + iffi a constant bivector. &.6)^p(aP&). Thus in atomic radiation problems.? &. In view of the 4 postulate of 4 they are A(a. the polarization is called leftelliptic.rrvt # t sin2irtf.lt.p . (6) For transitions in which Am = the vector Pis of the form VfP (i if). that the location of the principal Usually the form of the calculations is such from symmetry. we may P2 by 4(aP6)j 2 in equations (5) For and either (7) to find the angular intensity distribution. It is i8 leads to the following imaginary parts of Se are perpendicular. in the clockwise direction for =41 the positive ^direction. } ^{Se^ivl} = Sr is GQs2&. ". in which case they form a pair of conjugate semir and f i may be oblique. write down the transition probabilities. The variation with time. &.lt.lt. value of Am. In either case the intensity in a direction making an angle 6 with is 7.f If this direction is were to enter your eyes). This readily equation for S. let us consider 27 the general question of the type of wave represented by &{$e }. o * 1.lt. for the transition (8) from the upper state a to the lower state replace 6. and in the opposite sense for viewed from 1. In general. We may write Se^^Se^e^ diameters of the ellipse. so The vector when Am = rotates in the xy plane. the axes is evident axes are along the meridians and latitude circles of the polar coordinates.
Using (1). in the sense that momentum crossing unit area normal to n toward positive is n in 2&.lt. and left elliptically polarized in the southern hemisphere.gt.lt. Then. . Hence the momentum transported radially outward angularmomentum transport corresponding to this is and the rx (&. The corresponding density of 2 angular momentum relative to the origin is therefore r x S/c and as this is field. moving outward with velocity c. .lt.p THE THEOBY OF BADIATION respectively so that r . the direction 5 = e right elliptically polarized in directions linearly polarized in the equatorial plane. 54 9 . (11) in which Z is Maxwell s stress tensor for the electromagnetic field This shows that the negative of the stress tensor gives the transport of Z*n gives the amount of electromagnetic momentum. The factor it? occurring in $ attends to the obvious detail that the phase in the light wave sent in the direction 9 has a constant relation to the phase of P relative to the direction of observation.gt. upper sign.77/2.p 9 Hf tj) = (0 cos0 icp )e^ 9 . if P = VfP (i ex (6 e is. Another way to find the angularmomentum transport equation o to consider the S) = 0. we need to consider the next term to get the angular momentum trans port.r unit time.lt.r ) =  ( rx to Since the leading term in S in the dipoleradiation field is perpendicular r. the transport of angular is momentum through unit area normal to r is r x Sjc. cp are the unit vectors of a righthanded system. Next we consider the transport of angular momentum in the radiation The volume density of electromagnetic momentum in the field is given 2 by S/c where $ is the Poynting vector. we find the time large distances to be mean angularmomentum transport at . (10) The radiation therefore. for the 0. ij) 9 + &. For this case the electric moment s variation in time is represented by a point rotating in a circle in the &yplane in the same e sense as the rotation of the electric vector in the light wave. right circularly polarized in 0&.92 of increasing 6 and &.#&.
To be sure there is no change in the ^component of the atom s angular momentum in this case. PROBLEM Show and replacing that the magneticdipole radiation field is obtained by writing 34? for in (1). For Am = I. Quantentheorie. or better that the classical analogue of the quantummechanical state for an assigned j and m 9 3 must be considered to involve an average over all orientations of the com is zero by symmetry. (12) all oTT the axial symmetry we see that the result of integration over directions must be a vector along the zaxis. The qruadrupoleradiation field may be handled in an analogous fashion.54 THE DEPOLEBABIATION FIELD 93 per unit solid angle. 19. momentum vanishes. Part I. since we found no radiation of angular momentum for Am= 0. where F is of value of Tav is ij).UBDJOWICZ. direction to compensate Moreover the rate of radiation of angular momentum bears the correct ratio to the rate of radiation of energy to insure that the angular momentum is The radiation for f 1 is Am = thus in the direction for the increase in angular ft radiated in the same time as the energy hv. the .* be objected that we have proved too much. 440 (1918). For brevity we omit the discussion of the transport of angular momentum * E. Hence show that for magneticdipole radiation by and  & for 34P P M !HMW. From and also since the diagonal have an average value this standpoint the perpendicular components of of zero before and after radiation. der Linienspektren. Zeits. as when Am = 0. If the radiation of angular the form VP (i F is real except for a phase factor e^. Phys. and was selection rule in the angularmomentum It very satisfactory for used as a foundation for the formerly is quantum numbers. (13) The quadrupoleradiation field. Its value is From k which is in the right momentum of the atom. ponent ofJTin theo^plane. j according to 9 11. but there may may be a change in the resultant angular momentum. p. 6. . This the correspondence principle. so there is no change in their value. and this agrees with the vanishing value of the angularmomentum transport in J this case. BOHR. The answer is that the classical analogy breaks down here. 48. This time average of Jx or J^ matrix components of Jx and Jy are zero.
r&. 8 3 et seq. S(Ara). are f ( 1) = J[+ ik i(kj+jk)} (4) ffi(O) =V[Miijj]. tials 3 9. a dyadic formed of the sum of dyads er^ for each electron 4 and so is a sum of dyads formed from vectors of type T considered in (4 9).lt.j( Am = ) 1.lt. except that (aj m\TT\oLJm) also includes an extra term which is a numerical factor times the identical dyadic. Thus. 1.gt.3r&. in making to get a symmetric dyad. the calculations we may as well put 1\ = 2 = Calculations of this type were first made by Rubinowicz.* It turns out T T that each matrix component can be expressed as a numerical coefficient multiplying basic dyadics.m \T^ j m ).t Y&ro) (1) is. . Z*6 3~r We r H91r )pr . normalized so that ! Am ( )". We can find the dependence on m of any such dyad by calculating 9i is its matrix components from the matrix components of (ocjmri T2 a7m )= / T given / by r 9 3 11. from 54 3. ((i}m\Tl \ofj m^(^j". . These dyadics. (3) This enables us to see that the selection rules on j and Am = for T^T* are Aj or In this way we may prepare a table of all nonvanishing matrix components for any dyadic made up of a linear combination of dyads of vectors of type T. fur Phys. S at* j* m". m or 0. 61. Zeits. The latter is equivalent to a vector whose as a vector of type T. them.lt. ^ = ii+jj + kk. fl3 p 2iri(vtor) e 64 from the poten *^ so that the Poynting vector r &. out. If this be done for a general dyadic the formulas can 2.94 in this case. intensity distribution They determine the angular * and polarization in its ETJBEJTOWICZ. 338 (1930). which depend on Am only. be expressed as the sum of the matrix components of the symmetric part and the antisymmetric part. (2) are not readyarmed from Chapter in with the formulas for the so we must stop to work dependence of the matrix components of 9 on m&. 4 THE THEORY OF BADIATION The terms responsible for the energy flow are. matrix components show the same dependence on m Since any symmetric dyadic is the sum of two symmetric dyads.
+v)(a . a relation.0.lt. r j = S(aj:ri a . 1. 2 2 1.* a and TT mean linear values of I the elliptic polarization becomes respectively. between them. With these factors it is easy to see that the polariza and on tion of the light depends on the direction of observation Am according to the scheme Am=i2 Am=fl Am=0 Here the senses right and left are for the positive values of Am.lt. = for the dyadic a* r^ Here occur three sums.. 12 4 and 12 9b) hare vanish forv=l. The vanishing of the matrix of rt x r^ here shows that If we let .64 THE QUADRUPOLERADIATIOH FIELD 95 readily calculate the values of the vectorial factors occurring in (1) for these basic dyadics: dependence on Am. the matrix components in question become + 2:) ft( l)=D(2m l)V(j + m)(jm+l)( 1) 2) = Similarly for Aj JS? 1 v there occur :a". Am &.)$( .for (3 tVo)fl( (S 2)*r = sin# e 2i*(6 cos0 9 (e o cos20 *9 l)fo = ^ icpo) oos0) (3Vo)(0)^o VsinooBfle (3Vo) 3r =0.+vjrf :a ?l) J for v = 0.gt.f Am= .D . First we consider AJ = A. we find (2j If we write + 3)1)! . .lt. so that the spherically symmetric part of (&.jm\TT\afjm) does not con tribute to the radiation._! = 0.lt.x.(2? D = j + 1 )D^ jD^ ( !)!&. Byrec[tdringthatr i xri =0(cf. We may &. (ajfoja* j+v) (a* j+ vi^ja j). They are opposite for negative and opposite at an angle TT Q in the southern hemisphere. For along cp and polarization with circular at 7r/3 and 27T/3. &. two sums. ing matrix components.
have J&. jlml) (6b) Finally for Aj = 2 the matrix components are multiples of the single sum the complete expressions being 2). and F which are matrix components are formally like those given above with new eS of the D.j=0 intensity.radiation formulas the transitions J = &.jm\r i i \ot lE(j + m)(j*ml)(j + m2)(jm+l) ft( 2). This gives for the corresponding probability of spontaneous emission A(*jm.* j m )= ?^ J(ajm%ay m 0&.gt.gt. (6c) Aj= h I or f 2 can be written down from eSr^rz i  these since the matrices are Hermitian. JJ. m The matrix components so that for 2 )[(j 2 l) m2 ] t(0).. These are special cases of a general rule. 5 2 )] . D.Q. vanishing intensity. its The dyadic 9J is of the form .lt.x.gt. To m where the square of the dyadic indicates the doubledot product of the dyadic with its complex conjugate. must then have We . and F for the individual electrons. Hence using the postulate of 44 . U. i we need to know that the integral of the product of each of the first three expressions in (5) by its complex conjugate over all directions is 4Tr/o. the total rate of radiation associated with the transition (oy oc / ) is calculate the total rate of radiation m&. Likewise in the dipole.gt. Since there is con have vanishing servation of the total angular momentum. (7) Examining the formulas for the matrix components we see that transitions between the following values of j: and 1 ^ 0. The 2 n pole radiation is connected with a change in the resultant angular momentum of the electromagnetic field by n units.96 THE THEORY OF RADIATION 64 these matrix components are = r (&. the vector sum of that of the atom plus that of the field remains constant.
beam * BRINKMAK. . . 1932. ergs/second is equal to & ^ r/ x state a to state b in (1) .64 THE QUABBUPOLEBADIATION FIELD 97 where j is the resultant angular momentum of the atom before radiation and / its value after the transition.j 7. Brinkman* has developed a grouptheoretical method of obtaining the qiiadrupole moment matrix components. 842 (1930). When an atom is unperturbed by external fields. The next term. We shall always assume natural excitation unless the contrary is stated. levels. 1934. T/ . Such a set of (2/+1) states we shall call a level. This is called natural excitation. In most light sources the conditions of excitation of the atoms are suffi ciently isotropic that it is safe to assume that the numbers of atoms in the different states of the If the excitation occurs in tion same level are equal. Dissertation Utrecht. is the number of atoms in state a and A(a. states The actual emitted intensity of the component from . This equation holds only when the radiation density present is so small that the induced emission is negligible. Rev. All components have the same wave number unless the atom is perturbed by an external field. 38. Asa. Phys. so we shall also use level in this wider sense. When the atom is perturbed and all have the same energy it is still convenient to such a set of states by a generic name. Spectral lines in natural excitation. ). Resonance Radiation and Excited Atoms. as by absorp from a unidirectional beam of light or by impacts from a unidirectional of electrons. some definitely nonisotropic way. b) is the spontaneous emission probability for that transition. In actual practice it is very difficult to know N(a) and hence to make where N(a) absolute comparisons between theory and experiment for emission inten sity. Most work is therefore on relative intensities of related groups of lines. j For a review of this field see MITCHELL and ZEMANSKY. Cambridge University Press. its Hamiltonian com mutes with the resultant angular momentum J. or octopole radiation. The study of such effects J raises a whole complex of problems some what detached from the main body of spectroscopy. large departures from natural excitation may be pro duced. each of the different states being characterized by a different value of m.. Likewise we define the word line to mean the radiation associated with all possible transition between the states belonging to two the different states do not refer to The radiation resulting from a transition between a particular pair of we call a component of the line. f HUFF and HOUSTON. consequence (3 3 8) an energy level corresponding to a given value of j is (2j+ l)fold degenerate. has been considered briefly by Huff and Houston.
This means that we expect the mean life state must be the same. B) = N(A) hv A(A. B) = S 8(0. A For the strength of a line it will not matter in such formulas whether or B is the initial level. since the excitation is isotropic and there is no external to field the radiation to be of equal intensity in all directions. B). C. b and to introduce the partial sums over a and 6 alone. It has the is not symmetrical in the initial and final levels owing 1 I)". 9 We shall also ponent notation 2 find it convenient to call (&j. otherwise if the excitation . 6) . First. belonging to 64TAr3 all lower levels B.1) N(a). S(A. B). and unpolarized. (2jA 4. B) let us consider what properties we expect have. This represents a slight departure from the traditional procedure.d... D. . where the intensity is NA ( written as proportional to the total ) : number of atoms in the initial level. multiplets). A states b. which relates it to the symmetrical S( A. the two cases. The intensity of a particular line is therefore proportional to the number of atoms in any one of the initial states.". I(A. if the initial conditions are isotropic we expect the physical situation to remain so during the radiation process. B(A B). B(A 6 9 b) = S \(a\P\b)\^ a b . B) = S B(A a = b) a& S(a. (2) in the case of dipole radiation. whereas if jA ^jB the Einstein A s are different in . That is. it is the reciprocal of  This should have the same value for each state a.. with the ^ j?) =  ( a \P\b)\*. this gives As N(A) Here A is disadvantage that it to the factor (2jA f the spontaneoustransition probability of Einstein. The mean life of a a is the reciprocal of the total transition probability from a to all lower of each state of level .. Second. Before calculating S(A..98 THE THEORY OF RADIATION 74 The total intensity of a line is the sum of the intensities of its components.c. In later work we shall find formulas for the strengths of certain classes of lines where one level belongs to one group and the other to another group (e.g. B).P6)f the strength of the com a. by 5 4 8. to a4 and to S(A. Therefore we shall regard the strengths as the more con it venient theoretical measure of line intensities. The sum of the squared matrix com ponents occurring here we shall define as the strength of the line. Hence in natural excitation for the line from level A to level B.
74 is SPECTRAL LIKES IN NATURAL EXCITATION cut off tlie 99 numbers of atoms in the different states of level A will be un equal after a time. if we replace P by M. Because of this.and leftelliptically polarized radiations whose intensities (5 4 7) are respectively proportional to (Am* +1) (4b) (4c) (Am=l) That the sum of these three quantities 13 3 is independent of 8 follows from all directions. By 5 5 the intensity in the direction 6 of radiation proportional to S m=j 2 2 I(ajmPa /m) sin 0. Since there is no very simple general relation between the levels we expect this to be true for each suramand because of the symmetry of (#P6)I 2 with regard to a S(a. b) is indepen y B C. &. it is. and a nonisotropic situation will have grown out of an isotropic one. it follows that if S(a.gt. (Am = 0) (4a) There will also be right. Sf(ajmPaY+l) ponent is 2 cos 2 along 8 2 along j mf I)] 54 10 and 54 9). B) is independent of a. it follows from 13 3 3 that the resultant radiation unpolarized. When the cp and com added to that is for Am = 0. so for the whole strength of the line a j to a j we have .gt. The summations over the three values of mb which go with where S (^".. Likewise and b. then B(A. 1 is no longer elliptically polarized because the righthanded radiation from m&.gt.&. partially plane m polarized with relative intensities S^ajmlPla (cf. . however..mf 1 is of the same intensity as the lefthanded from 1. summation over m merely introduces the factor (2j + 1). dent of 6. since the dependence on m of 4 (4 9) is the same as that of P.gt.&. 3. * J ) = ( 2 ^ X) K*/5 W 2 ) S 0". A () Everything we have said here about electricdipole radiation is true for magneticdipole. We shall now show that the dipole radiation in the transition a j planepolarized in the direction 8 is a / is 4 isotropic and unpolarized. B). for all atoms.gt. ma = m have been evaluated in 13 3 1 where their independence of the value of m already was noted. M For quadrupole radiation the analogue of (2) is (6) The strengths for quadrupole lines are defined exactly as for dipole with % in . hence the intensity of radiation is the same in The sum of the terms for Am= h 1 and Am= m&.
Of the 87ra2 da waves per unit volume (we say waves z as a short expression for degrees of freedom of the field) there are 2a dada) associated with waves which travel in directions contained in the factor two arising from the two independent states of polarization associated with /)&!&. .6)/(fl. then we can say is the transition probability for processes da&.S) . and with the polarization I we s for the probability of b with emission in the solid angle dw at to Hence A(a. From is given by combining 147 with 7 4 3 or 7 4 8. 4 4 probability (5 8 or 6 7).&.gt. as discussed in 5 . may write = A(a. The emission in the transition a~&. and let /(0. We suppose for con normalized so that its real venience that / is and imaginary parts are 4 perpendicular. This and the emission spontaneous constitute the inverse process to absorption from a beam whose range of directions is dcu at 0.6 is a spherical wave whose intensity and polarization in for the important special cases._. If A(a.=l over all directions. interaction of the following argument.gt. In view of the relation found in I 4 between the probability coefficients for spontaneous and induced emission and absorption. at 6. That gives the result for the an atom with an isotropic unpolarized field. 9. 9. ? )&&. the formula for B(A. (1) There will also be stimulated emission. This emission takes spontaneous transition from a 6. The partial sums here (3) is also equal intensity in all directions.&. 9.p)da&.. The results are j. Expressions for the strengths of the various quadrapole lines are easily calculated from the values of the matrix components in the previous section.6 fl.^) S27rVS(4.lt.gt.lt. (8) Induced emission and absorption. f(0 9 &. which gives the wave emitted in the direction B. b) is the whole transition statistically that A(a. we expect this to be simply related to the A(a.gt.p)&o in which the light is sent out in the solid angle place with the polarization described by /.gt. There is a further point on which we wish information. have the property of giving unpolarized light of The spontaneous transition probability analogous to A^. b) for a line component. &)/(0.p) be the unit bivector (// 1) polarization of the normal to the direction of propagation.100 THE THEORY OF RADIATION 74 place of P.9.. 9.. namely the pro bability for absorption of light from a unidirectional polarized beam. B) in terms of the matrix components of dipole or quadrapole moment 8.3) F*.lt.gt. n. ^j^jy. different directions we have calculated Let the angular distribution factor be where Jfda&. da&.gt.
d. 1) [*(&.p. (2) The same equations hold have chosen for the other state of polarization. Using the MaxwellBoltzmann law 8?r to get and the Planck law 1 5 divided by and realizing that here the statistical weights are each unity. I in accordance with the actual polarization of the 5.t.lt. I) = B(b.lt. to Let the intensity of the beam be p(a. I) da da*.gt. emission processes in the form m) = 0. m. Let us consider the description of the polarization a little more closely.b.&. 6.p 9 and 6 4 that the elliptic polarization always has for its principal axes when the transitions are between states 5 4 and labelled by m. 8 ^ 2rr covers all possible types of polarization according to the scheme Left . 9. 9.6. 8.(*. /) B(a. 1) A(a. m orthogonal to / in the sense l*m = 0. This is the volume density of energy in wavenumber range da of waves whose directions are in the cone da} and with their polarization described by I. I). A(a. 1)] = N(b) B(b. 9. The bivector I may be written in the form direction beam in the and polarization state /= 8 since cosS F icp sinJS.l). as in 1 6. p(cr. 9. I) 4 we have B (a. We define the probability of absorption (or induced emission) of this radiation so as to cause a transi tion of the atom from a to b as 4 Then. a.&. b. The range &.b.e. absorption coefficient vanishes.lt. 9. is to choose I as one of the canonical states 3 of polarization and to introduce describe the other. 1 44 /)/&. but as we wave sent out in the emission process.b. and 1 48 Analogous to we may write da&. We are at liberty to choose the independent states of polarization in any convenient way.84 INDUCED EMISSION AND ABSORPTION 101 each direction of propagation.lt. 8. the balance of emission and absorption between these degrees of freedom and the atom when in thermal equilibrium gives N(a)[A(a. (4) we have found in &. 9.. 1) + P (a.gt. if a is the upper state.lt. 9. a. &. 9. 6. so the corresponding the rate of N(a) A(a. b. The natural way in discussing the transitions a ^ b of the atom.l) = hco*B(a. 6.r) + 1] (3) where n(a) = p(cr in the 5 fyjhca* is the mean number of quanta per degree of freedom under consideration.
lt. flCcr %f a Using (1) and the expression 54 8 for A(a. simply 2 f ^ times the value has when the If the incident light is unpolarized. that this equals We have seen in 7 4 that the total emission of all is components of a line in unpolarized and of equal intensity in all directions.102 THE THEORY OF RADIATION bfvector orthogonal to I is 84 The m=6 reversed. (5) In this case the absorption is is I. B. S(A. I and m. If the incident light is polarized in some other manner than with regard to one of the canonically chosen forms. states b of level The is total number of by e is transitions per second from the B to the states a of level described A caused by absorption of light whose polarization a b. say with its electric vector a scalar multiple of the unit bivector e. The sum here is the total strength of emission per unit solid angle with polarization e\ this is accordingly l/8rr times the total strength of the line natural excitation A.between each of any two orthogonal states of polarization. which represents a wave of the same ellipticity as that for I but with the major and minor axes interchanged and the sense of turning. it depends only on the energy density and is independent of direction and polarization of the light. Finally let us consider the absorption by a group of atoms in a state of natural excitation. B) as defined in 7 4 as line in ~ 03 (6) This gives the number of quanta per second absorbed from a unidirectional of energy density p(&. for example in the case of dipole radiation. right or left. . then it may be expressed as the resultant of two components polarized as in I and m by the formula it e = l(!*e) + m(me). 6) we find. the intensity is polarization along distributed equally ". beam The Einstein B for isotropic radiation obtained 877* from this relation.e)dadu) As we expect.y. sinS icp cos JS. Therefore we can express the rate of absorption for the whole terms of the strength S(A. so the absorption is half what it would be if the polarization were along I.B] 47 bears the proper relation to A(A B) } (cf. 1 and 7 4 3).
This occurs when the light frequency corresponds to a transition 4 frequency to within a small range given by the natural line breadth (1 10). where v(A. Quantum Mechanics. where n is the index of refraction. to a certain extent they have a definite phase relation to the phase of the incident light). We wish now to consider the interaction of light and matter when there is no such exact agreement. is regarded Dispersion theory. Raman effect.B) is the Bohr frequency associated with transition from level A to level J3.84 INDUCED EMISSION AND ABSORPTION 103 The results we have reached by the phenomenologieal method follow from the Dirac radiation theory. is a scattering to all sides of light in which the frequency is an amount corresponding to one of the atomic transitions. In addition there are terms which oscillate with frequencies vv(A. in the wave(6) There is a scattering of light to all sides without change number. This is by the Raman scattering. Scattering. When these are calculated by quantum mechanics it is found that they include some terms which oscillate with the same frequency as the light wave. but the best * modern treatment is by DIKAC. This dynamical theory of refraction goes back to Larmor and Lorentz. 173. There are essentially three phenomena: a phase velocity cjn (a) The macroscopic light wave is propagated with instead of c. so it is necessary to consider the phases in summing the scattered waves due to different atoms to find the resultant field. This is called Rayleigh scattering. for they are all con nected with the oscillating moments induced in the atoms by the perturbing action of the fields of the incident light wave. . they are of different frequency coherent with the incident radiation. p. (c) There shifted As subheads under (a) is produced when the gas effect and the Faraday effect respectively).B).* 9. using the form of the perturbation theory in which the perturbation as causing transitions. Raman and so The forced oscillations of the same frequency as the incident light are to a certain extent coherent with it (that is. Another derivation which gives correct results for the stimulated processes but does not give the spontaneous emission is to treat the electromagnetic field of the light wave as a perturbation. there are special effects like the double refraction in an external electric or magnetic field (the Kerr All these phenomena belong together in the theory. The latter are responsible for cannot be scattering. It is unimportant in monatomic gases but we mention it to complete the picture. In the preceding section we have considered the absorption of light by matter.
so & and &P are transverse to the direction of propagation. n. so the two eigenvalues * DARWIN. the total dipole moment per unit volume is N&*$. Using the form of Maxwell s (2) equations for a material medium devoid of free charge and of unit magnetic susceptibility: IdS c 57. a tensor. 1 (1915). ibid. OSEEN. The induced dipole moment P is related to the electric vector P=a&.104 THE THEOHY OF RADIATION 94 Darwin.e.* The net result of such calculations can be simply stated. der Phys. 137 (1924). is equal to an eigenvalue of the tensor a regarded as a twodimensional tensor in the plane normal to n. 23. that is. becomes $ e=3 + 4^a. 42. see also ESMAUCH. at (3) =. We shall see when we calculate a quantum mechanically that it is always Hermitian (with regard to the three axes of space). Assuming that Na&. . Ann. BOTHE. Arskrift. then double refraction for each direction of propagation. we and the macroscopic that the principal values of Na are each small compared may neglect the difference between the effective on an atom S\ hence the dielectric constant. = o. n is admissible and the (6) n==l + 27rj/ya (5) shows that 8/277^7". Soc. Univ.lt. Phil. 48. LTTNDBLAD.Q. 1257 (1913). nn x g =3tf. The two eigenvalues lead to two values of the index of refraction. by (1) where a is the polarizability tensor. Trans. 64. Then if N is the number of molecules per unit volume. any value of normal to .lt. i. 1920. c ct we may find planewave solutions in which each vector is a constant multiple of ariv(tnnrlc) where n is the index of refraction and n a unit vector in the 9 direction of propagation. Cambr. Upsala. The corresponding eigenvectors give the two types of polarization associated with the waves propagated with the velocities corresponding to the two indices of refraction. we may write n = 1 f S. ibid. Mi irrigating &C between the righthand pair of (4). we find that the part of &f which is perpendicular to n satisfies If a is simply a scalar index of refraction is a. 693 (1921). to unity. but if a is not a scalar. Since the prin cipal values of the dielectric constant differ from unity by small quantities. tions The constant amplitudes must satisfy the equa n .
94 DISPERSION THEORY. element which in excess of the the Rayleigh scattering. . This. 5. Then we calculate the matrix components (ajmjPa J w ) p of the electric moment of the atom with regard to these perturbed states. or in special cases. We shall not have occasion to consider in detail dispersion and the related double refractions produced by external fields are of importance in the theory of spectra in that they provide other The methods for measuring line strength than those based directly on emission or absorption. gives rise to scattered total volume. for an adequate discussion of this point. Of these the component (oyraPoyra) p gives rise to an electric moment which is coherent with the incident light wave and which is responsible for the various dispersion phenomena. Mod. in which case N is the number of molecules or atoms in unit volume. the scattered radiation. then the eigenvectors are real and we have ordinary double refraction. system. and correspond SCATTERING. and the major axis of one ellipse is the minor axis of the other. a will appear in the form. hence they give rise to scattered light. There are two cases to distinguish: if a12 = 5 12 so the components are all real. and the matrix components (aJmPjoc^ml) also contain terms p which are of the same frequency as the incident light. Choosing /. together with some non coherent parts of the induced moment of unshifted frequency. where N is calculated by dividing the total number of molecules by the The waves is by the number of atoms in each volume mean do not interfere in regular fashion. of the molecules in a gas the medium is not homogeneous. For their theory we need to calculate the polarizability (1). This is obtained by calculating the perturbation atom by the field of the light wave. Therefore the two states of polarization are orthogonal as discussed in 8 4 so they have the same ellipticity but one is right and the other left. whereas if a12 ^ 5 12 the eigenvectors are bivectors and the two fundamental states of polarization are elliptic. When the atom is unperturbed by other external fields the energy is independent of m. RAMAK EFFECT 105 are real real unit vectors / and m so that to propagation without absorption. 106 (1933). Phys. Owing to the thermal motions .* * See BEEIT. circular. two and n form a righthanded coordinate m. The foregoing discussion applies to the effect of the waves scattered by the molecules if the medium is absolutely homogeneous. but these are not coherent with it and so they contribute an additional amount to the tensor a introduced in of the states of the Rayleigh scattering without contributing to the dispersion. a = an ll+ ai2 fo+ 512 m/4. Rev.a^mm. the number of molecules in any volume v at a given instant fluctuates about the mean value Nv. It is easy to show that the two eigenvectors 2L and 2% are orthogonal: St^St^Q.
jm)^^^ (8) we find that this is a solution if (9) The matrix component of F with respect to these perturbed states is. first approximation the perturbation is the electric vector of the perturbing light wave.im fi will to the first order whose unperturbed eigenfunction is $(&. .jm)e.y. and H Assuming the expansion for the unperturbed Hamiltonian. where ^{?e27rM} is become where ^(ctjm) is chosen so that this expression satisfies (5 3) 2 (ir~. (11) be found by using 9 3 11 for the matrix components of F. This transitions. (10) ajm: therefore W J". the last two parts vanish when the sum is 5. first order. To a .4Wi=i[J*^^ L dt] \ Here we have written E = hv to represent the frequency of the light. ^(ajm) = f S ^(a7mO[(aym&.gt. The state (ocjm) neglects efiects connected with quadrupole .106 THE THEORY OF RADIATION 94 The calculation is based on a slight modification of the perturbation theory of 8 2 required by the fact that the perturbation depends on the time.lt. and a gyrotropic part which is a multiple of i(jiij)* When there is natural excitation and no external fields. to the Using the results just found for ^(ajm) and ^(ajra) this can be written as (ocjmFocj w) ^{afcjmKe2 where a(ajm) a(ajw) is the polarizability tensor of the state /w / _ y n ~*LI aJ w p a W m/ + E 1 p W ll )( a/ QC l ^ m ) m f \*J m T\ + (*j\P\* f~^(* f WE \ __ *}. When this is done it is found that the tensor can be ex pressed conveniently as the sum of three parts: an isotropic part which is a The dependence of a on m can multiple of a doubly refracting part which is a multiple of S(0) of 6 44.
The dispersion formula for this case was discovered before quantum mechanics by Laden In case all one term like burg* from a correspondence principle argument. J KRAMERS and HEISENBERG. 26. Zeits. fur Phys. in the absence of external fields. a j) = \W(&. leaving only the isotropic part. not the sum. negative for those lower. RAMAN EFFECT tlie different 107 taken over m values. 113. fur Phys.*. fur Phys. This shows that in natural excitation. This is the average. LADENBURG. The ex perimental reality of negative dispersion has been very thoroughly demon strated by Ladenburg and his associates. 192 (1928).. The existence of the negative dispersion terms for atoms in excited states was recognized by Kramers f and later Kramers and Heisenbergf reached the complete formula from the correspondence principle.j)]jh. aj) are positive. The term (6) to obtain the index of refraction. 51 CARST and LADENBURG. 4. In this all the v(oc /. . KCXPFEBMANN and LADEKBURG. 451 (1921). oc j) is positive for those energy levels W(&. Raman electric vector is f + [2jT v(a where the actual motion * is 0l{r}. t KRAMERS. n (12) gives the average contribution of atoms in the energy level W(CLJ) so that the effective average value of a is obtained from the distribution of atoms: I N(&. 31. The frequency v(&f. 2 a)] r = ~SeMv{ A } The solution of this equation represents LADENBTIRG. as distinguished from line strengths. 673 (1924).94 DISPEBSION THEORY.x!j ) which are higher than TF(cy ). of j ) the polarizabilities for the different values of m.x. Nature. 48. 15 (1928). 48. 48. Zeits. The matrix components occurring in the isotropic part are proportional to the strengths S(aj. and where v(ct! f.oc /) of the lines. 681 (1925).lt.lt. This is based on a comparison between any one term of (12) with the term given by classical theory for dispersion due to an and natural frequency isotropic harmonic oscillator of charge e. including scattering JLC. mass The equation of motion of such an oscillator when perturbed by the v(v! a).lt.W(y. the gas is optically isotropic. use this value of a in The KramersHeisenberg dispersion formula is obtained at once when we = 1 + S. ibid. SCATTERING. In the discussion of the dispersion formula (12) it is convenient to intro duce a new set of quantities called the oscillator strengths.j) (13) the atoms are in the lowest energy level we need here only (12). ibid. so that finally the isotropic polarizability oc for natural excitation may be written as . (1928). Zeits.
For the latter 2 . The oscillator strengths f( /. a j) called the oscillator strength. Haturwiss. negative term in the brackets is the correction due to the negative dispersion arising from atoms in excited states. 879 (1925). Using (13) and (14=) it is possible to express the effective polarizability in terms of thef s as the sum of contributions associated with each line 5 spectral : in which a j refers to the lower energy level of each line and a / to the and the sum is over all the lines in the spectrum. fiir Phys. 627 (1925). Zeits. Zeits. each spectral line contributes to the polarizability a term whose form is that of the contribution from a classical oscillator. KTJHN. so the classical value of the polarizability of the oscillator is Comparing with (12) we see that the quantum theoretical formula be written as where W ^ ^ for oc(oy) (M) J . &. 7 3 multiplied by a dimensionless quantity f(a /. aj) is equal to unity. It is a simple consequence of the law of commutation of and p r and is important historically in that it was used by Heisenbergf to find this commutation law in his first paper on matrix mechanics.108 where THE THEORY OF RADIATION we find that r = i 94 the sum of free and forced oscillations. 33. From the commutation law 5 2 1 we have THOMAS. * .gt. The rule states that for a system containing a single electron the sum Sf(a /. cy ) we find that . aj) satisfy an interesting sum rule which was discovered independently by Thomas and by Kuhn* from consideration of the dispersion formula from the standpoint of the correspondence prin ciple. JJ j) ~ 8 ^/ a ? j) S(q j? g/) 3e*h 2j+l In other words. 408 (1925). 33. The proof is very simple. fiir Pbys. 13. t HEISENBEEG. The higher. Like the Einstein A s and B s the f s are not symmetric in the initial and final states owing to the occurrence of the factor (2j+ 1)1 From the symmetry of S and the antisymmetry of ^(a /.
RAMAN EFFECT single electron in 109 is For a an arbitrary potential field the Hamiltonian from which by the commutation law we find that so that the matrix components of p in terms of those of r are j m )= 27r^v(cc a)(ajmrloc Hence a diagonal matrix component of (p*r T*p) is f / / (cf. hence we have b(J?.A. SCATTERING.4.lt. have been evaluated . (2) The intensity of a light beam is measured by the energy I (a) crossing unit area normal to the direction of propagation in unit time in the wavenumber range da at o\ Since p(a) is the volume density of energy. but with v 2 v3 .* This is independent of ra and can therefore be summed over m by multiplying . number of transitions In the ordinary treatment in which we neglect the natural width this total is written p(a) N(B) B(B.(cr). if p(cr) is essentially constant in the neighbourhood of the line. Measuring a from the centre of the line we may write for the probability that a quantum between a. Then. a). &. account of the Let us now consider the actual shape of an absorption line in a gas. 4:7Tjji a S Ka ? m".aj) = ". 0). * Sums of this type. l. 432 (1932). /m / ).gt.94 DISPERSION THEORY. / a)I(aj?mroc /m 2 )I = 3S. The finite arises in the coupling of the width atom and the radiation field and so 4 applies to absorption as well as emission.and a+du produces a tran sition in unit time.jm\p\a. . the total number of transitions produced by radiation in the is neighbourhood of the central frequency b(S. definition in (14) this Substituting the oscillator strengths f(& } from their becomes a Sf(a j . 5 which is the required sum rule. taking finite width of spectral lines as given by 1 4 10. evidently JT(a)=c/&. A). and v4 written in place of v(a by Vism. Phys.4)/TOp . Natural shape of absorption lines. Rev.xj) by 2/fl. 41. 10.0) = B(J3. When we take account of I IO we find that the absorption probability varies with a over the natural width of the line.
gt. we may calculate the total absorption by expanding the exponential function.110 THE THEORY OF RADIATION 10 4 The ". But if there is a larger amount of absorbing matter. In Fig. the amount of matter present gives rise to appreciable absorption at fairly large large distances from the centre.gt.gt. Although the absorption becomes very small as we go away from the centre of the line. where _. This is remarkably close to the true asymptotic value. This gives for the total absorption V 2V/I^2 = 239l a V. + Vo Jf line. thickness A# in time AOJ/C. thickness x of absorbing (3) . mi&.beam goes through. . Then height is the thickness of the absorbing matter. becomes essentially complete in the centre of the band and the curve be comes much broader than the natural breadth. 7T(7 The coefficient of N(B) x in the istic of the line in question. = C  N(B) x. so that its diminution in intensity can be found by multiplying the number of transitions it produces in this time by the average size of quantum. The absorption is 50 per cent. I 4 it is The integrand gives the shape of the absorption For large the absorption for several values of plotted . kv.lt. so that ~I we have to calculate * 1. The amount of energy removed from the incident beam in da at a is If we are dealing with a small amount of absorbing matter. [1 0&. saving only the first 77&.^w53*] do/a =I *o /(O W to get the total absorption. to give the relation Hence the material is intensity after going through j a 2 .7 / two terms and integrating with respect to o. is the number of atoms in the initial level of the absorp tion process contained in a cylinder whose base has this area and whose We expression for is an area that is character shall call it the effective area for absorption of that line.^ I(a) . for coefficient For large values of we can estimate the integral by supposing the integrand equal to unity out to this point and zero beyond. finite = V~^&. This recovers the result or hvB(B.A)N(B)x[c which applies when we ignore the natural or &. __ _ . line width. e".lt.
10 4 NATURAL SHAPE OF ABSORPTION LIKES first 111 Considerations of this kind were Beiche* on the basis of the classical electron theory. for 1. J. 42. Using the known asymptotic expansions we have. 199 (1931). The natural shape of an absorption line for several values of first . ibid. Adopting any convenient definition for the width of the absorption line. &. 300 (1930). MDTNAEBT and MULDERS. 30 (1924). 2. exponential function. and thus find that for the Thus the strength at a given point in the wing is directly proportional to number of atoms in the line of sight. 2. ibid. Astrophys. 59. 165 (1931). we see that the width varies as the square root of the active number of atoms in the hue of sight. * LADENBUBG and REICHE. where the absorption is small.gt. . integral in (4) developed by Ladenburg and They evaluated the and found where the J 5 s are Bessel functions. but we cannot go into this interesting topic here. These results have had important astrophysical application! to the theory of the Fraunhofer lines in the solar spectrum. Out on the wings of the * line. we may develop the 4 Fig. 181 (1913). I . UNSOLD. retain only the the absorption is given by two terms. f STEWABT. Ann. Zeits. such as the wavenumber interval between points where the absorption amounts to some fraction of the total intensity. fur Astrophys. SCEUTZ. der Phys. 1.
f&. 2 and Ls determines its depend ence on 6 and 9 according to 43 12.gt. may Centralforce problem. Lz and 2 2 . LZ9 may be taken as constants of the motion. In this chapter we treat the hydrogenlike spectra and the alkali spectra. etc. We single electron. 1.CHAPTER V ONEELECTRON SPECTRA simplest atomic model and the only one for which all details of the spectrum can be accurately calculated is that of hydrogen and the hydrogenlike ions. We and Lz The Schrodinger . Neglecting electron spin and relativity effects the Hamiltonian for the electron is where r is its From 83 4 we see that H commutes with Lx Ly . This model consists of a heavy nucleus of charge and a law. ju We consider the motion of an electron of mass its is in a central field in which distance from the centre potential energy given by U(r). .g. so we may write &. (3) In this case the equation for the radial factor of the eigenfunction becomes * The allowed values of the energy W are the values for which this equation . and therefore 2 and any component. look therefore for simultaneous eigenstates of H. Li III. equation (6 2) for this Hamiltonian is If we express the Laplace operator in polar coordinates *2 i and use 43 27. Zte The Hell. this becomes a / The requirement that be an eigenstate of I. of force. 2 e. anticipating for the latter the justification of the assumption that these to a good approximation be regarded as oneelectron spectra.lt. interacting principally according to the Coulomb shall see in later chapters that the spectra of the alkali metals may be treated by regarding one electron as moving in a central nonCoulomb field determined by the nucleus and the average effect of the other electrons.
1 s CENTBALFOBCE PBOBLEM 113 and remain finite at infinity. The separate Schrodinger . so that n f * for the lowest state I 1 is the number of nodes of the radial eigenfunction. principal. The quantum. etc. This scheme arose in connection with the interpretation of various series of lines in the alkali spectra. possesses solutions which vanish at the origin value of Lz does not occur in the equation for W. Also in accordance with custom among spectroseopists we introduce a letter code for the values of I. Expressing this in terms of momenta and substituting the Schrodinger operators for the momenta. it is customary to distinguish the states by means W of a total quantum number n which has the value I f 1 and increases by unity for each higher state. Let X. z the coordinates of 9 the electron relative to the nucleus. as in classical mechanics. known as the sharp. the kinetic energy of the whole system becomes where p is as in classical dynamics the socalled reduced mass. not counting the origin as a node. o u The energy levels will be labelled by the quantum numbers n and I according to the scheme W(ls) W(6d). numbers nl will be said to specify the configuration of the electron. Let us now consider the twobody problem in which the electron moves under the in fluence of the same field due to a nucleus of mass M. Z be the coordinates of the centre of mass of the system and x y. the Schrodinger equation of the twobody problem becomes where Ax is the Laplacian with respect to the internal coordinates and A^. The variables may be separated by writing $ as a product of a function of the internal coordinates by another function of the centroid s coordinates. diffuse. Then.. and fundamental series.) since fold degenerate. (This result follows also from 3 The equation (4) for the radial eigenfunction is formally that of a onedimensional motion under the effective potential energy H the second term corresponding to the effective potential energy of the centri determined by this equation fugal force.. T. according to the scheme Value of Z: Designation: spdfghiklmn 9 1 2 3 4 5 6 7 8 9 10 11 12 q 13 r 14 t 15 . The preceding discussion has been for a fixed centre of force.is that with respect to the centroid s coordinates. It will be noted that the hence each value of W associated with the quantum number 38 I will be (21 f 1) commutes with JL. Starting with the lowest value of for a particular value of Z.
The total energy E breaks up into the sum of the internal energy W and the energy of translation. Hence we may allow for the finite mass of the nucleus simply by using the reduced mass in place of the electronic mass in equation (2). . 2. so the finite (2) solutions are defined by the requirement that n be integral. The energy of translational motion does not need to be considered farther as it does not change appreciably during a radiation process and thus does not affect the line frequency. In this ease. it will /&. An attempt to solve the equation with a power series in p shows that the solution which l is finite at the origin starts off with p +\ This suggests the substitution which leads to the following equation for/(p): / P P If this equation be solved in terms of a power series in /O.gt. The polynomials obtained in this way belong to the set usually known as associated Laguerre polynomials. Chapter xvi.* recognized as the equation of the confluent hypergeometric From the form assumed by the equation near p = 00 we see that finite the solution which remains there contains the factor e~# 2 . We shall now consider the radial equation 1 5 4 for the function U(r) Coulomb potential = Ze*/r: jit r \ By making the substitutions Z this equation takes a * = on the more concise form which is function. (4) be found that the series breaks o2 as a polynomial of degree n I lif^isan integer greater than I.. while that for the external coordinates is simply the Schrodinger equation for a free particle of mass fi + M. atoms: ue4 gives just the wellknown Bohr levels for hydrogenlike W * ^Z* A _ WHJTTAKEE and WATSON. series defines If n is not an integer the power &.114 ONEELECTRON SPECTRA I5 equation for the internal coordinates is then found to be just (2) with the reduced mass in place of the electronic mass. Radial functions lor hydrogen.gt. Course of Modern Analysis. a solution which becomes infinite like e+f* as p oo.
He showed that to within a norm alizing factor the radial wave function r 1 R(nl)jr is nt~i( /d\ / Z\ n + 1 } (S=f:nji(sy in M=) it is 1 is which z is set equal to Z]na. easily seen that Tlie Laguerre polynomials may also be studied with the aid of their xt generating function. R^v. Carrying out the indicated differentiations.!)(*). (10) An equivalent definition for the associated Pp^^). = L^(p). 927 (1926). defined (8) The associated Laguerre polynomial L(x) I%(x) = It is is DL by (9) n (x). the polynomials so defined that satisfy f(P ) the solution being a polynomial of degree n Laguerre polynomial is I 1. (6) the symbol for differentiation with regard to x. (*) *~1 + M2(M 1} If the indicated differentiations are actually performed.l)f. (11) Applying either of the the general formula: definitions we find that the polynomials are given by From this form they are easily seen to have the following relation to the hypergeometric function: Eckart* Another form of the solution for the radial functions which is due to is useful in some calculations.gt. after the differentiation performed.. Phys.. 28.25 RADIAL FUNCTIONS FOB HYDBOGEH The ordinary Laguerre polynomials may be defined by the equation 115 Ln (x) = ex Dn (xne~x where D formis is ). + (. according to the following expansion * ECKAET. (4). this becomes V. 82 . An equivalent (7) = (&.
116 ONEELECTEOK SPECTEA is TMs the relation used by Sckrodinger* for calculating certain integrals involving Laguerre polynomials. (Abscissa is the radius in atomic units. Ann. 80. Radial probability distribution a R\nl) for several of the lowest levels in hydrogen. 485 (1926).) In order to normalize the radial functions we need the result (17) which is readily obtained from the generating function or * from Eckart s SCHE6DHJGEK. 32 36 40 B Fig. . der Phys. 1 .
The average o 2 4 ^i[63w* .gt.357i 2 (2Z 2 j 2Z . and replacing r by Zr/a* 5 6 f The average values of r~ and r~ may be found in VAN VLECK. Koy. Several of these functions are given explicitly in Table I 5 The probability of finding the electron in dr at r is 2 (nT) dr. I &.25 B. 679 (1934).3) + 51(1 + 1)(3Z 2 + 3Z . 1 s for some of R the lowest states. Normalized radial eigenfunctions for =!. this distribution function is plotted in Fig. Soc.*  =  3V3 * = 64 = 5 81V30 *r V wave 2V6 768V35 values of various powers of r for the hydrogenic functions are given in Table 2 5 . Proc. . .10) + 12] 5 72 2 3 * * In this table r is measured in atomic units.ADIAL FUNCTIONS FOB HYDROGEN 117 formula. Therefore the final formula for the normalized radial function which is normaKzed in the sense . The general eigenfunctions for any Z and arbitrary length unit are obtained by multiplying the functions of this table by Vz/a.f TABLE 2s a*.o R\nl) dr=l. A143. TABLE 1s.
We shall keep only the third term. We shall thus solve the equation i \ = E$ 9 (4) under the assumption that the ift*s and energies do not differ much from those of the nonrelativistic equation (5) which we have considered hitherto. To obtain the wave equation we take the relativistic expressions for the Hamiltonian (total energy) H=^j==l] + U(r) and for the 9 (jS=^/c) (1) momenta IJLX u. of this expression are very small (in atomic Appendix) compared to the second and regarded as a perturbation.* We shall now investigate the effect of the relativistic variation of mass with velocity in the centralforce problem. .y = pi /ov where ft is the rest mass and v the velocity of the electron. COTEELECTRON SPECTRA 35 The relativity correction.118 3. Under this assumption we may set Now from (5) ip * See the sketch in 5 of Dirac s more rigorous treatment.gt. particularly in the case of hydrogen. c==137. = V 1 1 f oo j 2 2 AL ! C Hence JE? = ac 2 The third and succeeding terms units. Then so that V] _ #2 &. may safely be jLt=l. cf. hence p~l.
with the quantum numbers m and t an eigenstate of angular momentum and obtain the radial equation In the case of hydrogen and hydrogenlike ions we rigorously..35 THE BELATIVITY COBBEOTION 119 since p 2 commutes with ( W U) we may apply p* again to obtain or to our approximation Hence the relativistic centralforce equation becomes (7) Just as in I5 we may take this iff to be Z. For simplicity we rewrite the above equation in the &.gt.lt.oo fine structure constant e 2 /#c= 1/1373. (11) . Of these it is y+ which gives our previous solutions Hence we proceed to find a solution of the form nfXr*. We set U~ Ze*/r to obtain may solve this where a denotes the c~&. Near r = oo s the solutions of this become asymptotically of which the solution with the minus sign remains finite for the energies in which we are interested.gt. and that may be dis cussed in the same way.oo. We see that for it this equation reduces to the equation 2 5 1.. we find the indicial equation whence r= in the limit c&. At the origin if we attempt to find a power series solution starting as r^.
t FBENKEL. 37.c . negative kinetic energy occur of necessity in any relativistic theory. and is of the sort occurring . 514 (1926). We shall now complete the picture of the fine structure in the absence of by considering the effect of the electron spin. E= .gt. From the picture of an electron as a spinning top Thomas* and Frenkelf have obtained a formula which gives experimental agreement. Nature. RZ 2 ( &.x?Z* n Spinorbit interaction. (1926).lt. relativistic variation of mass as a mere perturbation on the ordinary energy levels to which (13) reduce if we take the positive square root and let c oo. fur Phys. in Dirae s 5 theory of the electron.120 OHEELECTRON SPECTRA leads to the following recursion formula for the coefficients b k : 35 TMs The series lLb krk determined in this way converges as e l ^~ A r except for the _ particular values of Setting the coefficient 6 of degree $ it to terminate as a finite polynomial. as in all considerations involving electron spin. in wave numbers E 4. the value of E which gives a polynomial gives in place of the infinite series. to terms in a4 : or. THOMAS. This value of E is found to satisfy E which cause m = ~* _1. The effect of the spin in oneelectron spectra arises from the interaction of the magnetic moment of the electron with the effective magnetic field set up by its motion external fields around the nucleus. with a continuous spectrum below Such states of 2ju. 5 Their result for the spinorbit interaction energy of an electron in a central field with potential U(r) is where L is the orbital and S the spin * angular momentum. we obtain. we must in the last analysis choose the term in the Hamiltonian which repre sents this interaction to agree with experiment. (13) If we take the negative sign for the square root in this expression we get a 2 set of energy levels just greater than and converging to a limit at 2fiC 2 that point. 117. If we expand (13) in powers of a 2 . Zeits. Here. 243 . but here we may just ignore them by falling back on our treatment of the &.
m8 ) as in 5 3 2: m^ The matrix components of H1 in this scheme (nlm8 m \H l (2) are I / \ril mm s l) = Jo 2 ".45 SPmOBBIT INTERACTION 121 for the We must then consider the energy levels and eigenfunctions Q is the (relativistic or nonrelativistic) where Hamiltonian interaction. ms) and m l merely by multiplying 1 5 3 by 8(&. l m ". the first factor in the second factor contains $(l. We should ordinarily say (n I m. OK ".lt. 8. W f Jo Jo f The expression evaluated in 7 we can write* 3 in braces 3. so we may form an eigenfunction characterized by commutes H +H . the perturbation theory shows Although it is not diagonal with regard effect that the nondiagonal elements in which n s differ have a negligible on the energies since states of the same I but different n have large energy differences. Since r2 73 3 the commutes with L and 5. .Z ). H Q H . We shall use a representation in Hamiltonian without spin in which Q L 2 S2 LX9 and Sz are diagonal. I ) S(T.*Z".lt. T). The eigenvalues of fi are 3 3 8 since of spin (this follows from dependent of ms the zcomponent with S). theory in which these elements are neglected On the other hand if it had turned out that there were matrix components * This method of calculation is given to show the relation between the Schrodinger and the matrix type of calculation. This shows that the first approximation of the perturbation will be a good approximation. rf\L*S\* V m t . I. jjo = w nl . . Z .). component of L*S which was This matrix component contains a factor S(Z.Hence is just the matrix / f j o (3) This shows that our matrix is rigorously diagonal with respect to L to n.r. Hence the whole I I summand contains ^(Im8 m t Z*wmJ). ilMK V &. by sum reduces to (n I m s wiilf(r)K ms m^(n m a which is seen to equal (3). &. mA&r) L S\n f I m rf) = Sm .lt. # .7?i*7n I (* * .
Since H and S2 p . We thus consider the diagonalization of that portion of the matrix of H which corresponds to a given configuration nl. the centre of gravity of the two levels remains at mining the centre of gravity the levels are W nl if in deter weighted according to their degeneracy. corresponding to the 2/+1 values of m[Js =mfi. 2 W * represents the matrix whose diagonal elements have the constant value nl and whose nondiagonal elements vanish. The terms are designated as 2/S ( doublet S*). nl times the unit matrix. The only nonrigorous quantum number is the quantum number n. levels are 2 2 } value of j as a subscript..122 OKEELECTBOK SPECTBA 45 joining states of different I and the same n this approximation would have been very poor. S .m^L Slnlm^ll. 2 2 t Not only to this approximation.. J J 9 (6) j=l+ except 5 configurations split into two levels. the eigenstates of 2 with the values l(l+l)Jfi and but also eigenstates of JL*5.J. and J\ since commutes with these three ohservables. thus *# t P^ Pj.f From 6 3 4 we see that the quantum number j [ 2 =j(j + 1) W\ may have either of the values I + \ l . according to the I value of the configuration The from which they arise. To our approximation. and to specify an individual state frequently prefixed to these the value of is given as m a superscript. ^z W H H . are the eigenstates of eigenstates of I . the parameters are all nl Hence essentially positive.]. of 2 are not only eigenstates then. 2P. Each of these levels is still (7 + 1) fold fa andJ degenerate.f o this portion of the matrix of H may be written as (5)* W^n^^nlm. but in general. thus 2 p or 2p 2 2 2 P^. With the notation (4) &. corresponding to = Z . D3 2^. Since aU reasonable potential functions are increasing functions of r. except for l=Q 9 when we obtain only J= J. Therefore the level of the higher j lies above that of the lower. hence they are eigenstates of 2 = (Sh) 2 . is designated by adding the etc The quantum number n or the configuration label nl symbols.e. (one or) two levels into which each configuration is split are together said to constitute a doublet term. 2D. The separate 2 . where these states lie very close together. at least for hydrogen. . i.
lt. nlms mi. nl is r 3X&. This follows from the fact that near the origin the screening of the orbital electrons must become zero. With such a 3 (Ze". and hence have the form /r) 4. U(r) = 5 given at once by Table 2 : e*/r. shall return . potential just as in hydrogen. the two energy levels given by the spinorbit inter nrrn nrvn action are n . easily verified that the 1C 3 TJiis are positive as in it is . Hence the spin displacement of an S level is essentially indeterminate in this calculation.4s SPINORBIT INTBEACTIOK 123 I The eigeni/r s 3 going with these states are given by 14 6 and Table 3. R starts as r*+1 We to this point in the next section.const. the value of t. labelled by the quantum numbers l is of importance in manyelectron spectra. s on the right are those of (2).gt. so that U(r) must represent the full potential 2 due to a charge Ze. nondiagonal elements (nl*L^\Sz \nl*L^) correlation of S. . For S levels one must not conclude from (7) that the displacement due to for in this case the integral spin is zero since Z= diverges at the origin. } . This transformation 3 3 altering the phases in Table I according to 14 7. L J to Jt J2 J respectively we shall adopt as standard. (8a) (8b) where the &. using the value . where we shall speak of it as the transformation from the nlms rn scheme to the nljm scheme. #*) = fliwiO). and for I &. In the case of the Coulomb potential. + H F same order of magnitude n ". In obtaining (8) we have correlated $ with J 1? I with J 2 .gt. It will be noticed that the spinorbit interaction gives a correction of the as the relativity correction 3 5 15. so that the integrand of (4) becomes essentially 1/r for small r when 1= 0.2/ R( With this value of .
The relativistic spin displacements Ra 2 24 4n . which we have obtained by perturbation theory. Fine structure of hydrogenlike energy levels. is the same to this order of accuracy as that given by a rigorous solution of Dirac s relativistic equations ( 5 5 ) and agrees with experiment ( 7 5 ).124 of ONEELECTBOK SPECTBA nl there 45 W found we obtain for the finestructure levels of the hydrogenlike atoms the formulas l j 2 D 2 F 2 6 J tf i 3/ 2 /2 =i *3 I 3 C5 Fig.n Q\ o\ This system of levels.lt. 2P. different values of These formulas show that the two levels having the same j value but I have the same wave number er= 1 + 71 &.
Soc. becomes (2) In these equations a and the three components of the vector $ are real observables whose squares are equal to unity and which anticommute with each other} and commute with the positional coordinates and momenta. &&.55 SKETCH OF THE RELATIVISTIC THEORY 5 125 2 4 4 using Roc J /4?& as a unit 5 in each.. A is (1) which in the case of a central field. displacements given by 3 15 are indicated by the broken lines.. 5. In other words. is The characteristic feature of it is that the Hamiltonian in order that the operators d/dx operator on an equal footing with the djdt which occurs linearly in the funda be mental equation 5 2 3.. Zeits. See also a report by RUMEE. BLACKETT and OCHIAMNI. Because of the occurrence of n~4 in the unit. The wave equation for an electron of charge e in covered an electromagnetic field whose potentials are 9. It turns out that this introduces changes in the theory which are akin to the electron spin. Roy. 43. the spin is not introduced ad hoc but is a consequence of the relativity requirements. Sketch of the relativistic theory.+&. f A205EBSOH. Chapter xn. 5. etc. aj8 z f jS x a=0. Proe. 32. * DIBAC. 491 (1933). 2 for ?i = 1. made linear in the momenta In order to factorize the nonrelativistic quadratic Hamiltonian into two is found necessary to introduce some new noncommuting observables. If the energy linear factors it of the electron. W are reckoned to include the rest energy 2 by Anderson. case. 601 (1931).&=&.lt. each of these splits to form a spin doublet as in (10). but now it appears likely that these are connected with the positive electron or positron recently diglevels /^c . Quantum Mechanics. Dirac* has developed a theory of the electron in an electromagnetic field which satisfies the relativistic requirement of invariance under a Lorentz transformation.). . 699 Ihat is. } Rev. Piiys. (1933). The relativistic very rapidly as n increases. the actual splitting decreases of these levels are shown in Fig. besides the usual energy levels in the neighbourhood of + /*e 2 the theory also gives 2 This was for some time negative levels in the neighbourhood of /z. .c regarded as a serious difficulty for the theory.f In this section we shall give a brief account of the oneelectron atom pro blem as it appears in Dime s theory. Pkys. with no magnetic field. A139.
The vector p is the quantum analogue of the ratio of the velocity of the electron to the velocity of light. ! } Jt J o o J J 000 it \i i i* t It (1) may be shown (Dirac. the second = +i.lt. Nat.) Hence a and p are represented by fourthorder matrices acting on the coordinates which distinguish the (This is four components of ^ and these we write as a matrix of one column and four rows. * BEETT. near to The states ^ for this problem are required. . In fact. Sci. to have four component functions of position. Hence we may say first component of refers to a = 1. . Acad. ms 553 (1928). in order that we may find four anticommuting matrices. 14. as Breit* has shown. Proc. exactly the values postulated by Uhlenbeck iff and Goudsmit.ms = ~^. hence the allowed energy levels are near to Each quantity has the allowed values 2 pc as stated before. and the fourth 1. In problems in which relativistic effects are small the aspect first term in (2) is the largest.x = 13 m= Sz = m/i^ f JS. Sz is diagonal in the scheme we are using. the components of this vector are proportional By to the components of the spin vector of 5 3 written twice over: (4) that is. 72) that because of the & form of the Hamiltonian the electron must be considered as having a spin angular flC momentum S and a magnetic moment that the to S. the allowed values of 2 a/ttc . component to a = l.126 ONEELECTRON SPECTRA 55 1. 3 analogous to our use in 5 of ^ s with two component functions of position to allow for the spin degeneracy. We may work with a representation in which oc is diagonal and in which a and p have the forms 5 vector p x p It follows directly from the properties of the satisfies the commutation rule components of p that the 3 comparison of this with 1 3 we see that p x p is a constant times an angular momentum. the third to a = &. that is. The quantity a we shall call the of the electron.
5 a = 1 the third and fourth components of x vanish and for given by 4 8.55 Dirac s 127 SKETCH OF THE BELATIVISTIC THEORY Hamiltonian (2) commutes with J= 1 + S.vanishing by (jmZa ponents of are y ^ w. The ) determines the state except for a function of the Tlie fornls of these states are radius. The allowed values are + i) and the states labelled by (jmfcot ) which we shall denote by (j ijt(jmk&.(Z m^) may These written for the spherical harmonic 2 5. namely j\. so we may introduce a set of states labelled two possible labelling m there are by j and m.1 the first and second components vanish. are related to the x s by It is convenient now to transform (2) /}*== 1 g =r *p.tm t) (5) where states this &. does commute with the Hamiltonian and of k so its eigenvalues may serve as quantum numbers. For a definite value of j and values of a and two possible values of I. They are not suitable in be regarded as labelled by I or by is m pi* 2 form to be eigen^ s of energy since JL does not commute with the Hamiltonian. where rQ =rjr. For com a = . this becomes . The quantity whose eigenvalues we denote by k.lt. We denote such a state by xtfmZa ).lt. Since by introducing the operator the second term becomes SALS\ The last form here follows from the fact that the dyad pp = 3^ operator ( On introducing the Schrodinger ifi grad) for p.x. ). The non.
654 (1928). 4&. DABWIN. * . 11 (1928). The details are given in Dirac ( 74). The relation of the quantum number k to the ordinary doublet notation is given by the scheme: i= 1122 3 . Proc. A118.gt. .. In this equa tion the allowed values of s are where a=e2/Sc. 48.lt. 1 i.gt.1 K& 1&.* The allowed discrete energy values found in this way are (ii) the fine structure constant introduced in 3 5 9. Soc. (10) Substituting this in (2) and using (8) and (9) we find the equations which determine F(r) and G(r): These equations may be discussed in the usual way for U(r) = and Ze 2 [r by and seeking the conditions for polynomial solutions for f(r) g(r).2. Q 19 o.128 ONEELECTRON". ". Roy. The levels which lie close together are those quantum number n=s+\k\. fur Phys. for ior ff\T&. (9) will The eigen^ of the Hamiltonian going with definite values of &. ).1. z. j.. *fs( SPECTRA j 5s initial Let us now consider the action of /?r on tion ]3r has the form m&* ) In the representa cos&. = $(jmk(x.lt.*&. 5 = 0. for a definite value of the total (14) * See also GOBDON.. . of ifj(jmk^l) and tff(jmkl) which we write in be a linear combination m the form j?/ r \ iGM I). Zeits. .9 sin0e*? sin#e* ? cos# sin0e* COS0 with the aid of 4 21 3 we readily fir find that ) 4t(jmkcx...3.gt.
lt. the third and fourth components. giving Pf.i = 3. I. l + : J In actual atoms (E so f(r)~ If everywhere except very close to the nucleus. if we save the first term in the interaction. . &. (2) becomes j cOjl +m in which the dependence of a and p on the values of a is shown explicitly in terms of a vector whose components are (2/#) times the spin matrices of The first equation of the pair implies c which may be used to eliminate *//_ ifr + from the other equation of the pair to obtain as the equation for 1 o/(r) in f_ + U(r) $_ = . treat f(r) as exactly equal to 1. Df giving Df . 4 the energy levels (11) are close to H~/^c2 In the s belonging to these levels.*) we simply =P cs 9 . are large compared to the other two.Et/L. and 4 5 Replacing a . W W . 2 2 2 2 2 Pj. ^_ satisfies the for the nonrelativistic problem without spinorbit Schrodinger equation 2 *However. (11) gives. 1 c *_ cp . which refer to states in which oc = + 1. H 2/xc 1. is just what is to prevent the appearance of half of the 2 term and so preserve the needed structural similarity with the nonrelativistic theory. which i/r refer to oc = 1. W by E + ^o 2 . It is instructive to discuss the Dirac equation for the centralfield problem (2) in a way which exhibits the connection with the relativistic and spinorbit effects as discussed in 35 01 53 1.gt. In other words. to terms in so that the lack of the allowed value s = with positive k F the same system of levels as we found in 4 5 12. 0. ot . 7ZT1 (15) which U) 2 &.lt.SKETCH OI THE RELATIVISTIC THEORY 1 129 The lack of symmetry of (12) with regard to the sign of k is just such that for a given value of n we have the same doublets occurring as in the nonrelativistic theory. quantum number. giving #j. e.g. (13) and (14) show that levels of the same n and j have rigorously the same energy. expressions.lt. for n = 3 we may have $ = 2 k= 3 I. the aspect is an almost exact For small values of Z .fc=2. Besides the discrete levels there is an allowed con 2 2 We shall not have and for tinuous spectrum for f /zc ~/zc any use for the exact radial functions and so do not work out the detailed &. since (P*&.
This last term.S becomes indeterminate for S terms since the integral 1 f U (r)ijt*dv diverges and L S vanishes.c . v .lt. The 5 2 5. first term of this becomes simply /(r) p^ifi. Near the nucleus we can have ( E U) 2 &. (Here B(r ) this Hence Vc% a 3 ~ 3 2 n* the value of the spinorbit correction of S terms as given in 4 5 10 if we suppose those formulas to hold without change for S terms On the other which is . Ze z jr interpretation. as already remarked. ~ A/ * ! 13 ^ ~ 3r (16) nonrelativistic Hamilapproximation to the effect of variable mass as considered in 3 5 the fourth is the spinorbit term as considered in 4 5 The last term is peculiar to the Dirac theory and does not have a simple classical first The two terms constitute the simple nonspin is tonian. in the case of a Coulomb field. Using the value of the radial factor from 2 5 18. the third the first 5 . 2/zc and .130 OKEELECTBOK SPECTRA 55 first development of /(r) we get both the spinorbit interaction and the approximation to the relativity correction. the amount contributed to the ns energy by this term is since B(OO) = 0. the term in I&.gt.2ju. hand. gives rise to the following change in the energy by a firstorder perturbation calculation: U= is the whole radial factor R(nl)jr of the wave term contributes nothing except to S terms.gt. By a simple application of we find that fif (r) so the second term is i r Now to the first approximation Hence the equation 1 * i for 1 $_ is rr. We now see that that is simply a consequence of the approximation procedure which implies (E U) 2 &. for they function.) are the only ones for which n(0) is not zero.
GOBDOK. hence the f (r) B 2 dr is really finite. der Phys.ri (n 1)! 4(2Z1)! V w _Zl)!(rc Z)! + (1) in which the F s are hypergeometric functions and n r and nr are the radial I Z 1. cases of the formula have been written out and simplified. quantum numbers n * SCHEODINGEE. Since the results of 93 and 1 13 P 3 all J r rK(nl)R(n o l~l)dr. 92 . 1031 (1929). Ann. 927 (1926). p. 361 (1926). Hence we have shown that the approximation pro cedure for Dirac s equations when properly applied leads to 45 1I even for the energy of the S terms. Sci. f BATEMAN. as a result his equations gave the hydrogen levels correctly except in regard to the 6. Proc. S levels. Partial Differential Equations. so this term vanishes on account of the vanishing of L*S. It is of some interest to note that Darwin had discovered (16) prior to the work of Dirac but without the term in difj]dr. The evaluation of these integrals is rather difficult. Rev. Ann. Acad. 453. Eckart. and Gordonf BatemanJ has generalized Epstein s result. Phys. and n respectively. tegral above * is equal to 1) ! i)* l(n + ( (n + 1 1 ) 1 n . Intensities in hydrogen. 2. Nat. Schrodinger* calculated them by use of the generating function for the Laguerre polynomials. der Phys. f EPSTEIN. 629 (1926). According to Gordon the in . and Special numerical values of the integrals have been calculated by several persons. If we avoid using the expansion off(r) we see that so near the nucleus the quantity radial integral / (r) approaches a finite limit. 79. In order to calculate the transition probabilities or the line strengths in the hydrogen spectrum we need the matrix components of the electric are applicable to of the hydrogenic intensities are expressible in terms of the integrals moment. 12. Cambridge University Press.55 for SKETCH OF THE BELATIVISTIG THEORY 131 S states this is important because of the relatively large probability of the electron s being close to the nucleus in these states. P= er. 28. Other simpler calculations have been made by Epstein. ECKABT.
Let us now consider the strengths of the lines in the fine structure of hydrogen. de Phys. 511 (1928). we may express it in terms of the nlm8 l scheme of states in which the spin and orbital angular momenta are not coupled. I.lt.132 most fully O1STEELECTEON SPECTBA 65 5 by Kupper. ^IAXWELL. 259. 68. 700 (1930). 704 (1931). 38. where z l 1 2 (I/ 1)^). iJo * 86.* (3) KDPPEK. the latter being based on Kupper s work as revised by Bethe. . 31. j SOMMEEFELD and UNSOLD. is given in 11 8. According to the discussion just following 11 3 8. we hence.. Phys. Zeits. this quantity is really independent of the spin and so.n given by 7 45 dependence f in terms of the (nl\P\ril in terms of the quantities (nl Lj\P\n 3 of these on and. Rev. 113 (1927). In this case the integral is easily found to have the value %ann*l*. Using 9 3 so for a non vanishing component I must change 1 1. fiir Phys. 442 (1933). ed. SAHA and BA^EEJI. r 11} dr foos0 Jo we integrate l over 9 to obtain c == r (nlms mi\Pg \n Similarly lmg raj)= (n I s V4? t \ 2 rR(nl)R(rill)dr* J o s l l m m Pz \n m m^ = 0. Arm.gt.. The they are expressed 1). but is important in the Stark effect (Chapter xvn). 38. Since z = er cos# we have m P (nlm$ m^ Pz \n ll m8 m^ f = e \r R(n 1) R(n Jo 3 Using 4 2I. 6. Zeits. does not occur in the intensity problem in hydrogen.} We could go at this directly by calculating the matrix com 5 ponents from the eigenfunctions (4 8): this would provide ample exercise in calculation of matrix components. t BETHE. so jz = The strengths of the lines n 1 2 L^ . 8. J o (2) This integral. 1664 (1931). SUGIUEA. &. by one unit.f The expression (1) is not applicable for n = n. BECHERT. In applying 1 1 3 we identify J^ with the electron spin. Handbuch der Physik 24/1. der Phys. fur Phys.* In Table 3 we give some of the most important formulas for special series and in Table 45 numerical values for the most important values of the quantum numbers. 527 (1928). finally. 36. Jour. 2&. SLACK. so j^ = f and JF2 with the orbital angular ll 2 (L l)^/ are momentum. But it is more instructive to work them out as an application of the general results of Chapter m. Rev. 237 (1926). Ann. der Phys. as in 11 3 9. Phjs. of course.
the ensemble of the * in atomic units for n~ 3&. 2 . 2s 3* 4s 5s 2 83 ?t 2 .1) dr J n f ^ n.4) 2n ~ 10 (7i Fofees of (re 1) R(n I.1) dr in atomic units.9)(n .gt. Values of\ r L/o E(n 1} R(n I. J .INTENSITIES IN HYDROGEN 133 4 quantities occurring in 7 5 are thus completely expressed in terms of over the radial eigenfunetions.3) 3n.4}{%2 .^ =2 r* I TABLE 3 s nl np Jl Is .27) 2 (n nd w f S) U U U TABLE 45 . the integrals The calculations may be exemplified by a detailed consideration of the The line strengths in the fine structure of r Ha .4){n .9 { .
gt.gt.% a (6912) ( (b) (c) In the same way. and the strengths in atomic units. The relative strengths of the different doublets are not so simple since these involve different radial in tegrals.gt. 2 2 = 2..2 21 3 5 5~ 12e2 a 2 8(3 j) 2 2 8(3 Pj^2 $j) = L 2 2 = 1.107 IV2 sec". For a particular 7*3. 3 2Z}&.&.gt.2 2 2 /5j&. Using 11 3 8 we have is 2 2 65 TMs doublets .gt.2 2 2 P) = 0536 (6) 2 2 (d) (e) (f) P&.134 transitions. . e a Then the numerical coefficient probabilities. This is a special case of a general result for multiplets discussed fully in 2*.2 2 P and 3 2$&. (d) (e) (f ) (g) Pf)=L = S(3 P^) 5.gt.216 3 7 512e 2 a 2 8(3 5j^2 Pj) 2 2 S(3 Pf) = 2.gt.2 2 2 768) 2 2 . It is .2 600) (4) 800) 75) ( .gt.2 (3840) (1 ( Pf~&. D&. 3 2 P&. in this table give the relative figures in parentheses at the right 14 2 2 16 6 of each Iine 3 the common factor being 2 3 5~ e a . 1 .gt. OKEBLECTBON SPECTRA made up of three 2 2 P.2 3 5.O O ==.2 2 1 2 2 24 7 P) = 9.2 A(3 A(3 A(3 P&. 9:1:5 and 2:1.2 ( 150) It will be observed that the relative strengths of the lines in the same doublet bear simple integral ratios.2 2 $. in 743 becomes ^4^402  eg a 2 = JaV1 = 2662 x 10 9 sec".gt. (a) S(3 2 D&. j&. The absolute values of the transition probabilities involved in the first Balmer line are therefore (a) 8 2 2 = A(3 P) 0643 x 10 2 2 A(3 D^2 P) = 0.2 (g) #) = 0223 2 = 0223 #j) 2 = P) 0021 2 = j*2 Pf) 0042. we find for the strengths of the lines. strength transition next consider the theoretical values of the Einstein The We A line these are expressed in terms of the convenient to express a with the Bydberg constant as strengths by 2 2 unit. (5) where oc is the finestructure constant and r the atomic time unit (see Appendix). S(3 Df&.gt. (3 (3 (3 Df:P:2 P) = 2 Df :P:2 Pf ) = 2 2 D:P:2 2 From Table hence from 35 7 45 and (3). 1 (b) (c) A(3 A(3 2 Df&. (ScZjPjSj?) =6 a 2 2 22238 J.gt.gt.
The 3 2 $2 2 P will be emitted much longer time than the others on account of the greater lives of their initial states. while the A s are not. M but 3p can go to Is as well as 25. which are proportional to the strengths. but the intensity ( ratio of the two lines is 2: 1 because the A s have to be multiplied by the . B) B the sum being taken over all of the levels B of energy lower than A. The atoms are subject to disturbing electric fields and to collisions which tend to produce a mobile . relative intensity of the lines are Such an experiment has never been performed. P the ratio e due to a factor in the statistical weights while in the second it is due to a factor in the transition probabilities. and so the mean lives [the reciprocals of the total transition probabilities kA *=k(nl)] of each level of the three initial con figurations have the values Configuxation 3a 3j? 3&. Since the mean lives of the two component levels of 2 P and 2 of different for a L value does change with. . The number of atoms in any level A after time t would be reduced by the factor e~ k^ where JcA = SA(4. give intensities. The sum of the two transition probabilities from 2D is equal to the single transition pro 2 bability from J5f This is a general result true in more complex spectra 9 2 ). the 3s and . Suppose we have an experimental arrangement whereby at 2=0 equal numbers of atoms are put into each of the 18 states belonging to n = 3 and that the atoms are not subject to any external disturbance.gt. In the states can only go to 2p.lt. for appears so that in both cases the intensity ratio is 2: 1 although in the first case it is statistical 2 weights of the 2: 1 initial levels to 2 $&.gt. We may calculate that j) A(3 for either 3 2 Pf or 3 2 2 P~I 2 = 164 x 10 8 sec1 Pj .2 $ are equal. Then the relative intensity of the different doublets would depend on the time after the excitation at which the observation is made. The actual studies of the made with an electrical discharge where the excitation and emission reach a steady state.2 Mean life 160 xlO. But the relative intensity of the lines originating in levels Z&.8 sec 054 x 1G~ 8 sec lo6xlO~ 8 sec are equal the relative intensity of the lines originating from them will not respectively. particular case of the first Balmer line. in the transition probabilities themselves. .1)A. On the other hand. time. are thus symmetrical with regard to initial and final states. The quantities (2/4.65 INTENSITIES IN HYDBOGEIST 135 The values illustrate several important properties of the A s. change with time. The two transition probabilities in 2 P.
corresponding to a total transition probability k(n) which is a weighted average of the individual total transition probabilities: TABLE 5s. Transition probabilities and mean lives for hydrog&n.gt.. * This is ^ 2 A(y &. .136 ONEELECTRON SPECTRA equilibrium between the states of differing I and the same n. n Zj ). a quantity which is independent of the value of j. The result is that when the disturbance is sufficiently great all of the states of the same n have the same mean life.
Let us consider briefly the relation of the foregoing theoretical results to the 5 experimental data.INTENSITIES IN 5 HYBEOGEN 137 In Table 5 some of the important values of the transition probabilities for hydrogen are given together with the mean lives of the individual states. is the reduced mass ( I 5 ). 7.Angstroms) Final 1 Name Lyman Balmer Pascken Brackett 2 3 4 The Lyman infrared. the term values p__#2 R TT ~ ^H p T^^ * (}\ A \ / is known as the The quantity obtained by using the Eydberg constant for hydrogen. reduced mass of the electron with tespect to any other nucleus is known as the Rydberg constant for that atom and we write R^ (or R) for The universal constant RH occurring in this expression the Rydberg constant obtained formula. of lines * by using the electronic mass in this The spectrum of hydrogen divides itself naturally into a number of series . We have found in 2 that the energy levels in hydrogenie atoms are given by In spectroscopy we are concerned directly with the wavenumbers of the lines which are obtained as the differences of where /x. and in Table 6 5 are given the average mean lives for several values of n. Average hydrogen mean life lf&(n). the Balmer series is the pro hydrogen spectrum. TABLE 6 5 . The is discussion of the experimental results of intensity studies in taken up in the next section. Experimental results lor hydrogenic spectra. series lies minent feature of the visible deep in the ultraviolet. the other two are in the . each series being the set of lines having a common final n value: Wavelengths (.
: Thus for the first Balmer line. J. Phys. 503 (1932). the observed pattern in a Balmer line is that of two close groups of lines with this separation. f HOUSTON. KracHNER. Rev. Ha . 1. j PEHRY and CHASYEE. the ratio of its mass to that of the electron. 975 (1931). 608 (1927). Phys. UBEY. =10973742 The smallness of the difference between R H and R He means that some Hell lines are very close to certain HI lines. For the final states of the Balmer series in hydrogen Aa= 0365 cm1. 512 (1933). in the Hell spectrum. 12. Ann. Chem. Phys. Taking this in combination with the Faraday constant in electrolysis. it is possible to measure the mass of the proton in atomic units. This effect was the means used in the discovery of the hydrogen. Rev. while the states of n = 4 in ionized helium have a splitting three times as great. good agreement with the recent precision measurements on free electrons in deflecting fields by Perry and Chaffee ? and Kirchner. * BIBGE. the distance of the extreme components of the nth energy level being 5 according to 4 12. data made by Birge* led him to adopt the values is 7s The Rydberg constant critical one of the best A R H = 109677759 R He = 109722403 Rco 005 em. Rev.138 study of all the ONEELECTRON SPECTRA known atomic constants. 1. 464 (1932). 8. The relativityspin structure for hydrogen and Hell is very fine. Since the higher levels show a much smaller splitting. . 1 1 By making an accurate measure of the the ratio of the nuclear masses as separation of these lines and taking known from the chemical atomicweight determinations. deuterium 5 by is This in Urey. 904 (1930). that is. Phys. BEICKWEDDE and MUBPHY. The most accurate study of this kind has been made by Houstonf who finds JfH //t= 18382 18. 1 (1929). Mod. 3D. = R H I__1 is and close to it.J Thus the theoretical effect of the finite mass of the nucleus is fully verified. isotope. the value of e/jLc for the electron becomes e//Lt = (17602 7 00018) x 10 EMIT.1 005 006 . 1. 40. der Phys. Rev. Phys. 36.
Acad. r~i^7 ^fcroIX * SOMMEBFELD and UNSOLD. theory of the Doppler effect. see also SLATER. 3 . 3 where the ordinates are proportional to the relative intensities of the lines as calculated in the preceding section. 36. 259.EXPERIMENTAL RESULTS FOR HYDROGEKIC SPECTRA fine structure for several lines. dcr. fur Phys. The theo retical 5 pattern for this line is shown in Fig.if moving toward the observer with speed u will appear to emit radiation of wavenumber a where is according to Maxwell s law for absolute the fraction of all atoms whose speed toward any direction temperature T. Proc. 11. . 732 (1925). 38. so the experiments are air. The broadening of the velocities of the lines by the Boppler is effect due to the thermal atoms in the source performed with the discharge tube immersed in liquid considerable. According to the t ^ s Pig. an atom emitting wave*mmber o. Zeits. Theoretical fine structure of Ha . 237 (1926). If the distribution of velocities is between u and u+du is given by 2rrkT hence the intensity of radiation between a and a+da is proportional to / mc a ^dr. Ha . Sci. 139 Sommerfeld and Unsold* have discussed the modern interpretation of the We confine our attention to . Nat.
452 (1933). Handbuch der Physik. Phys. since on the original finestructure theory of This is Sommerfeld this component is forbidden. Rev. fur Phys. exactly what was found experimentally. CABST and LADENBTJBG. They conclude that the oscillator strength ratio is between 466 and 5*91 for H a are :H0. SHAKE and GRACE. j SNOEK. Its presence therefore lends support to the present interpretation of the finestructure levels. KENT. 45. fiir Phys. HOUSTON and HSIEH. The uncertain element here is the amount of correction for negative dispersion due to atoms in the n = 3 and n = 4 states. 192 (1928). EANSEN. 263 (1934). proportional to the absorption. 52. Phys. Zeits. 600 (1928). Rev. 47. if T is expressed in thousands of degrees and atomic weight units. Archives Neerlandaises. The relative intensities are found to depend somewhat on the discharge conditions.* . so the width of the lines is comparable with some of the intervals in the pattern.140 ONEELECTRON SPECTRA 75 Numerically.. 2&.(f ) will produce an asymmetry on the curve produced by (c) f (d). 45.! The relative intensities of the absorption of the first three Balmer lines has been studied by Snoek.lt. WILLIAMS and GEBBS. 78. a~0*07 cm*1 . Phys. 50. for the two finestructure groups arising from the two initial levels. Rev. Utrecht (1929). 266 (1927). 24/1.gt. 164 (1929). 48. Phys. 475 (1934). Rev. ed. m is expressed in The liquidair bath does not prevent some warming of the gas during the discharge and the observed widths correspond to a temperature of about 200 K. der Phys. With this in mind we expect that (g) will be too weak to show. we see from the foregoing figures that the * The principal papers are. 12.* Especially important is the occurrence of (e) + (f). t See BETHE. SPEEDING. Ann. J He found the relative values to be. a/(7o== 958 x 10V5&. 38 (1935). while those for absorption from the 2si are 100:24:99.654(1928). H a :H The theoretical ratios j3 :H y = 100: 188: 74 (from j = f ) (fromj==). that (a) and (b) will be lumped together and that (e) 4.. Diss. 30.. Zeits. 558 (1925). Since the oscillator strengths t . 100:202:85 for absorption from the J = f or from 2p are 100:176:63. The experimental values from J=f are in good agreement with the theory and those from j =  correspond quite closely to a mean between the theo retical values for 2s and 2pi The same question was studied by Carst and Ladenburg by measuring the amount of the anomalous dispersion around H a and H^. TAYLOR and PEARSON. that is.
75 EXPEBIME3TTAL BESULTS FOB HYBBOGEOTC SPECTRA 141 theory gives 416 if all atoms are in the 2s states and 568 if all are in the 2p states. General structure of the alkali spectra. 8. . An interesting absolute measurement of the life time of the excited states of He + was made by MaxwelLf He excited the helium by electron impact occurring in a narrow electron beam. f MAXWELL. 62. The mean life is fa that of hydrogen since the frequency cubed varies as ZQ and the radius squared varies as 2~ 2 inthe expression for the transition probability. Theory 355 34 32 H^/Pa Hy/Pp (4&. so for neutral atoms it is of the form 2 e2/r at large distances from the nucleus and is equal to (Ze /r) + C at small distances. to a good approximation. fur Phys. * OKSTSTEIN and BUBGER. 38. Rev. while the theoretical value is ! 17 x 10~ sec.gt. 1664 (1931). The departures indicate that this is not the the case and that there must be an extra supply of atoms in/ states since these contribute to the Paschen lines but not to the Balmer lines. When for maximum number is we speak of these as 6 forming a closed shell ( 5 ).gt. beam because of the presence of a controlling longitudinal magnetic The ions move various distances in the transverse field before radiating. For the n = 6 states of He + he found a mean average 8 8 life of (1* 1 02) x 10~ sec. shall formulate the In the next chapter we electrons in the field of a nucleus and shall problem of the motion of see that there is a limit to the N number of electrons of each a given value of nl the nl value that can occur in the atom. just that of a single electron moving in a central field ( 10 6 ).3) 26 25 (5&. Pfcys. 636 (1930).gt.2):(63) 20 The theoretical values are based on assumption that each initial state has same number of atoms in it. The results were Obs.2):(4&. while the average according to statistical weights is 537. Zeits.2):(5^3) H 5 /Py (6&. where G is the constant potential at the origin due to the electrons in closed shells. If we have an atom in which all the electrons but one are in closed shells. This effective central field for the extra electron outside closed shells is the resultant field of the simplified nucleus and of the other electrons. present. Ornstein and Burger* studied the relative intensity in emission of Balmer and Paschen lines having the same initial states so as to eliminate the un certainty as to the number of atoms in the initial states. the mutual interaction of the electrons is greatly and the energylevel scheme is. By studying the spatial distribution of intensity of light he was able to infer the mean lives of the excited atoms. corresponding to the probability distribution of life times. The excited ions produced were drawn out by a transverse electric field which did not sensibly affect the original electron field.gt.
". the P to n = 59. which is called the quantum defect. These facts are illustrated in Fig. The only doublet terms which have . is almost constant in a particular series (constant I. the difference is greater for smaller values ofZ. The S series is known to n= 14. of A with n along a series. 4 Energy level diagram for sodium. the energy corre sponding to each nl is lower than for the corresponding hydrogen state.142 Since this states is ONEELECTEON SPECTRA a centralfield problem. The dependence of ri* on n is almost linear.been resolved are the first seven of the P series. since the difference between the potential energy and the Coulomb law is greater at small values of r. This shows clearly that the/ terms even in Cs are approximately hydrogenlike although all others in Cs show large displace ments from the hydrogenic values. 8s I5 and classify the numbers n and I. Moreover. and the F to n = 5. . where R is the Rydberg constant for the atom in question. 5 varying n) of terms. The angular factors will be those corre by quantum we may apply sponding to precise Tallies of angular momentum. It is effective convenient to discuss the empirical data quantum number n* defined by by introduction of the R/7i* 2 . Since the potential energy at each distance is less than in the simple Coulomb law. so that the difference (n n*) = A. (I) HYDROei/t UK 65 s Fig. the D to n = 15. 5 where the empirical values of the quantum defects are plotted for the various series of the alkali Each plotted point on this scale is big enough to cover the variation spectra.
from constancy is proportional to the term itself which means that the quantity represented is contained implicitly in the it. as in the old theory.143 GENERAL STRUCTURE OF THE ALKALI SPECTRA The much smaller dependence of A on. (Ritz). A1III. A(wZ) minus the a function of n.lt. Other special formulas which are in use are (Ritz). the former being those which extend into small enough values of r that the field has a nonCoulomb character.). and Si IV is plotted against Z . 5 . Therefore we expect the terms to become more hydrogenlike as Z increases in such a sequence. This means that the &(nl) tend to zero as Z Q increases. Z A 2 (2) as the equation defining n*. 6 for several typical A for the first member of the series. Mgll. n in a given series is shown in s series. formula which represents In considering the variation of the oneelectron spectra along an isoelectronic sequence. 7 where A for the s and p terms of the elevenelectron sequence. (Hicks). two for singlycharged ions. The various empirical formulas for the terms in a spectral series which are in use among spectroscopists may all be regarded as formulas for the dependence of n* or A on n. The simplest is the Rydberg formula which simply regards A as a constant. Variation with I and quantum defect in alkali spectra. This is illustrated in 5 Fig. Nevertheless the states of the higher I values penetrate less. as shows the difference. it is desirable to take account of the large dependence on the degree of ionization by writing s of Fig. etc. This distinction is not so sharp in quantum mechanics as all of the eigenfunctions have nonvanishing values near the origin. In the orbital form of the atomic theory there was a sharp distinction between penetrating and nonpenetrating orbits. where ZQ is the net charge of the Ion around which the single electron moves (one for neutral atoms. It will be noticed that decreases in the s A increases with n in the d series and and p series. In the first of these the deviation of A &. For the nonpenetrating orbits the old theory gave an explanation of the slight . For higher values of the nuclear charge in an isoelectronic sequence the departure from the Coulomb law caused by the inner group of electrons is smaller in proportion to the whole potential energy. This Fig. Na I.
For fields not deviating too greatly from Coulomb interval to be given roughly we may expect the value of the doublet by 4 5 11. O J in alkali spectra. is polarized by the field of the outer electron. 2 a doublet structure caused by the .144 OKEELECTEOK SPECTRA 85 departures from hydrogenic values by assuming that the core of the atom. composed of the inner groups of electrons. this gives a fairly satisfactory account /2r*&. .0 j O". This . I7 _ . the polarizability of the core. which can be written in the form : 5822  cm~ for the alkalis. (3) If this form has any kind of approximate validity we expect . the level with higher j value is higher in energy.at of the lowest term of the series order fields is called normal. .cte2 where a is of the deviations. of course. The difference tween the quantum defect of to which it belongs is plotted numbers of these terms.gt. spinorbit interaction discussed in 45 Since nl is essentially positive. i. so that the electron s motion was perturbed by an interaction term.gt. z_. The 2 alkali spectra have. f i &.e. Using values of a inferred from ion refractivity data.
in their values so that hi the case of tt Rb . as abscissa for alkalis. In the case of Cs the intervals for = 13 and 14 take a similar sudden jump upward and become nearly equal P intervals for the same T& S. the doublet interval as ordinate and n . The approximate variation as i/% 3 is shown in Fig. For example the D series of both Rb and Cs show a remarkable discontinuity &. on logarithmic scales. to the j^ t 7 s.1 which pected value of about 1 is twice as big as the interval for n = 5. . jump from an ex 1 up to 6 cm". the first member of the series. Variation of doublet interval with n in alkali spectra. SPECTRA 145 that the doublet Interval will vary about as 1/n The absolute value of the Intervals we do not expect to be given at all by the formula. 8 5 in which Is plotted. 8 . Variation of he Nalike A in isoelectronic se 2 4 5 6 7 8 9 (0 il 12 & 14 5 Fig. From this it is clear that in the . for =11 the interval takes a cm". the variation also is aH the known doublets of the main 3 like 7i~ or ^~ 4 but the diagram shows some striking exceptions.GEKBBAL STRUCTURE OF THE 3 .lt.". thus far unexplained.
for Phys. The separations.TJgAK and BOWEN. this tends to make for a p state greater than for a d state in a larger ratio than for hydrogen. the interval for 2p is known and agrees quite well in absolute value with the value given by the theory for hydrogen: Various somewhat empirical modifications of the doublet interval formula have been proposed. however. where 8 f LAOT&. expect them to be less than this in the alkalis. That those expectations are borne out is shown in a table for Cs: 10 11 12 13 14 0078 0115 0135 0182 0164 0192 0096 0964 102 The anomaly of the last two terms. already mentioned. Landef from an analysis of the classical penetratingorbit picture proposed replacing Z* by Z\Z\^ where Q is the net ion charge as in (2) and Zi is an effective nuclear charge in the inner region to which the (3) Z orbit penetrates. We turn now to the relative intervals of corresponding series. 23. 764 (1924). 209.gt. terms in D and P We According to the hydrogen formula these intervals should be as 1:3. Another modification that has been used a great deal by Millikan and Bowen J regards the entire orbit as determined by a Coulomb field of effective nuclear charge (Z S). Bell. are very small: The first order perturbation theory is is quite inadequate for explanation of this inversion since essentially positive. Bev. that is. Phys. Zeits. . the level with the higher j value has F the lower energy. 24. etc. But terms are inverted. j MTT. 233 (1924).&. indicating that the in the case of Cs it is definitely known that the usually small. 25. is here striking. and replacing nz by n**. 46 (1924). In the case of the isoelectronic sequence Li I. since the p eigenfunctions have appreciable values for smaller values of r than the d eigenfunctions. Since the deviation from the Coulomb law is in the sense of stronger fields than Coulomb at smaller distances.146 Data on doublet interval is ONEELEcmoisr SPECTRA intervals for 85 doublet F series are scarce.
The theory goes exactly as for 5 hydrogen ( 6 ) with these integrals replacing the ones based on hydrogenic eigenfunctions. of the 2 9. Intensities in alkali spectra. 4. TEUMPY. This value* is observed for the first doublet in Na and K. although it is 20 for the first doublet. Calculations of the f values np of Li have been made by Trumpy f using on a Hartree field ( 814 ) The ratios of the f values of successive doublets were measured by FilipovJ by the anomalousdispersion method. Most of the experimental data is expressed in terms of effective f values for the unresolved doublets. which was already calculated in our discussion of hydrogen. figuration nZ . t The experimental data are summarized by KORFF and BREIT. 471 (1932). In Table 7 the experimental values of Filipov Pliys. Mod. The explanation of these departures. . 526 (1931). For Rb the ex series ~&. they are found (third row in the above table) to be nearly equal to two.gt. t FILIPOV. defined in a way exactly analogous to For the doublet of wave number a connecting the lowenergy configuration nl and the higher con the definition in 9*14 of the f values for lines. Zeits. Key. The first point to be noticed is the 2: 1 strength ratio in the principal n 2 P 2 $. 720 (1930). we may use the eigen functions of this field to calculate the radial integrals J o r r(nl)R(n ll)dr which are needed for the intensity problem. is considered in515 . In the older theory the formula (3) was derived as a relativity effect and therefore should have applied to the interval between s and p terms rather than to the P interval. fur Piiys. 136. If one chooses values of S to fit the observed 2p intervals in the Li I to OVI sequence. due to Fermi. perimental ratio for the second doublet is 2*5 while in Cs the ratios for the second and third doublets are 40 and 47. 69. . Zeits. 66. of the first * 5 to the second doublet.nl) I where S is for the principal series 25 radial eigenfonctions based the total strength of the doublet. The striking thing is the very large ratio. Next we consider the relative strengths of the doublets in the principal series. 61. After tion we have found a central field which gives a satisfactory representa of the energy levels of a oneelectron spectrum.85 GENERAL STRUCTURE OF THE ALKALI SPECTRA 147 represents the amount by which the full nuclear charge is diminished by screening of the field by the inner electrons. This puzzle was solved by the interpretation doublet formula as due to the spinorbit interaction. 54 (1930). which is a reasonable value. = 1 l*\$(n l ~~ . fur Piiys.
Monthly Notices B. PBOKOFJEW. ibid. 61.A. f values in the Li 2s . 86. Zeits. . and A(4p*4a) = 155 x 10 8 sec". Sugiura s method is similar. SUGTOKA.).1 . 458 * (1929). fur Phys. HIKN~E.148 have the OKEELECTEON SPECTRA 95 are given as calculated from the measured ratios assuming the first one to theoretical value calculated by Trumpy. Zeits. cit.np series. The experimental ratios were measured by Filipov and Prokofjewf and as to. t FILIPOV and PROKOFJEW. 85. 4S 495 (1927). 58. fur Phys.S. 8 (1925). we have given in the last column the values obtained by using H hydrogenic radial integrals together with the Li frequencies in the theoretical formula.* ProkofJew s method of 14 obtaining the central field is discussed in 3 . 54 (1929). 84. 111 (1924). the table for Li have been reduced to absolute values by assuming agreement with Trumpy s calculations for the These are given in Table 8 5 The small inset table gives the values by Prokofjew for several other doublets. TABLE 7 s. Ga II using The values are for 14 eigenfunctions of a field determined by the method of 3 of interest in connection with Milne s theory of the support of calcium in the solar chromosphere by radiation pressure. Trumpy used a Hartree field. 56. j ZwAAtf. TRCMPY. To show how much the values are affected by the departure of the Li eigenfunctions from the functions. as calculated series in and Eb are given in the report by Korff and Breit has calculated the spontaneous transition probabilities Zwaan 8 1 A(4p*3d) = 013 x 1C sec K (loc. 255 (1929). Biss. Utrecht. Phil. Mag. Values for the principal series of Cs (for which no theoretical calculations have been made) and of the ratios of the first two doublets of the principal first line.been made in dependently by Prokofjew. 354 (1924). Trumpy and Sugiura. 1929. Similar calculations for the 3s np series in Na have ". .
is for a particle of charge +e. DABWEN. where Jtf euxlA. electron may be written (1) The effect of the magnetic field on the orbital motion of the electron is best = Haniilobtained by using the vector potential A. SPECTBA series. Now since p= fftgrad. effect. Proc. (Note that their development f See CONDON and MORSE. 264 (1928). Zeeman. K.TTATT in tUe. 149 NaZsnp 10. Zeits.iffy div4 . 263 (1926). in place of the term &. fur Phys. Soc. The . AT. Roy. A118. pp. Quantum Mechanics. using a formula of vector analysis. = . i we obtain. 3 the spin hypothesis ( 5 ) an electron has a component of magnetic moment of magnitude + eS/2/xc in the direction in which the component of of magnetic a is %K. giving which produces these displacements con patterns. A115. The interaction energy from the spin of the electron and that arising sists of two parts.e in the field of potential A is obtained by tonian for a particle of charge the momentum p in the Hamiltonian for the writing p f (ejc)A in place of 2 /2^ we have case without the magnetic field. 1 (1927). t Then.ifi drr(Aifr) = . 2627. that arising characteristic Zeeman from motion. the energy levels are split into several components.ift^grad^ = A*pff * HEISENBEKG and JORDAN.95 INTENSITIES IN TABLE 8 5 f values . 37. DARWIK.) . Q. Since the energy of particle spin angular momentum the interaction energy of the magnetic is in a field moment its orbital On M ^ M%^ .* When an atom with one valence electron is placed in a magnetic field.gt. C. ibid.
hence curL4 =3if. 200. /z is from 10. so that divA = 0: ".000 gauss. is an energy which may easily be limit of spectroscopic accuracy in the cm1 On the other hand. since the visible is of the order of 0001 . Note that this is 2?r times the o as usually defined (the classical Larmor f frequency). and the first term of (2) ~065 x 10~ 5 atomic units of energy 15 cm". Hence the energy due to the magnetic field may always may be written as this For a uniform magnetic terms in magnetic (2) field 3%?. (5) arising from the interaction of the atom and the mag diagonal in a representation in which Lz and Sz are diagonal.e. In atomic units (see Ap = 1. from 06 to 18 x 10~3 atomic units. This measured spectroscopically. even if we take^ as . v (3) } 2/iC When field this is added to (1) we obtain as the whole effect of the magnetic (4) the energy In particular if we take the z axis in the direction of energy becomes ^ this interaction where o is a coefficient proportional to the magnetic field strength Thus the energy netic field i. the second is is about the highest field anyone has ever succeeded term represents an energy of only 00002 cm1 This magnitude certainly at present undetectable. Similarly div4 =0 as required. in the representation 4 5 2. is * To show that this represents a uniform magnetic r) = field ^. Hence weshaEconsideronly the firstterm of (2). i. r and p for an electron are of the order of 1. ^ . The third term is and the fourth 3^. The usual magnitude of ffi in Zeemaneffect measurements thus far used in the laboratory.be done). c= 137.000 gauss (which in using). e= 1. The larger of these values gives . we may take A = \(^f x r). the first two terms are zero.e. 1 . this interaction Whenweset4 = becomes Ap = * \ic ~^f x rp = ^^*r x p = * * 2jjLC &!*.000 to 30.* We shall now make a rough calculation of the order of magnitude of the which will show that the second is entirely negligible for all fields pendix). we have Since &f is constant.4~09 x 10~ 3 atomic units.e.150 if OKEELECTBOK SPECTRA as 10 5 we clioose A a solenoidal vector (i.
. 1 as the magnetic perforation caused .* The accuracy with which cm". In the case in which the Zeeman splitting is small compared to the spin on each of the two levels doubling we can consider (5) as a perturbation 2ZM41 ". the splitting being proportional of the value of the total quantum field. this formula holds for by a all field * Not the accuracy of our estimate of 15 of 30. (8) 2Z The factor + 11 is ~T". This derivation holds Ztb A 0. We must thus calculate the M matrix components (nl*Lf\H \nl*Lf) for the different degenerate states 5 of the level nl ^Lj These are easily obtained from 4 8: .105 Weakfield case. and being independent ^ 4 8 represents the eigenThus. a given I. gfactor. A table of yvalues is given below: gvalues for doublet spectra. n+i 2 * f * H * (8) is t In terms of wavenumbers the displacement given by (9) ^ is in gauss. known as the I Lande &. each level is split symmetrically s of the components magnetic number n and of the atom in question. This matrix Zeeman of the different already diagonal so that the displacements are given by level 2 Li components of the is . the level of higher j is more widely split than the level of lower j . ZEEMAN EFFECT 151 obtained by the spin interaction separately. . 5 for 5 levels as well as for those with 5 to the into 2jf 1 equally spaced states. to the accuracy with which of the spin doublets. *S *P  2 D f *F 2 # *B H^i where . The interval between the states after which depends only on I and j. for weak fields.gt. For splitting is determined completely by g.000 gauss.
that in the spinorbit.(wyrajLS wynj) = mzras 3 we note that because of the (cf. pared to the spin interaction. We have been considering the case where the Zeeman effect is small com the other extreme. + 2) + ( two ways of obtaining : . which may or may not split the component. . affairs is This state of known as the PaschenBack effect.152 doublets of all OKEELECTBOISr SFEOTEA oneelectron atoms 10 5 was early discovered experi one of the methods mentally. Of these the two highest and the by . components corresponding to the 2Z f 3 possible values. . two lowest are of m + m 5 = Wjh2ms ). diagonal and the matrix of 3 shall again consider just the matrix for a given nl.1) a given value of (m^ f ( 2m. the eigen functions in this case being those labelled by The transition case. that the spin splitting is negligible compared to the magnetic splitting. of obtaining e//i is by the accurate measurement of this Zeeman effect. In this case we start with the degenerate configuration nl and the system of eigen where the magnetic field is so strong. (m. spinorbit and magnetic perturbations simultaneously. and m . mz In order to in which case the eigenfunctions are labelled by s and between these two extreme cases we must apply the obtain the transition which the magnetic interaction is small compared to in which case the eigenfunctions are labelled by j and m.J) are matrix will split up according to m. ) (11) We use the fundamental system which the matrix of HM is of eigenfunctions labelled by nlmsm t . Z. From 7 3 we see that this = I + J and (1 4. We shall now consider the spinorbit interaction so small. that in which the magnetic interaction is large compared to the spinorbit. and is expressed by Preston s Rule* Indeed. Hence each configuration is split symmetrically into 21 + 3 equally spaced (Z f 1). or functions ^(nlm/n^ in which HM is diagonal. while the others are doubly degenerate corresponding . We have been able to determine very simply the Zeeman splitting in two extreme cases. See 2 16 .+^)^msm = ^o(m+ms ). the nondegenerate components represented by fr.. 7 3). so that each state is displaced by the amount m#n tf . . Z + 1. treating H!+Hv^(r)L*S+o(Jz }S3 as a perturbation.) (mz ) f ( 1 ). in 5 1 is given by 4 3. ( to the nondegenerate. The magnetic energy z) is then given (10) (^^m^o(J. and ions The strongfield case PascJienBack effect. The values H We m * This rule applies also to atoms with more than one electron outside of closed shells. For the degenerate components in 7 3 3 there are no matrix components of L*S joining the two 2 If we now superpose a small spinorbit interaction we get a displacement for S(m 5 m ) states.
this corresponds to fto/ = 916. 1 . s energies corresponding to these states are obtained immediately 2 ZEEMAN E1TECT way. we obtain Here which agrees with the weakfield case as given by (8) and 4 5 7. The complete transition (12) is plotted in Fig.t*l (I + 1)}. (12b) represents the magnitude of the spin perturbation while Ho represents the magnitude of the magnetic perturbation. The best experimental data is 2s*S. so large. 2 P term. which is not of sufficient accuracy to be fairly reduced to term values.1 ( = f). is by plotting the line the 2 P of Fig. The broken lines on the complete Zeeman effect are furnished the work of Kent* on the Li doublet A6708. For most doublet spectra the doublet interval is so large.10 5 realizable in just one Hence the from 7^3:  respectively. which arises from the transition by 2p 2p_&./. 95 for the case of a &&. the 2p 2 P has a splitting of only 0338 cm. that the highest utilizable magnetic fields will correspond to only small values offioj^i hence a good PaschenBack effect is not obtainable.gt. a value even beyond the limits of Fig.gt. 9 5 . 9 5 and pattern which should result from a transition between The best way to * KENT. i..e. and since fio = 4670 x 10~ Jf 5 cm". 337 (1914). m= i ^ ^ For the other values of m we obtain the secondorder secular equation: which has the two solutions . J. compare our curves with Kent s data.200 gauss. namely with m =  153 1. Astroptys. the ratio of magnetic The splitting is plotted in units of as a function of at the left are given by (13) while those to spin interaction. If we neglect we obtain =  which agrees with the results obtained in the strongfield case. . at the right are given by (14). If we neglect 2 ($o/) compared to I.Kent used a maximum field of 44. 40. But the doublet splitting of lithium is very small.
using circles for a components and crosses for The abscissas are fixed by the relation &o/ = 2O8 x components. the pattern at abscissa 112 is certainly to be shifted bodily toward the red.154 a 2 ONEELECTRON SPECTRA From fio 10 5 $. PaschenBack transformation of a P term. Kent s observed patterns are plotted on the TT same figure. The agreement of these experimental values with the theory is excellent in view of the difficulty of accurate measurement of such fine patterns. For most of the patterns. using fall lines for perpendicular (a) components (Am= 1) and broken lines for parallel (77) components (Am = 0). It is pleasing that the theory of the Zeeman effect gives. 10 5 is completely determined in absolute value if one knows the doublet splitting. purely from symmetry holds in this particular case. 9 a $ uniformly into two states with would be represented 4. For example. hence to the scale of Fig. 9 s. &/&.+* 2 * Fig. 10 5 we have plotted the line pattern for transitions between a P and a 2 S. (12a) we see that a 2 $ is split energies and 5 2 So. so that the pattern of Fig. the absolute values of the perturbations. . * oft/c.1 by two lines through the origin of slopes and I corresponding to m= . 2 In Fig. but the relative values are certainly to be taken as of more value than the absolute. considerations.gt. the absolute which values of the ordinates were obtained by Kent by comparison with another line in the same exposure.
ZEEMAN EFFECT .
OKEELECTRON SPECTRA 105 The relative strengths of the allowed transitions in the weakfield case .156 Intensities. we may at once obtain the strengths from the Since $(np*Pl) = &.(n = (4) is .lt. Allowed transitions and strengtiis in the weakfield Zeeman 5 Fig.lt. 12 The strengths in this case are readily obtained from formulas like II 3 9. In the PaschenBack limit we have the selection ride to the rule ( Ams = in addition f Am = Am.f&. 4 respectively become asymptotically parallel to and equidistant on either side from the outer com ponents of a normal Lorentz triplet of interval fio. II . 1 1 5 shows the expected line pattern for . Similarly the strength of s^Q). independent of field.gt.) =1. with the relative strengths for observation perpendicular to the magnetic field indicated by the lengths of the lines.(np%l) and 2 iff(ri$ S^) eigenfunctions for these states are of component (5) is independent of field. The allowed components for 2P2 5 .gt. For large fields lines 2.gt. 12 . fields. Allowed transitions effect.j&. the hence the strength &. 5 and 3. /S are in dicated in Fig. For intermediate eigenfunctions. Hence Kent s pattern in which these lines are unresolved forms almost exactly a Lorentz triplet. 2 2 S 3 (a) . may be obtained by use of the matrix components calculated in 9 3 and 1 1 3 The details are given in 4 16 Fig.0.. (si (9)(JO) (7) (8) I 1 TT cr ! I M M &)(*) 5 Fig. and strengths in the PaschenBack hmit. P&.
and (9). of sufficient (7) independent of ffl. roughly by the widths of the lines the 5 of Fig. . greater than 21. lines (4) and (5) are of constant to the 10 In Fig. 2 2 Since a 4. a PaschenBack 2 The variation in strength of the components of P transition. have been made with While no intensity measurements and of (10) and these changes in intensity. 13 5 which . in . 13 .10 5 ZEEMAN EFFECT = may find from a 157 set of equations like . Darwin. for the a components. (2) and of (3) and for the n (1).gt. For m 2 coefficients in the expansion 7 2 the From these we find 2 2 So the strength of the component from one of the states to $^ is a from the other. are indicated intensities of the transitions of Fig.gt.]3 = I./ taken from the paper by K.) &&. (The numbers are values of 2 &. 10 5 . 5 Fig. the sum of these strengths is a constant. /J 2 times the strength from np f m+ in the PaschenBack limit. we accuracy to check quantitatively of the lines which are forbidden in the may note that Kent observes none PaschenBack limit at values of fiojt. is numbering Referring the sums of the strengths of (6) and strength. we independent of field. . . are (8). components.
Phys. 1. But relativity effects are usually small so that of the several electrons. . This fact provides a natural place in the theory for an empirical rule known as PauWs exchmon and makes principle possible a fairly complete understanding of the periodic table of the elements. we may its approximately regard the nucleus as a fixed centre of force instead of treating coordinates as dynamical variables. 1293 (1929). surrounded a number of electrons. we regard an atom as made up of a central massive positively charged nucleus. Since for all is This dynamical model atoms the nuclear mass is more than 1800 times that of the electrons. more than one electron which takes into account relativity effects: in fact. 34. and chemical behaviour of different elements. According to the nuclear model. In all atoms there will be terms in the Hamiltonian which represent the magnetic interactions of the electronic orbits and spins and terms which represent the Coulomb repulsion At present it is not known how to give a satisfactory theory of atoms with. This amounts to treating the nucleus as of infinite mass: the correction to finite nuclear mass is treated in I 18 . one can give a fairly satisfactory treatment of the subject in spite of this defect. by described in the theory by a Hamiltonian function whose proper values give the allowed energy levels and whose proper func tions are of use in calculating various properties of the atom. This made the startingpoint for a calculation in which the interactions actually shall see that the relative import occurring are treated as perturbations.CHAPTER VI THE CENTBALFIELD APPROXIMATION* We shall now proceed to lay the foundation for the theory of spectra of atoms containing more than one electron. The mode of describing spectra that is used by working spectroscopists everywhere is based on the idea that the atoms can be treated to a fairly good approximation by regarding the elec is trons as moving in a central field and not interacting with each other. Rev. even the exact relativistic treatment of hydrogen which allows for the finite mass of the proton is not known. We ance of different kinds of interactions varies a great deal from element to and that this is in a sense the origin of the different spectroscopic element. In this chapter we shall also study some of the features of the atomic problem which have their origin in the fact that all electrons are believed to be dynamically equivalent. The * principal interactions between the particles are in this due to the Coulomb The method used and the next chapter is due to SLATES. The Hamiltoaian for manyelectron atoms.
The mutual repulsion terms. tend to cancel the negative 5 terms which represent the attraction of the nucleus. . 2. For most purposes we can neglect the relativistic electrons moving variation of mass with velocity. (i) is Here subscripts of the i ih 1. From poten we know that if the other electrons have a distribution with tial theory . We shall adopt this of atomic spectra working hypothesis and to a large extent base the theory of the approximate Hamiltonian on the quantummechanical properties (2) In this Hamiltonian.I 6 THE HAMTLTONIAlSr FOB MANYELECTRON ATOMS 159 electrostatic forces. the terms expressing the mutual repulsion of the electrons prevent a separation of variables. thus for a system of about a nucleus of charge Ze we are led to the approximate Hamiltonian N pi W s and r . this compensation becomes less exact.. being all positive. Now Fi p as ri diminishes to a value comparable with the values of the other r s. screened the force field of the nucleus.". If r+ is large compared 2 2 1 values to all the other r^ then r^r^ and e /r^~e /?v Since there are of j associated with a particular value of i. there are so many of them that their total effect is comparable nucleus. The exact way of doing this of the electron s along the lines of a generalization of Dirac relativistic theory its relation to a system of several electrons is not known. r t the distance of the i electron from the nucleus j is the mutual distance th and^ electrons. . In addition to the terms written down it is essential to treat the magnetic interactions of the electronic orbits and spins.. some work in this direction and 7 to the helium spectrum we shall report in 7 An approximate . t31 N serve to distinguish the different electrons. for 2 is small compared to a Ze /r although if Z is fairly great any one of them with the term. allowance for the spinorbit interaction may be made by including for each 5 electron a term of the form gfa) L^St such as we have introduced in 4 for as our the doublet structure of oneelectron spectra. The procedure generally interaction between the electrons and the used is based on the idea of screening. one N sees that at large distances the electron moves * in a field that approximates to(ZN+ I)e2 /r^ .. These terms cannot very well be neglected as small and treated later by perturbation theory. We say that the other off (NI) electrons have .. according to which the greater part of the mutual repulsion terms is taken into account in the approximate solution on which a perturbation theory treatment is based.
. The approximate Hamiltonian E which we make the starting point of our calculation takes the form (3) while the perturbation potential will consist of the difference S 2. In Chapter xiv the theory will be for U(r) extended by detailed consideration of the question of the best assumptions and the actual evaluation of quantities that depend on the choice made. ri is small compared to the other r^ so as a function of ri will approach the form . hence the the potential due to the shell is constant and equal to potential energy of an electron inside such a shell is ee ja. its potential energy Ze\ (Nl)e* rt a which a is the harmonic mean of the radii of the shells in which the other electrons are distributed.160 spherical THE CENTRALMELD APPROXIMATION I6 f symmetry. r small and r large mean respectively r^a/Z and r&.gt. From these general remarks we see that a large part of the effect of the mutual repulsion of the electrons can be allowed for by starting with a Hamiltonian in which the potential energy of each elec tron at distance r from the centre is such a function U(r) that in T i C for r small. J */* (1) of this is the sum of a number of parts each of which refers . For an electron near the nucleus.Z JVf 1) where a is the Bohr 5 5 hydrogen radius of 2 2. (4) Equivalence degeneracy. then inside a shell of radius a and total charge e e /a. . f for r large. be to build up a systematic theory of the spectra of atoms based on the use of such a screened potentialenergy function as the starting point of the perturbation theory. Later we shall see that in this characterization of U(r). We shall see that a large amount will Our programme of general information about spectra can be obtained with hardly any more detailed assumption about U(r) than this. The Schrodinger equation for the allowed values of E (1 6 3) takes the form i=lL Since the left side ^^+U(rj^4 = ]B t.a/(.
each u is the same function of its coordinates for the same set of quantum numbers at.. be separated if we write evident that the variables can N = n UiW^u^a^u^ . eracy. We shall let A stand for the com quantum numbers. and is therefore known as equivalence degeneracy. &. there is the individual sets of quantum degeneracy that goes with the fact that the m m N numbers of the complete set of necessary to specify the state $ can be associated in any way with the electrons 1.. Second. we denote by at an individual set of four quantum num bers which specifies the state of motion of a single electron in a central field. there is that which may arises simply from the fact that the Hamiltonian for the individual electrons does not depend on spin or on spatial orientation the energy E (at) is now that the Hamiltonian and s . i. This degeneracy arises because the Hamiltonian 4JV". Physically this means simply that in the absence of interaction each electron moves in the central field U(r) exactly as it would move if the other electrons were not present. the E is a symmetric function of the coordinates of the N equations for the N factors of the wave function are all of the same form so that it is not necessary to carry a subscript to show to which electron s coordinates we refer. Then let the operator P stand for a particular permutation . Thus at represents a set of values (n I s l ) or (n Ij m) according to the way mm in which we wish to It is clear treat the oneelectron problem.$&. which E possesses a high degree of degen be regarded as of two kinds. because of the dynamical equivalence of the electrons.. to give a which belongs to the same total energy.e.gt. The equation for each u is For convenience.(A) the particular function which the first electron is associated with a1 the second with a 2 the third with a3.26 EQUIVALENCE DEGENERACY it is 161 to the coordinates of only one electron.lt. This kind of degeneracy we have already really independent of t studied in connection with oneelectron spectra. &. 2.lt. . Since the Hamiltonian different electrons. 3. . First.a of oneelectron understand by in &.lt. . and so on. A convenient notation for the different s associated with a particular shall set of quantum numbers is now desirable.. and L z N plete ordered set a a . is a symmetric function of the coordinates of the several electrons.
the result of the second.. We therefore postulate that a physical ^r function be such that spins. Before considering this question we may note that unless a number of the C^s vanish. contrary to experiment. P where the an arbitrary set of coefficients. the occurrence of the summation in (6) makes it impossible to speak s are CP of a definite electron. where P represents a permutation of the electrons.162 THE CEKTBALEIELD APPBOXIMATIOlSr &. the third remains. etc. Thus with P operation by P on is &..* is Any state associated with the quantum numbers a1 a 2 a? . the permutations are considered distinct nevertheless. There is.lt.. momenta and The idea of the last sentence is formulated by the requirement that the mean value of any algebraic or differential function / of the electronic coordinates be the same as that of the function P/. these do not all lead to distinct eigenfunctions.lt. even under the action of a symmetrical disturbance.. there are 2V! such permutations. all electrons have exactly the same properties the same of having various probabilities of being at various places. that electron would behave differently from the rest.gt. If a particular electron occupied an essentially unsym metrical position in a $ function representing the state of a system. * If two or more sets of quantum numbers are identical. thus of the form (6) rtA^ZCtPftA).. . as having a particular set of quantum sets of quantum numbers. The next problem is that of determining the particular values of CP which correspond to the states of the atom as observed in nature.(a*) 3(a) %(a*) %(a 5 ) . however. but there electrons and numbers. If this were not so.j&. of all electrons in the world). and so on.. the particular electron occupied an unsymmetrical position in the form of some observable We which would be observably distinguishable from the rest.(A) PftA) ^(a 1 ) u. recognize immediately that all physical observables are symmetric functions of the coordinates of all electrons in the system (in fact. 26 of the electron indices relative to the quantum numbers in A particular P can be specified by the scheme /12345...gt. say the first.j&. The dynamical equivalence of the electrons. There are is not a definite correlation of electron identities with quantum numbers.. the fifth replaces as in (5). another phase to the complete dynamical equivalence of the electrons. N N 3..\  \25314./ whicli means that after the permutation has been carried out the coordinates of the second electron appear where those of the first were.(A). (5 ) With N electrons.
but only that $ have sufficient symmetry that calculated from it. etc.01. By interchanging i and j again we (3) then requires that ^&.lt...gt. or j& = $?. which does not involve x i .... Then if /=S(a:1 a1 ) S(a:2 a2 ).o. tjnff=f&.lt. = et V#fc. . Then is 2^. In the same way.03. for all operators/.f&. or since ^r a function of a^.9/3x #01. A $ function has physical significance only through the probabilities which may be Hence we do not postulate that symmetric.. &.. . fe.. (b) t Pividing (b) by log ^=z  log c^ at all points.= e2 see that iikmm and hence that ^ lfc ..f&. then ^ = e*s ^. *jt were otherwise related we could find some operator for to bring out the distinction. if/ be actually (i) for all permutations and operators /. which does not change its value.02. dr oXf (a) gives r  at all points. we find that ^^... hence a physical observable must be a really symmetric function of the electrons. .gt.36 THE BYNAMICAL EQUIVALENCE OF THE ELECTBONS 163 The form of an observable has physical significance as such. . (a) we take /=(! oj Sfo %).. P we obtain __ (2) Now it seems obvious that if lff*fs= ff(f&.. Applying the inverse permutation 1 P". the equation becomes or If #01.gt.* Pe/r Hence we require that (3) = e% any permutation P. ^^. &. (for any i) and which is therefore a a continuous function which vanishes at infinity.. ... =^z. = ^. as for the case of the spin coordinates. Let us write our eigenfunction as ^fc...0*. to satisfy (a) .. formal generalization of this proof to the case of continuous coordinates may be made by use of the 8 function... arSJ .. .j) at all points. =^1.. .. *V#A&. the function which is obtained from this by interchanging the coordinates of electrons i and j as ^&... . the interchange of any two electrons in merely multiplies the *[r ..... = e*V#fc.gt.. Denote the coordinates by x19 x2 . to all factors in the integral on the right. 2.lt.a4 . for if and &. where ^ is constant.gt. i/r A * An immediate proof of this may be given for the case in which the coordinates take on only discrete values so that the integral becomes a summation. where S is a real constant.. ...a iy a*.
c12 = c 13 . for aH (5) Here^hasthe parity of the permutation P.e.  Any permutation can be regarded as made up of a number of simple interchanges. d 24/1. Handbuch der Physlk. for a. Then Hence. p. since c 3 =1 . i.. i.f The antisymmetric eigenfunction (5) can be written as a determinant VFJp v ^". of permutations in which (2V 2} indices are left unaltered and the other two simply interchanged. or multiply it by In the particular case of eigenfunctions 26 6 of the Hamiltonian JJf. and the per mutation is accordingly said to be even or odd.. an odd number for an odd permutation.* the function unchanged in the one case.e. the choice &. In the same way all the c s may be shown to be equal. The number of such interchanges for any given permutation is uniquely even or odd. Since the functional form of $ is completely determined by function by the position of the indices. so that a $ function for a physical state must be either completely symmetric or completely antisym metric in all the electrons . let the interchange of the first two indices multiply ^ by c 12 ( = 1). not necessarily of the form 2 6 4. 2 ed. we may build a . the interchange of the second and the third indices by c 23 . of the first and third by c 13&.lt. while Q* = ( l)p p gives us an antisymmetric state. the interchange of any two electrons must leave 1 in the other. . p is an even number for an even permutation. vm (6) in this form the antisymmetry follows from a minants. known property of deter From any eigenfunction ifi. grouptheoretical discussion of this restriction. symmetric eigenfunction and an antisymmetric eigenfunction by the use of the operators (7) * See PAUU. etc.=! for all P P (4) is seen to give us a symmetric state.gt.164 THE CENTRALFIELD APPROXIMATION 36 1. 191.
Hence Suppose that p if 2 (7P P^ is symmetric. The factor 1/VFI is placed in and j/$ will be normalized if it is. Thus the mutually orthogonal. it will 5 2 3.l)^j/ we see unique antisymmetric linear combination of the Nl P^ s. For according to always an atom has at a certain moment the antisymmetric eigenfunction show that the rate of change of its eigenfunction with time is given by J?$a which itself is antisymmetric. Then y^ CP Pj= VWl E CP P$ by (7)./r. that PS P Pijs = S CP P$ for all P. I From the third it follows that if $ is an eigenz/r for VN the zero eigenvalue of &.36 THE DYKA3HCAL EQUIVALENCE OF THE ELECTRONS 165 which we shall call the symmetrizer and the antisymrnetrizer. it is possible to do so. j always remain in a symmetric state. is one for which P$ = fy for all P. respectively. $ is But &(&ilt)=VWl&fa hence That f$ is essentially the only symmetric f$ symmetric. any 7 linear combination of the A P^ s is shown by the following argument.e. S CP P$ is symmetric. Similarly. seen to be symmetric. if ! of &. i. Now we may state. and zero eigenvalue of s.lt. These operators may be studied by purely operational methods.$& it belongs to an eigen^ for VN of I ff* it belongs to the Now a symmetric for is &. then sets a* of quantum numbers are state (6) is normalized provided that the ^ & and sf so that N if all Nl of the Pf s are all distinct. since ! ^P = P^=^. observable operating on a symmetric state gives a symmetric state.lt. But ^S(7P P^= (S P )^. If S^^^VWl^. If stf an antisymmetric eigenfunction if it not possible to do so the functions 5^^ or j/$ vanish. if if an atom is at any time in an antisymmetric remain in an antisymmetric state. j/P= PJ/ = . oper symmetric state ating it will on an antisymmetric state it gives an antisymmetric state. if the atom is at a certain moment in a ^ a . from the fact that ( that *$/ is the Hence is & produces a symmetric. A symmetric. From the definitions we have the relations (8) From the first two it follows that the eigenvalues of Sf and sf are VN and 0. Similarly. .
9 We see at once that the quantum mechanics provides a natural place for the introduction of this principle. . as a matter of convenience. D: (00). It is now evident that the antisymmetric system of states satisfies the exclusion principle. since if 6 any two individual sets in 3 6 are identical the determinant vanishes.166 4. so that an interpretation of the fourth quantum number was lacking. fur Phys. according to the four choices of the values of l and ms m . while and C do not give independent A D B * PAUXI. This gives four possible sets of quantum numbers. 46 of In the empirical study of atomic spectra which. Hence Pauli J for free particles to the experimentally verified Fermi electrongas theory of metals. antisymmetric states. Particles having symmetric eigenfunctions are said to obey Bose statistics photons are particles of this nature. shall. We found in the last section two systems of functions appropriate to equivalent particles such that which ever one actually occurs in nature must be the one that always occurs. . Zeits. X. Y. preceded the development quantum mechanics. When one forms antisymmetric functions 3 6 6 from these sets one sees that and are ruled out by the exclusion principle. We . He noticed that if four quantum numbers be assigned to each electron. . written as a superscript to the value of 7%. One would expect that the lowest levels would be given by states in which each electron is in a la state. Although the interpretation of this quantum number in terms of electron spin was soon given. .e. for ) for states satisfying the exclusion principle. THE OENTBALITELD APPEOXIMATION Tlie Paul! exclusion principle. For this reason particles having antisymmetric eigenfunctions are said to obey Fermi statistics. the curious fact remains that the two individual sets of four quantum numbers of each of two electrons cannot be alike. then states of atoms in which two electrons have all four quantum numbers the same do not occur. Pauli* discovered a simple generalization applying to all atomic spectra. 31. This is known as Pauli s exclusion principle. This requirement is substantiated in other ways for example by its equivalence states. completely The simplest case in which the Pauli principle makes a restriction is in the lowest energy levels of helium. reserve capital Greek letters i. since transi tions between states of different type are impossible. principle describing the state of a system must be antisymmetric in all electrons. where the sign of ms is B: (0+0). A: (0+0*). C: (00+). Kothing of the sort occurs for symmetric is s empirical introduced into the theory by the requirement that the $ function. 765 (1925). This was a rather perplexing discovery at the time it was made because it preceded the hypothesis of electron spin. (Y.
sum of the m and of ms are both say S. since such states are eigenstates only of the centralfield problem. and if in any scheme] yjm is allowed for one m. But for Jx +iJy is easily shown not to if Jx + iJ has a zero eigenvalue. and since for it the zero. are prohibited by the exclusion prin on the ground that one cannot find a nonvanishing antisymmetric ciple function characterized by those quantum numbers. then we can find nonvanishing antisymmetric functions ^(yjm) for all m. certain other wise acceptable states. it is a term of the type %(seeF). and Y(yjm) an anti function. Presumably a more fundamental theory of the interaction of two equivalent particles will provide a better understanding of the matter. y have a zero eigenvalue unless so also has (Jx i has the eigenvalue (or j 1). j if we can find a nonvanishing antisymmetric function by the quantum numbers yjrn. although we have found a natural place for the Pauli principle in the theory. but such a theory has not been given as yet. It is to be observed that. m(m+ 1)]P. which is zero only if m=j [j (jf 1) A similar consideration holds for the operator Jx iJyi which * We shall call any scheme in which the state of a system is specified by giving a complete set of oneelectron quantum numbers as in 3 6 6 a zeroorder scheme. we have not a theoretical reason for the particular choice of the antisymmetric system.46 THE PADXI EXCLUSION PKINCIPLE Thus there values of is l 167 functions.*F(yj 3 very simple. consider the equation 3 3: ( Jx iJy T(yj m) = ) Here to be a symmetric operator. Then Y(yjmf 1) will also be an antisymmetric func symmetric tion which will not vanish unless Jx f iJy has a zero eigenvalue for the state Jx + iJy is assumed yj m. In the zeroorder scheme* which we have been considering. it is allowed for all m. say w). In the same way in other schemes. but furnish a useful starting point for perturbation calculations. one wiH find certain otherwise acceptable states prohibited. steps the m value down. namely those in which two electrons have the same quantum numbers. in which one has no criterion so simple as the identity of the individual sets. There is however one important theorem concerning this exclusion which we can prove here. But m=j. The proof is This means that characterized ". namely: individual set of jfea the state symmetric angular momentum. . left but one set. This is one of the unsolved problems of quantum mechanics.
in the complete of an individual set having quantum numbers nl. This list of nl values is said to specify the Then the firstorder perturbation theory will need to consider only that part of the perturbation matrix which joins states belonging to the same configuration.e. and one in the 4p. we let the nl Since the energy in the oneelectron problem depends only on nl. values label the different Here. energylevel problem configuration figuration of an by configuration. and we may to the first order treat the electron configuration. the second 2 total 41 + 2 sets as above. } m . i. positive value so that the sums of the l We have seen that the antisymmetry of the eigenfunction makes it im possible to speak of a definite electron as having a particular individual set of quantum numbers. formed the habit of speaking of a state of the atom as involving. two Is electrons and one 2p electron. shells. two electrons in the 3d shell. * If we calculate this using the jm scheme: j may be values of m. l and l since s is restricted to the two values ". on the list of nl values of the individual sets. and there is no harm in con tinuing this convenient mode of expression if it is understood that in such a statement the term *nl electron refers to the occurrence. It is to be noticed that for a closed shell a negative value of l and s occurs for every it m m and of the s values are zero. usually the quantum num bers nlms ml or n Ijm. which consists of a list of individual sets of quantum numbers. we say contains a dosed shell or amiplete shell of that type. spectroscopists m m say. 35. 3s 2 3p 6 3d 2 42? } (1) Is. the energy in an unperturbed state of the centralfield approximation depends only on the distribution of the electrons among the shells. I +\ or I J.168 5.* When a maximum number of individual sets of a given nl. which indicates an atom (really the ion Ti+) with Z = 21.with. Each individual set contains four quantum numbers of the oneelectron problem. 2p shell. In the centralfield approximation the state of an AT electron atom is specified by a complete set of quantum numbers. In a complete set there can be only two in dividual sets the same n. ril there can be but 2h 1 different values of m fi so that altogether only 2(21 f 1) complete set contains the individual sets may have the same nl. as was done early in spectroscopic theory. THE CENTRALHELD APPROXIMATION 56 Conventions concerning cpiantum numbers. closed 2s. In specifying a con atom a notation of the following type is used: Till Is 2 2s 2 6 2jt&. m f For a given . complete or incomplete. Now the Pauli principle requires that all individual sets be distinct. and it is this requirement which gives rise to the occurrence N of closed shells of electrons. 2p. and 3p shells. before the theory was fully developed. However. the first of which has 2Z f 2 .gt. Closed shells. In the same way we may say that an atom has two electrons in the Is shell and one electron in the set. N = 20.
as in 5 &. i. m values. in terms of eigenfunctions based on the centralfield approximation. Rev. all the sets of a given shell being placed together.* We need to know the matrix components. 1121 (1930). Let F be such a quantity. CONDOK. Having agreed on this standard order. but two different orders may lead to 6 Now the eigenfunctions (3 6) with opposite signs. It is easy to reduce the matrix components of this type of quantity to those for the motion of a single electron in the central field. the sets for a closed shell need not be listed explicitly. The order of listing the shells will in each case be specified by the order of nl values in the con figuration designation of the type (1). In the m sm scheme we shall use a notation of the type . Within a shell we shall for con 9 venience adopt a standard order of listing the quantum numbers.56 CONVENTIONS CONCERNING QUANTUM NUMBERS 169 order of listing of the individual sets in a complete set does not affect the state in an essential way. 47. the sets will be listed shell by shell. the sets will be listed in decreasing order of 1 + f then those with j = I \. The matrix component (A\F\B) connecting states of the antisymmetric 6 type whose eigenfunctions are given by 3 6 is given by P where the integral means integration and summation over the 3 and the spin coordinates respectively. the sets will be listed in decreasing order of l values. the set m with ms = + i being placed before that with ms = J. For this reason we must for definiteness list the quantum numbers in a specified way.lt. In the nlmgrii scheme. Nel l5 2 2^ 2 2j) 5 4 (2) m3 values Matrix components for S$/(). then of the 3cL 6. Zeits. fiir Phys. in case both have the same m^ In the nljm scheme. of certain symmetric functions of the coordinates of the N electrons.e. In the first place.t&. where the numbers specify the ml values and the superscripts the first of the five 2p electrons. 36. Then we may write & a) where /(i) operates only on the coordinates of the iih electron. 631 (1928) on second quantization. The symmetric functions which actually occur in atomic theory are fortunately of two very simple types. * . first all sets with j  l 3^(!+I~0~l ~i2). (2) 3N positional N . with different choices of the arbitrary phase.gt. Phys. and only the m/n^ oxjm values need be listed for the incomplete shells.(B). These matrix elements follow also from the considera tions of JQBDAN and WIGNER. The first is that in which there exists a function of the coordinates of a single electron which is written down once with each electron s coordinates taken in turn as the argument and the results added.
[ number of interchanges. The latter point of view will usually be the most convenient. Jt f *APcf)fuAP b&. We may think of P as an operator acting on the quantum number of each electron and turning it into a different quantum number.gt. electron in P&. or of quantum numbers relative to electron indices. Since (2) will P f is i the same as there are P the sign of each term in be positive.170 THE CBNTBALMELD APPROXIMATION 66 are considering only antisymmetric states. (4) F\ to (3) should not vanish.lt.j&. (4) need not equal Pa It follows therefore that all matrix components (A\ F\B) of a quantity of the type F vanish if A and B differ in regard to more than one individual set of quantum numbers. we may suppose that k except for one individual set.. and must be such as to put the unmatched individual quantum num We may calculate iih B r P bers with the electron s coordinates. and hence (A\F\) = {}(A\F\B (5) In order that the summand ) quite simply. since the nonvanishing of the l summand requires that P b = Pa\ P b* = Pa\ except that . ( J N % (Nl) (3) contains integrals simply of products of eigenfonctions of single electrons in th Therefore it vanishes unless of the in every place except the i .. Continuing the calculation. of B are arranged in the order a This will not in general be the conventional order for the set pass to the set B but we can B by an \ . P b N = Pa*. The summand in (2). For a given (Nl)l P s satisfying this condition. O(jB){}*( ). so we obtain for the sum over P and P in (2)... dividual sets in A agree with those in B.). We then have ).(A) We can thus denote the quantum number of the i th by Pa*.. which is the set a of conventional order. 1 Pb 1 .. .. since all the in dividual sets of quantum numbers are distinct. must be the same permutation corresponding as P. The same argument applies for each value .lt... it is immaterial whether we When we regard P as a permutation of electron indices relative to quantum numbers. Denote A is the same as B A when arranged in by B the set obtained when the individual sets .
which cancels the l/Nl of (2). E=A.gt.. giving a total of Nl. j) The second type of symmetric function which occurs in atomic theory is . From the form of the results it is evident that if/ is a diagonal matrix in the oneelectron problem.66 MATRIX COMPONENTS FOR &. i) which is summed over all pairs of electrons.lt. P we obtain N t* ~XX A i f J j i S *. N (6) Here In the case of the diagonal element (^tjjFx4) the argument is similar. the diagonal element is (A\F\A)=%(af\f\a?). The summation over i thus depend multiplies the above result by N. (J = 1./(* ) 171 I to and gives the same result. Hence on summing over for which Pa =a&. i p l * j 1) ! Now of the permutations P there will be (N N). 7. then F is diagonal in the ^electron problem. (A\I\B) = fc has the value (a /6*) k (8) if all the sets in agree with all those in except that a ^ b*. Hence we obtain finally of i from. Matrix components for 2^ f g(i. To summarize the matrix component (A\F\B) of the quantity (a) (b) vanishes if B differs from A by more than one individual set. Thus the sums of the z com ponents of spin and of orbital angular momentum are each represented by diagonal matrices in the JVelectron problem if the representation is based on the rilmri scheme. } that in which one has a symmetric function of the coordinates of two elec trons. We suppose . i~ I (9) This completes the reduction of matrix elements of F in the ..(oO/^). g(i j) = g(j.. The sign is positive or negative according to the parity of the permutation which changes the con all stand ventional order of into one in which sets in which match those in A B B B A at the (c) same places in and if the lists . P f must equal P or the summand corresponding to (3) vanishes.^electron problem to those of / in the oneelectron problem. since a definite integral does not on the name of the integrated argument. Hence 3 N\ .5=1 J is (7) since the value of the integral independent of i.
s nonvanishing terms to the surnmand. a double integral we see that for each P there are two Consider ". In order that there be some nonvanishing terms in the expression one sees that B can differ from A by at most two of the individual sets... here P and P differ by one interchange. We shall have three cases. We must have or of and Pa = a 1 or a k Then P must agree with P with regard to the (N 2) electron indices other than i and^*. The most important quantity of this type is the Coulombrepulsion term which occurs in the Hamiltonian 1 6 1. a* a*. and by none.j=i g(ij). by one.172 THE CENTRALFIELD APPROXIMATION 5 76 that i^}. then P ss P.. Similarly there are (N2)l of the P s for which Pa* = a1 and Pa? = ak For each of these we can have P == P..gt. It will now be shown how the reduction from the Nbe made in this case. of If . if present. ! ". ak bk . a quantity to the 2electron problem can 6 is defined by (I) G= i i&. now the expression (2) for a definite i and j. Since P". those in which B differs from A by two sets.. we can have P b* = V and P W = b k but P otherwise 1 3 : t c r t the same as P.. hence this term is positive second. so this is a negative term. . let us deal with the eigenstate B in which (N^2) of the sets are matched with those in A with the latter in conventional order: A: a1 & 2 : .. P we deal with which contribute such that Pa i = ak Pa = a* and Pa = at* For each of these we get two terms first we may have P b = & P W = W and P otherwise the same as P. where the continued product of delta functions contains a term for each index except i and j.. The matrix component of G joining the states A and B becomes JiJj f f & (Pa*) fy . .. in which ?(^J) = 2 /%. (3) B Then B is f a* a 2 generally not in its conventional order. giving a positive term. so we shall have to multiply plus or minus one according to the parity of the permutation from the conventional order for to this order to obtain the correct sign for the by B matrix component. and P differing . for terms of the type S^(f i). Considering first the case in which A and B differ by two individual sets. 6 Corresponding to 6 i. constitute a quantity of the type F whose matrix components have already been calculated.. There are (N 2) of the P s for which 7 ... . .
. the diagonal element may be shown by similar arguments to be given by (A\0\A) In (7) we shall call the integrals with positive sign direct integrals and those with negative sign exchange integrals. change the conventional order of Next if B differs from A by but one set. . the sum over i. ak bk B By (A\Cf\B) : ay . . it is then easy to show that = (6) in which a runs over the ($"... / 1 sign in (7) may be carried out at . If g(i. ^ arguments similar to those already used&. then in the nlm^n^ scheme the sum over the spin coordinates a i 0$ implied in the . j) 173 from by one interchange.. sets with the conventional order in A. conventional order in up corresponding individual .7 6 MATRIX COMPONENTS FOR S^p(t. once.. Finally.gt. so we have exchange integrals only for electrons . Moreover. the first and third are equal and the second and fourth are equal. 1) individual sets that are common to A and B.. Altogether then the summation over P and P gives P Since these terms are definite integrals.j) is independent of spin. which is N(N (A\G\B) I) /2 so altogether we have 5 = (4) the sign being determined by the parity of the permutation necessary to into that of (3). we can take a permutation on the B which will match A: a1 a 2 a1 a2 .. This gives a factor unity on the direct integral and a factor S(m% mj) on the exchange integral. giving a negative term. aN .. j merely multiplies by the number of terms in the sum.
j)= S e/r&. The most general integral occurring is one in which four different individual sets. 2 Hence we shall have to (I) /* (ab\q\cd)=J J %(a) 2 (&) r I2 u^(c)u^(d).j) is independent of spin there are no matrix components connecting states A and B if these differ in G commutes with Ss 8.j=l which occurs in the Hamiltonian of the manyelectron atom.7icr so the spin components of a integral vanishes. where is in which r (1) the greater of rx and r2 Therefore the part of of spins can be written independent is . must be the same or the For farther progress we make use of the ! \ 1 relation 2^2 COSO) the angle between the radii vectores of electrons 1 and 2 from the This can be developed in a series of Legendre polynomials origin. which in the present notation becomes a Thus (1) positional coordinates 2 can be factored into the product of a sextuple integral over the six and a double sum over the two spin coordinates (2) SS(al3 m)S(al5 mpS(a^^ &.gt. &. and c.gt. i&. 78 of like spins.9 2 dd^^ dp a . the z component of resultant spin. This is consistent with the fact that in this case regard to their s . Inspection of (4) and (6) shows tliat if g(i. We wish now to carry out a computation of the integrals involved in this problem in the nlm/Yil scheme. and of b and d.lt. (4) .f^ c. the lesser and r . The most important quantity of the type considered in the preceding section is the Coulombrepulsion term Q= I q(i. /* are involved.. a. .lt. &.gt.j=l i&.gt.lt.lt. 2m Matrix components of electrostatic interaction.174 THE CEKTRAiFIELD APPROXIMATION". o&. b s OLlf II IS i". \ I f I J J J J f) sin^ sin&. The singleelectron eigenfunctions are given by 4 5 2. d.
2?T S(m.lc m$c k (ld mf. 175 depending on the spherical harmonics. (7) ^(ImtJm^^l^r^c^l If we m^lmt). V&. now introduce the abbreviation ^nW) R 2 (nW) dr^ (8) we obtain as the final value of our matrix component * S k=\m\ Jc&. only one term of the sum over m remains. the angle factor reduces to k (l c k (l a mf .mf S(m mf . They 3 give . since the c k vanish The values of the Mk here depend on our initial choice of central field and hence must be calculated independently for each different choice.lb m$R (nW (9) The range of k may equally well be written from identically for m. This expansion th term of (4) as permits us to write the angle factor occurring in the k The second 2&{l m =_fcjo . differ in this value. l c mf ) c d mf . mf .S ri(k m) O^Z* mf) 9^1 m o Jo c t ) sm91 dd^ f ff Jo ^( o The 9 integrals can be evaluated at once. c is defined by the equation (6) This expression is not symmetric in lml and V m^ but from 43 18. namely that for (5) m=mfm =mf l m\. When where this condition is satisfied. ^. can be further 3 expanded by making use of the addition theorem (4 22).m\) ) Hence in the summation over m everything vanishes unless that there are no matrix components connecting states which differ in the value of the z component of the total orbital angular momentum. mf ). c\l a k m. to oo. But the .lt.gt.86 MATRIX COMPONENTS OE ELECTROSTATIC INTERACTION factor. This For states which do not is consistent with the commutation of Q with Lz is 3 .
(g integral) l j These conditions limit the range of Jc to a few values in any practical case and serve to limit the seemingly infinite series occurring in (9) to the sum of a very few terms. the factorial of a negative number being meaningless. in the summation. for m^Q. V&.nblb ) (13) and K(a. Our integral is seen to be reducible to f m ). Trans. l a mf) c m*)] k (l .l b mb )Fk (na la .. equation (9). This formula cannot be summed except in certain special cases.gt. a table of values is needed for actual computations. 2g = I f V + 1". and V equal the sides of a triangle of even perimeter. m ^0. k . which requires that Jc. particular matrix elements which occur in the calculation of the 6 Table gives the values of the c s for The diagonal element of Q recur so frequently that the special notation: a b\q\ab) = J(a. k must satisfy the conditions . A228. In the first place ck vanishes unless 1% I. Expressed analytically in order that C A have a value different from zero. 86 c s are essentially definite integrals of three associated Gaunt* lias Legendre poly given a general formula for the integral of the product of the three functions Q (I m). Roy. p. l b mb ) mf = [ck (la mf (l". for m ^ 0. this form by means of 43 18. GAUNT. 194. m\ ) = c mf . Because of its cumbersome nature. d. m &.gt. V&. Gaunt s formula gives. I. b m\ .b) ( it is convenient to introduce According to (9). Q(l Qty m+m ). 6) = S(m. we may write J(a 6)= 3 S ak (la mf. I s.gt. r Jo f t mm +m m+ m ( ) where. t takes on all integral values consistent with the factorial notation. and/ electrons. 0. 151 (1929) in particular. l b m b ) ] 2 j .m*) k Here ak and b k are defined in terms of our previous ck by ak (la mf b k (la * . and l satisfy the socalled triangular condition.176 nomials and THE CENTRALFIELD APPROXIMATION may be calculated once for all. p. . Soc.
l ) l . First. If we are dealing with configurations involving closed shells of electrons. In 6 S 9 the summation extends over all the individual sets of quantum numbers. This case will now be investigated. The formulas of . This has the value +* ^ f 00 r^f 2 +i 1) individual sets m= S S S I mj= u Jo Jo Jo 3 m . d. and/ electrons. l ) . let us consider a diagonal element for a quantity of the type F. n a r /* y* J a a l .nb lb mOtb ) = I(na la m^ 3 O* where I equals / or K. namely F (n n = Rk (na a nb l l b . Consider separately the sum over the 2(2Zh associated with the nl shell. values in special cases. .86 MATRIX COMPONENTS OF ELECTROSTATIC INTERACTION 177 wMle F k k and a la . = 2e Tables I6 /vi y* 2 $rJ Jo Jor^ jSTi^ifa (15b) and 2 6 give the values of b k and a fo for s. we shall find G to share these properties when we calculate its Fk (na a na a = Gk (na a na a from its definition. we define in the K where Dk is the denominator occurring in Tables I 6 and 26 . the succeeding chapters will usually be expressed in terms of Fk and Gk It is seen that the R*s which are obtained in taking a matrix element between two states of the same configuration will always reduce to these F s and &*s. Specialization for closed shells. certain simplifications in the matrix components follow which are of im portance for atomic theory. For a pair of equivalent electrons. p. &. that Fk is essentially positive l . Gk are special cases of the b b l ) R k of (8). F*s and G s of the same k y are equal: We also note. Although from its definition we cannot make such a k statement.lt. shall use later the fact that We b m m^mf.gt. I(n \ a la 1 v tr J if J / (16) / \ 9. and a de creasing function of k.?*s To avoid the occurrence of fractional coefficients for the JPs and evaluation of J and matrix components. o J o ^j 1 1 2 1 2 n blb ) = E k (nala n bl b n bl b n al a ) r f k o J o /*QO r&.
where k depends only on I and I . calculated as if the eigenfunctions of the states in the nl shell were TABLE l e. 6*= +z/D k . Note that c*(J j. our final result is irp^ that is. In the table are listed only the sign preceding the radical and the value of a. c k(lm lf I mi) and &*(Zm z . k being given at the head of each column. &.lt. ) .gt. (1) the matrix component of the function/ averaged for all directions in space. We write ck = Vx[D Je .178 If / is THE CENTRALHELD APPBOXIMATIOK 96 a function of the coordinates r #9 a only and not an operator.p 2 . lm l )=( .l D D c k{lm lt I ml) for l+l odd .. Since 2 &*=(c*) . I mi). tMs /?r becomes /2 Jco oJoJo Now the sum in parentheses has the value (21+ l)/4rr. and Pj( 1 = 1 Hence addition theorem 43 22 by writing l = 2 ^ = . o&. this follows from the = 0.
ml) for l+l even spherically symmetric. and multiplied by the total number of electrons in the shell.SPECIALIZATION FOB CLOSED SHELLS TABLE I 179 I6 continued. Let us consider next the diagonal elements of the quantity .
180 THE CENTRALFIELD APPROXIMATION T4JJIJ32 6 . This (A\Q\A)= S N V \\v1 (ak )^z (af )q(l 2)v l (a k )v z (a )drIdT2 i i (2) r 7Y7 /\ It/ ( A. in the table we give values only for & &.0.lt. that part of the sum in (2) which results when ak has the nlm^ and a* runs over all the individual sets of the nT closed now JInl ril there occurs one term in this sum.z) is the spinfree eigenfunction Consider fixed value shell. but .1 for all values of the I. j ll 1 4~A JjL W/Jjt 4\1 ( A/j f JJj where dr=sin8drd8d and i?(&. As in the preceding table.S(. I . a*(Zm z . V ml) . &. that for which af=zak which does not occur in (2). arguments.gt. for kQ 9 a(l m tt I mi) . common denominator of several related values but once at the beginning of each For I = 0. we print the group.ZX ) The value of this coefficient is independent of the signs of m l and mi. a a (0 0. 0) for all V m{. We do not assume nl to be different from ril f . 7 6 7 and 8 6 12) electrons.gt. Note that which represents the mutual Coulomb repulsion of the element is given by the expression (cf.
This gives for our sum I g(l. complete set of functions in the interval to IT. new coordinate system for the a&. The coefficient this we expand  in this expansion is given by *1 rP^coMPHeosco) 2 . integral.gt. r* each of these integrals can be written as a sum over 1 /c of integrals involving 1 ) P^oosto) in place of g(l. The summation over mj may be carried out by the use of the addition theorem (4 3 22). on using the same expansion.) (Zrjdrg . jj r) 2) R^nl) R^(n 2 (Z l ) R 2 (nl) R 2 (n O^Zm.). The integration over 6^ 9 X may then be performed directly all . ^^ ^e direction $ 3 may choose a . 2) = e2 r !2 = e2 S ^~ ". S S f 2) Rl(nl) Rl(ril ) \(lm^ f f i(Z mJ) (Z^dr^ l ) ) f l. becomes 1M 1% i ". g( 1. (4) j Now writing 62 (r^/rf ".) &.gt. in detail. we have introduced only a vanishing term.) (B^) m .". which case = #2 Then x 9 X as pole. in in which case the integration over $ 2 . 2 (m.) 2 (Z wj) $ 2 (mJ) ^r^rJ . 8 6 15) (5) 2(2Z + l)! f (wZ.gt. 2). 9 2 . (3) The summation over ms gives a factor two in the first term and a factor one in the second. 1\ I Pr (coso) PJcosoj) (Zr^Tg (coso&.gt. . terms vanish except for /c = gives a factor 4?7.96 SPECIALIZATION FOE CLOSED SHELLS 181 the summand of (2) is seen to vanish.) .gt.gt.lt. 2) R^nl) R^nT) R^nl) R 2 (n f l ) Q^lm^^) f i\  ~^ (2r Pr (coso&.X&. 2A+1 Jo . for ak == a1 so is.lt. m^m^Z LJ J f".icjjr*". giving for the value of the direct integral / (cf. This sum J2(i. The exchange ff r &. In the direct integral one variables # 2 92 &. (6) (2Z To evaluate the product Pr P^COSOJ) in a series of This we may do since the P^(coso&.gt.ftT).) form a Legendre polynomials PX(COSO&.
(10) for the value of the exchange integral. (7) Cuvw is expressible in terms of the c s of 8 6 6 by the relation or the corresponding forms obtained by permutation of uvw.lt. (11) The most striking and important property of this result is that it is independent of the values of ml and ms entirely We may now obtain the contribution to (2) of all pairs of electrons in the same nl closed shell by multiplying (11) for nT = nl by the number 2 (2Zf 1) of electrons in the shell. GAUNT. where 2g = u + v + w.gt. p. n . (3) Hence the contribution of the nlm/n. . This gives for the contribution to the diagonal * HOBSOK. 8 6 15) . In each sum mand the dependence on Expanding the value is through the factor 2 (mj) 2 (Zm z )&.182 THE CENTRALFIELD APPROXIMATION for the integral of the product of three 96 where we introduce Legendre polynomials the notation J Pw (cos0) PJcos0) Pw (cos6) smd d9 = Cuvw o . This integral has the value* G is C are satisfied _ ~ 8 6 10). When we substitute the relation Pr (cosco) PK (cos co = 2 2A + 1 CXl K PA ) . A228.). this over the 9 2 vanishes unless A=Z. 195 (1929).I&. 9 ril )]. A ^ (coso&. The integral vanishes unless the triangular conditions (cf. A. 87. electron and the is n f l closed shell to the diagonal element of (2P Q given by V) + 1) [2 F*(nl. Soc. the exchange integral (6) becomes a double sum over K and #2 9 2 . we find that the integral of whole range of 2 . it PA (COSOJ) by the addition theorem. in which case has The constant factor. since symmetric in the three indices. Thus integration over 6^ 9 X can now be performed directly to give simply a we are left with (cf. Boy. SpTierical Harmonics.gt.J S CIUK G*(ril K . and dividing by two since each pair of electrons is to be counted only once. Trans. PA (cosco).
so the nondiagonal element that occurs is l just what would occur for the spinorbit interaction if there were but one electron in the whole atom. l But we have seen that the electrostatic inter and action energy is diagonal with regard to r g . m m and ms Since for each closed shell Sm. The conventional order of listing quantum numbers will make the valence electron in set B come at the same place in the list of individual sets as it does in set A. the Sm^ ms of the valence electron. * )]. according to given by the roots of a secular equation in which appear the matrix components of the perturbation energy taken with regard to all the states The 5 82 is of the configuration. so there are no nondiagonal matrix components due to this term in the Hamiltonian. The one electron not in a closed shell will be referred . For the configurations under consideration it is possible for B to differ from A only in regard to the and ms of the valence electron. Sm Sm As to the spinorbit interaction. which is exactly is what it would have been if the orbit interaction is others had not been there. nl)]. We label the states by a set of quantum numbers for the closed shells and an individual set ?zJms z for the valence electron. (13) One electron outside closed shells. electrons in a closed shell 6 applying 6 9 is obviously zero. it is a quantity of the type F. A the closed shell n The contribution of such terms (21 is ! 2(21+1) 10. ril ) JS K Vx G(nl. to as the valence electron.96 SPECIALIZATION FOB CLOSED SHELLS 183 element (A\ Q\ A) of all pairs of individual sets belonging to the same closed shell the value 2 (21 hi) [2 F(nl 3 nl) . + 1) [2 F(nl. so the results of 6 6 apply. The degeneracy is only in Sms vanish. so the whole spin as in the oneelectron problem. Therefore the only term left in that contributed by the valence electron. We are now in a position to investigate the nature of the approximation which permits us to treat the spectra of the alkalilike atoms as arising from the motion of one electron in an effective central field as was done in 8 5 We consider for this purpose the configurations in which all the electrons but one are in closed shells. and and Sma for the complete set is just the m and l . . so the sign in 6 6 8 is positive. K ( 12) will there Similarly if there is more than one closed shell in the complete set be terms in the sum in which k refers to the closed shell nl and t refers to l . . The diagonal elements of the spinorbit inter action are given by 6 6 9 where. i l . as in 4 5 / is of the form ftrJLfSi The tn diagonal matrix components of this quantity are of the form t i msm f r a electron in the state nlms m The sum of such quantities for all the single m .J S CUK FK (nl. first approximation to the energy of any configuration.
there are the terms which refer only to the closed shells and which are therefore common to all of the states of the atom and so do not affect relative energy levels. The exchange which is con The situation is thus as follows. The integration with respect to r 2 can be carried out to give rl (1) J fi so the direct integral can be written in the form In other words the direct integral is just the interaction of the valence electron with the classical potential field due to the spherically symmetrical charge density 2 (2V + 1) R*(n l )/r*.gt. For this part k in 7 6 7 refers to the valence electron while the index t runs over all the other individual sets. when the valence electron is in an nl state. These two parts refer to the interactions of the electrons contained in the closed shells and so are the same for all states of the atom under consideration. It will be unlike it in that states will occur only for which the valenceelectron quantum numbers are not those used up by the closed shells.184 THE CENTRALFIELD APPROXIMATION 10 e Turning now to the diagonal elements of the electrostatic interaction we use the results of the preceding section. integral has no such simple interpretation. The oneelectron centralfield problem has to be solved for this field to find the unperturbed energy levels and radial eigenfunctions. a sum of terms which it is convenient to regard in three groups. These include not only a term like 9 6 12 for each closed . To treat an atom with one electron outside we may assume all electrons to move in an effective central field U(r). The firstorder per turbation (except the spinorbit terms) will then be. For each closed shell there will be a contribution of the form 9 6 12 and for each pair of closed shells there will be the contributions of the form 9 6 I3. Then closed shells the ^electron problem will be like this oneelectron problem so far as the spinorbit interaction and doublet splitting is concerned. sistent with the fact that it has no classical analogue. Therefore they do not affect the relative positions of the different energy levels. . First. This gives a sum of contributions of the form 9 6 11 for the interaction of the valence electron with each closed shell.nT) the direct integral representing the interaction of the valence electron with the nT shell is * a 2 (2V H.1) f From Jo Jo f El(nl) S%(n V) dr^r* f&. The sum is in dependent of the ms m l of the valence electron. The remaining part of the diagonal element of Q is the part which depends on the quantum numbers of the valence electron. the definition of F(nl.
These results give us a little more insight into the way the approximation depends on the choice of the function U(r).^1 R*(nT)dr (3) shell.10 6 shell shell ONE ELECTRON OUTSIDE CLOSED SHELLS 6 185 and one like 9 13 for each pair of closed shells.1) f for the nT T.(r) to the solutions for the potential energy jj& +SFBT nT irt TT .i&. Altogether they are focr &.gt. another classification of states of the atom which rigorously a constant of the motion.U(r) . only those referring to the total angular momentum (/ and M) are rigorously constants of the motion for a free atom.i&. Second. This suggests that one might take (5) as a new U(r) for a second trial and then determine the eigenfunctions which belong to it and in turn calculate new from these as a means of approximating to the best potentialenergy Vn &. and results 11. Detailed consideration of methods of obtaining U(r) based on special central fields will be given in Chapter xiv. but also for each closed a term like 9 6 1 which. according to 1 6 4.(r) function. The value of (4) a functional of U(r) of a rather complicated sort. .gt. In this category there is one sum like the second part of 9 6 11 for each of the closed shells. has the special form 2 (2V 4. Jo ^ U(r) ~ f7 f72 p2  + X FnT (r) by  J and the summation is (4) where the quantities the Vn r (r) are defined (1) over nV of all the closed shells. Third. Each state may be characterized 5 rigorously as even or odd/ a fact of great importance in spectroscopy is c . Now (4) is of the form which would arise if one were trying to approximate is r &. however. (r) t ^ (o) having started with the known exact solutions for the field U(r). it depends on U(r) not only explicitly but also in that the S(nl) depends on 17 (r) and so also do the Vn through involving the R(ril ). Odd and even states. There is. so that it is in the one simply the combined effects of terms like (4) and the exchange integrals which determine the relative positions of the different terms. there are the terms of the exchange integrals between the valence electron and the electrons in the closed shells. A good choice of U(r) would be one that makes (4) have a small value for as many of the values ofnl as possible. In the course of the developments which follow we shall see that of all the ordinary quantum numbers.gt.gt. there are the terms which are integrals of the form of a function of r multiplied by the square of the radial eigenfunction for the valence electron.gt. The doublet structure has been shown to be the same as electron problem.
Since anticommutes with the electric moment & P defined in 44 9 3 it follows from 2 23 that the electric moment can have nonvanishing matrix components only between states of opposite parity.1 are called even states. the eigenfunction .N) of the electrons as follows : From this definition it is easily seen that with an observable which is a function of the position vectors ris the momentum vectors i9 and the angular momenta JL4 and Si3 8? has the following commutation property p * PftrapttLitSj^ftrt. is (3) Hence stationary states of the atom may be taken that From its definition it is clear ^ 2 1 (cf.D(m) = eim^^(m) = .l)O(m).l) Then if is applied to an eigenfunction like 3 6 6. States eigenvalues of belonging to the eigen value 4. concerned with transitions Let 3* be an observable* defined by the result of its operation on a Schrodinger $ function of the coordinates xi yi zi ai (i=l. 7 9 0&. ^ is 2Z multiplied by ( 1) . odd. . It is evident geometrically that in polar coordinates Hence if the function is of spherical harmonic only the latter the form of a radial function multiplied by a is affected by &. This is the origin of the evenodd for the terminology 1 eigenstates of 8P belonging to respectively. 2 & M * Real because we shall shortly find that tlie eigenvalues are real and the eigenstates orthogonal.H] = 0.. & also as eigenstates of 0*. or from the definition because clearly (notation of 3 s ).. ( while on 0(2m) the result is so that the whole effect on any spherical harmonic of order I is multiplication z by ( ..gt.: [0&. Similarly %l and commute with and so will have nonvanishing matrix components only between states of the same parity.gt.Li9 SJ0 (2) Now the Hamiltonian for the free atom is a function only of rf tyr 9p* Li9 and Si and therefore commutes with . Hence the state is even or odd according to whether 22 is even or odd.  . are I 2 )..186 in that all THE CENTBAIrMELD APPBOXIMATION atom is II 6 the dipole radiation of the between states of opposite parity.. pi . Problem 1. to the eigenvalue 1. the identical operator and so the We shall now see that the eigenfunctions we have built up for the centralfield approximation are also eigenstates of 0*.lt. On O(m) the operation produces ^&.
CHAPTER We VII THE RUSSELLSAUNDERS CASE: ENERGY LEVELS prepared to build on the results of preceding chapters by atomic configurations having more than one electron outside studying closed shells. The next chapter is concerned with methods of finding the eigenfunctions for this approximation in terms of the zeroorder functions for the centralfield problem. shells * in these three chapters. while quite general. J. This is also true of the spinorbit interaction terms. Chapter ix com pletes the general study of the RussellSaunders case theory of line strengths in this approximation.)L J7(ft 1 contribute quantities which have the same values for all levels belonging to a configuration. i. by developing the The theory covered in a form which is involving a very few electrons outside of closed shells.best . Slfo) LjSi . EUSSELL and SATTNDEBS. For such configurations there are generally a large number of are now energy levels giving great complexity to the spectrum.j incorporated with the general study of the centralfield problem which take up in Chapter xiv. 38 (1925). Chapter xm will show almost closed shells. . Because of this fact their consideration is we i&. In this chapter we study the scheme of levels belonging to a particular electron configuration..gt. i Experience shows that in many atoms the spinorbit interaction is small compared with the Coulomb interaction. E e^fr^ is different for different states of the same configuration and thus same serves partly to remove the degeneracy of the states belonging to the configuration that exists in the simple centralfield model of the preceding chapter. Therefore they do not affect the relative position of the any one configuration. Astrophys. In the first approxi\ (Ze* ri levels of ". For this reason it is useful to develop an intermediate approximation in which the Coulomb interaction is taken into account but the spinorbit interaction neglected. . The Coulomb interaction of the electrons. 61. This approximation is called the RussellSaunders case in recognition of the pioneer work of Russell and first Saunders* in which the main features of the theory of complex spectra were recognized. or treated as small compared with the Coulomb interaction. will be suitable for actual calculation only for configurations how the theory may be adapted to the calculation of configurations involving with just a few electrons missing.e.
Therefore in addition to the con out of closed shells figuration label states. is S 8 the same SL. the corresponding small letters will be used only for quantum numbers which refer to a single electron. 33. . The Hamiltonian without spinorbit interaction terms commutes with all components of the total angular momentum Therefore this Hamiltonian will have no matrix components connecting 2 2 states labelled by two different precise values of S JL J* y Sz Lzi or Jz We introduce quantum numbers S. Only four of these six observables are independent. Therefore to this of the Hamiltonian which connect states belonging to different configura approximation the energy states can be labelled precisely and of NN by the r configuration. for all the quantum numbers occur individual sets ring in a closed shell are prescribed and the nl values of the are also prescribed. . for this is the number of degrees of freedom of the system.SN this is most directly seen from. Rev. In whatever manner this is done each of the new states will likewise need to be specified by 4JV quantum numbers. . . L. . the configuration label amounts to a specification ) (NN f f 2N quantum numbers. . i . J. the considerations in the first part of 8 3 Hence it . M From 33 8 we is obtain the important result that in the S L s and L Since a definite state independent of M . In the first approximation of the perturbation scheme we neglect matrix components tions. SLJM scheme the representation of states developed in the preceding chapter is based on a set of states specified by a particular set of 42V quantum numbers. * In accordance with the recommendations of RUSSELL. SHENSTONE.188 1. for quantum numbers which refer 8 . one usually takes either the set SLMS L or the set SLJM to label the energy for convenience in labelling states 8LM M M scheme the energy SLJM a linear combination of states SLM ML with various M ML but states. THE EUSSELLSATJNDEES CASE: EKEBGY LEVELS The L^coupling scheme. to tlie resultant momenta of several or all of the electrons in an atom. . M M M .JL 2 + and of the resultant spin angular momentum S= SI + S% + 4. I7 + LN components ofthe resultant orbital angular momentum L = L 4. J.NER fPhys. S(^+1)^ S^M/i (I) which correspond to precise values of these observables. this has as a consequence that in the energy is independent of J and M. If there are 2V electrons not in closed shells in closed shells. MZ. L. The We have now to transform to a new set of states in which the energy is diagonal to a certain degree of approximation. we shall use capital letters S. and TUK.* . or ion. N we need 2N more quantum numbers with which to label M M . . 900 (1929)]. B according to the L 2 scheme 2/ = S commutes with all JS+L.
* By the methods of the preceding chapter we can individual sets comprising each complete set which occurs write down the Each complete set will consist of the individual sets In the N configuration. . we shall in what follows use the word configuration to refer to the of the closed shells is class of all configurations which have the same ril values for those electrons not in closed shells..gt. F. The notation for a term.. is to write $. 32. \ set of (2j8+l)(2ihl) states belonging to a definite configuration and 8 will be called a term. giving(2S4.lt. 1. Zeits.lt. Then the S and L which resulted spins were coupled might be coupled under certain circumstances to give a resultant angular momentum J for the whole atom. ibid. 3. P. Even if L S we ascribe to a term this multiplicity and say that its multiplicity is Working in an LJ &. If more than one term of the same kind occurs in a given configuration. we 5 shall for the present distinguish them by an arbitrary extra letter as a P. introducing the concept of parent terms. GOUDSMIT. . accord with the usage of 6 5 P. .l)(2i+ 1) states \  ^ J ^ $ 4. SLJM scheme. . This is in 45 for the doublets in oneelectron spectra. this counts up to the same total number of states in the term. in 28 we shall examine the possibilities of a more significant way of characterizing them. The quantity 28+ 1 is called the multiplicity: it Is the number of J values and hence the number of levels that occur in the term jL^S.. . 2 2 Any set of states in which JL and *S are diagonal will be referred to as an LScoupling scheme. L and \MS ^ S. Thus 5 P C quintet P ) indicates a term in which = 1 and 8=2. 2. then \ML in the term. we have $ not fully developed. A and to a SLMS ML scheme.and \M ^ J for each J. which has become standard.. 765 (1925). 31. As it will shortly appear that the number and nature without effect on the following discussion. fur Hiys.. . 794 (1925).I7 THE LS COUPIANG SCHEME In case 189 either 2 these are not in general sufficient and we shall need to find additional quantum numbers in order to give a unique 8 in many cases ( 2 ) by specification of the states.D. On the older vector model of the atom the orbital angular momenta of the individual electrons were regarded as coupled individual together to give a resultant orbital angular momentum. If we are working with an definite L \ &. list Having made a of the complete sets which belong to a configuration * PAULI. and the to give a resultant spin. We have now to consider the problem of determining which terms occur in a given configuration. fori=0. and to write the numerical value of the multiplicity as a superscript at the left of the symbol for the L value. This can be accomplished J M or M ML S N = 2 the four quantum numbers needed are provided by SL and . for electrons both in closed shells and out. For N &.
$. one. that is. P. W. dividual sets occur. for the con 2 have to rule out all complete sets in which identical in figuration p . 3 3 P. This accounts for all states with M M ML = 2. The resulting table of complete sets for pp classified by L and m m values m M M s values is (2) = = 1 there must be a Because of the occurrence of a state for L 2 and 8 L . that is 3D. the configuration in which two p electrons with differing n values occur outside closed shells. so there must be a M M M M D from the = 1 we infer the occurrence two states in the cell L = 1 and 8 presence of 1 3 1 of a 3 P term. From 4 1 we see We except that the exclusion principle excludes or permits whole terms so that its . Similarly terms are eliminated by the exclusion principle in case the configuration involves equivalent electrons. These terms are the same as one finds on the vectorcoupling picture according to which 8 as the resultant of two spins each of magnitude onehalf can have a value zero or unity. and must count but once sets which are now the same 6 for different order of listing of the individual sets. Let us see what effect the exclusion principle has in the case just con sidered if the n s of the two p electrons become equal. M M s 6 It will be convenient to use the notation of 5 2 for the m l and of the two electrons. only in each cell of the table. angular momenta each of magnitude unity or two. the superscript s value sign indicating the value is given by the integer to which it is set whose for the individual l attached. . However. Of the two states in the cell L = 2 and 8 1 3 term to account one is accounted for by the D term. and D.190 THE RTJSSELLSAUNDEES CASE: ENERGY LEVELS i7 we may classify them at once by the values of Emj= L and Ems = a To make the argument concrete let us consider np n p (=pp). and this will have a state term having the values = 0. Continuing this process we see that the terms are /S.2 and 8=1. the vectorcoupling picture does not tell us which of the for the other. and L as the resultant of two orbital can have the value zero.
we write 3 for the firstorder energy of the term. exclusion principle to 15 for p z Similar tables for other configurations may be made to find the terms occurring. g ^0.THE L^COOTLING SCHEME 191 operation does not spoil the possibility of setting up an i/Scoupling scheme. The S L table now is MM (3) so the terms are *$. we obtain. If. for pp. 3 P and 1D. Hamiltonian associated with 1+1+) . We make the diagonal matrix components occurring in it. one of therefore the secular equation for the whole configuration which is associated with each value of M ML S states that the sum use of the diagonalsum rule (2 2 21) which of the roots of a secular equation is equal to the sum of . and write tions. having states in that cell to the D (1* 1+) for the diagonal matrix element of the this complete set. Term energies. 3 for brevity. There are no matrix components connecting states of different ML and M& \ factors into a chain of secular equations. although for several electrons outside closed shells the tables become quite extensive. one for each MSML D cell. this rule allows us to write a set of linear equa equating the sum of the energies of the terms sum of the diagonal matrix elements of the perturbation energy taken with regard to the complete sets in that cell. Because of the symmetry which obtains it is necessary only to construct that part of the table which corresponds to ML ^0 and Jf 2. Since all the levels of a term have the same energy. Now let us calculate the firstorder perturbation energy for the terms of a given configuration in the approximation in which we neglect spinorbit interaction. A total of 36 states for pp is reduced by the .
(1).* winch are not needed From these equations we readily solve for the term energies in terms of the diagonal matrix components: l+)(l+l+) l+)(l+l+) ? analogous to i (1) etc. This formulation furnishes a procedure for obtaining the energies of the terms of any given multiplicity without first determining the energies of the terms of higher multiplicity. * should like to call attention here to a slightly different formulation by VAX VLECK [Phys. It is the electrostatic repulsion of the electrons which gives rise to the separation of the terms. Part (c) is what gives structure .192 THE RTJSSEU&. 405 (1934)]. (b) pairs between an individual set not in a closed shell with those in closed shells. The sum in (3) breaks up into (a) pairs between individual sets in closed shells. both discussed in 9 6 and (c) pairs between in dividual sets neither of which belongs to a closed shell.gt. case of such a calculation is taken up in 7 8 equations is A . = (l+l) *P=(1+0+) ( l) + (ll + ) + (0+0)(l+0+)(l+l).SAUNDEBS CASE: ENERGY LEVELS cells 27 and additional equations from the remaining except as checks in actual calculation. these may be still further simplified by making use of some special properties of the diagonal matrix components from the preceding chapter. In terms of a vector model proposed by Dirae. From 7 6 7 we see that a particular diagonal element of Q = Sea/r# is given by (3) (A\Q\A) = a&. Corresponding calculations for the configuration p* give the formulas. all pairs where the summation extends over of individual sets in the com plete set. hence this method the sum.gt.d=l Ka6e/ria la6)(a6e/r18 6a)]. the only way in which the energy of these terms occurs in the set of linear } i/S= s (l + as the sum of the energies of all like terms. In order to find the individual energies one needs then gives only actually to solve a secular equation involving the nondiagonal matrix elements. After the calculations for a particular configuration have given formulas like (1) and (2). Therefore any quantity which occurs as a constant added to all the diagonal matrix elements of a con figuration will come up simply as that same constant in the expression for the energy of each of the terms. We . From the way in which these formulas are obtained it always turns out that the number of matrix components occurring with a plus sign is one greater than the number with a minus sign. If a particular kind of term occurs more than once in the configuration. Eev. of the problem of obtaining the firstorder electrostatic energies. The parts (a) and (6) will be constant for the whole configuration. 45.
b) K(a b)] over the N electrons outside of a&. np) without basing the calculation on a definite assumption for U(r) we see from the form of this result that.lt. 189. This form of calculation thus provides relations between the term energies which can be compared with experiment independently of the more difficult problem of finding a good central field.P) = 3.27 TEBM ENERGIES Its JV 193 to the configuration apart from It is absolute location on the energy scale. 112 (1923). Although we cannot know the numerical values of the integrals F^(np.np)IDk where Dk is the denominator occurring in Tables I 6 and 2 6 Hence finally the electrostatic contribution to the energies becomes . On writing E$ for the constant part which arises from pairs (a) and (b) we have 1+ 0+) ( = EQ + F&. whatever the particular U(r) chosen.&. 19. Hie Lande interval rule.gt. but leaves these terms degenerate with regard to J. regarding this as small compared with the electrostatic interaction. (5) with the S as the highest term. in the notation of 8 6 12. (1) * LANDE. 9 simply the sum S [/(a. each character ized by a given L and 8.(np. and similar expressions for the other diagonal elements occurring in (2). The spinorbit interaction has the form t .5=l 6 closed shells. Here we have used the fact that GjJ(np. The electrostatic interaction breaks the configuration up into separate terms. (iD . np) .np) = F k (np. 2. fur Phys.gt.np) = F^p. Let us illustrate the method by considering p* in detail. From formulas 8 I3 and the tables of a s and 6 s ? it is a piece of straightforward computation to express the energy of each term with the F and G integrals. 15. np) and F%(np. F2 J2 (4) . So many coefficients vanish that the summations in 86 I3 seldom involve more than two or three terms in cases of spectroscopic interest. Zeits. np) .5F2 (np. their com 3.ID) . 13 . the firstorder theory predicts an interval ratio (i# I . Such predictions and 7 parison with experimental data are given in 5 .* The next problem in the theory of the energy levels in the RussellSaunders case is that of allowing for the spinorbit interaction.
The details of such effects are considered in Chapter xi. M matrix element L S=j(J* L 2 S2 this factor is recognized (SLJM \L*S\SLJM so that we may write r(ySLJM) = (ySLJM\H 7 SLJM) Since m ) as the ). l \ . In case the spinorbit interaction is small compared to the electrostatic. If we wish to L to a good approximation and distin For the individual levels we use the standard we write the value of ^ Lj specify a state M as a a right superscript. +l . perturbation of the level ySLJ is thus given in the first approximation by (3) From this result we see that the energy interval between levels differing by unity in their J value is (4) . In the SLMSML scheme we shall designate of validity of the characterization by S and L. . this permits the levels to be labelled by J values even when the spinorbit interaction is not neglected. for the loss The complete matrix of H 1 for A M ML Z$ . we need only consider the effect of the diagonal matrix components in a scheme of states labelled by SLJM. i. and to JF. From the fact that r commutes with Lit we see that (r f )jL 4 is a vector of i th type T with respect to L i to L.gt. and configuration. etc. a given term will be split by the spinorbit interaction into a close group of levels characterized still by S and notation. f&.e. These are re components sponsible for the breakdown of RussellSaunders coupling. here we confine attention to the diagonal elements. In this expression everything is independent of / and except the factor in braces.l. guished by different values of /. H 1 does not But commute with S and L so that these no longer furnish accurate quantum numbers. Hence the diagonal element of the term of (1) is given by the first equation of 12 3 2 if we make the correlation . however. state by 2S+1 S9 2S+ 1 all the states in the configuration includes that are nondiagonal with respect to the terms. as 2 (2.) and which is y (which specifies the entirely independent of J. The spinorbit .194 THE EUSSELLSAFISTDEBS CASE: ENERGY LEVELS ttiat this 37 Front 8 34 we see commutes with J. In this way. Hence the whole dependence on J of each term ofH 1 is given by this factor. L.(ySL)(SLJM\LS\SLJM\ where (y$L) is a factor depending only on S.
there is a possibility of a small finite displacement of a term of a configuration con taining s electrons through the occurrence of an infinite value of multiplied by a factor that is formally zero. which is thus equal to the energy of the term as it would be in the absence of spinorbit interaction.gt. which would be constant the rule were exactly obeyed. that is.37 THE LAOT&.gt. To prove this statement we merely multiply (3) by (2/f formulas 1) and sum J from L$ to L + S. 31. 946 (1928). The spinorbit perturbation given by (3) has the property that the mean perturbation of all the states of the term vanishes. In order to obtain the absolute term intervals in terms of the oneelectron parameters We ^^H^M). It has a quite general validity and is of great use in empirical analysis of a 5 term of the configuration spectrum. using the summation J=0 S/ = JX(X+1). ) I4 0000 5 Da 415934 704001 5 D3 !&. as in the case of oneelectron spectra studied in Chapter v. SJ . 132 . This is known as the Lande interval rule. J=0 (5) Here. Eev. This weighted mean of the energies of the levels of a term is called its centre of gravity.:6 INTERVAL RULE 195 that is. we do not need Chapter xi is * (i) to evaluate 3 7 2 in greater detail (which as will be seen in in general a rather complicated procedure) but can obtain all GOUDSMIT. the mean per turbation of the levels when weighted by the factor (2 Jf 1) is zero. the interval between two adjacent levels of a term is proportional to the higher J value of the pair. SJj:P(X+l)a.* have obtained the Lande interval rule by a simple use of the first 3 equation of 12 2. As an example we may take the 3d G 4s 2 which is the normal term of Fe I D : Energy Level 6 1 (cm". In such a case it is necessary to have re course to the relativistic theory as was done in connection with the 2 /8 levels in hydrogen.7=0 2 = p:(Z+l)(2X+l). Absolute terra intervals.". Ptiya.! 888126 *D 978068 is Here * observed if the observed interval divided by J. 4.
of equations to determine all the (SL) unless two or more terms of a kind occur..(SL) in terms of the nl and there will be a .#\Hl\tf) S = S tefrnfa* is this: . 1. 2 hence we ) D&.y SLJM^ ) 7 SLJM)( 7 SLJM\ySLMs ML 1 ) S\ SLM8 ML 3 (2) the last form being obtained from a quantity of type F. . . M M M M . 3 * See preceding section for notation. s L or we obtain of course only the result = 0. The manner of using the diagonal sum for rule The zeroorder states a configuration are classified according to the values of L and s and 7 the terms which have components in each cell noted as in I By the and 8 the sum of the elements for a given value of L diagonalsum rule. but the new terms occurring in those cells are either S terms or singlets.gt. In the zeroorder scheme. in which case only the sum of the (SL) for these sufficient number terms may be obtained. (3) for the zeroorder states is equal to the sum of the elements (2) for the terms which have such components. In the 8LM8 L scheme t M SLMS ML scheme and in the zeroorder 1 \ need to know the diagonal L \Hi\ 7 SLMS ML = S (y SLMSML 7 ) = (y SL) (SLMS ML \L = MLMs t(ySL). The intervals in this latter case are considered in 78 .lt. since H is is A = a1 a2 . . As a simple example discussed in From 1 7 2 we see that (I + 1 + 2 ( consider the configuration np rip which has been 3 is the state* 1. the diagonal element for the state 7 3. for which has no real significance.196 THE BTJSSELLrSATJNDEKS CASE: ENERGY LEVELS we desire 47 the information from the diagonalsum rule except when two or more terms of the same kind occur in a coirfiguration. shall In order to use the diagonalsum rule we elements of the matrix ofH1 in the scheme.lt. D. M M We thus have obtained the result that ) = (np rip P).gt. obtain the equation or ^D] ^ ^ + ^g are linear combinations of the states (1+0+) The and or states 3 (0+ 1+) . 1 1 and hence 3 3 P&. aN (3) given by (A \H*\A) = N N (&. 1 ^D) + ^P) 8 i(^p + j g Z( P) = 1 W + U) If we attempt to write a similar equation for a cell with either 0. This gives for each cell an equation expressing certain of the t. I7. JM \ SLJM)(&. ..
Rev. the second in Chapter xv. term for which ($) is negative so that the lowest J value is are all essentially positive (4 5 ).* We now turn to a systematic comparison with experimental data of the formulas for the electrostatic energies and Lande term intervals in the RussellSaunders approximation. lowest energy. 37.lt.F =F (ris. For the electrostatic energies in the 7 simplest cases the theory predicts certain interval ratios as in 2 5. This positive characteristic of all configurations which contain few nl A highest is said to be inverted. even though the spinorbit interaction be small. &. First. The first point is con sidered in Chapter xi. and the intervals are specified as negative. Since the situation mentioned at the end of the preceding section in which a single level has a spinorbit displacement cannot occur unless the con figuration contains an s electron. since the sign for (SL) is electrons the resulting order with the lowest / value lowest is said to be normal. the neglected matrix components of the electrostatic interaction which connect different configurations may be important. Pitys. In other 3 cases where there are more terms and more JTs and 6r s we treat the latter s as adjustable parameters. none of the singlet or S levels of np n p can possibly have a spinorbit displacement in the RussellSaunders case. nl). . 1025 (1931). nl). Formulas and experimental comparison.% = G (n s. Departures from these firstorder formulas we may regard as due to two causes. From 1 1 6 we know already that there are no matrix components of the Hamiltonian between con figurations of opposite parity.gt. these arguments need not be specified t * COJO&. 5. then it still has to be remembered that the F*s and 6? *s are not really independent.OK and SHOBTLET.47 ABSOLUTE TEEM INTERVALS is 197 which directly amenable to comparison with experiment. Is Here . This part of the considered in Chapter xiv. The actual values of F s and 6r s have y to be obtained from some particular choice of the U(r) underlying the problem is centralfield approximation. Second. This enables us to see if the formulas agree with the data in any sense: if they do. the spinorbit interaction may be so large that the L8 coupling is broken down. 3 and says that the total It will width of the D should be J that of the be noted that in this case the lowest J value of each term has the 3 P. Hence all perturbations between E/ussell Saunders configurations occur between terms of the same S and L values and of the same parity.
2p = 3^ 2 ( P)=0 Here again we can eliminate the unknown F% and compare observed with theoretical ratios: Atom Theory Configuration 2 ( P2 2 I&. with intervals in the ratio given by 2 5.4S) np* 2p* 2p* 3p* 4#* 5p* 0667 N O I n S II As I Sb I Bi I 0500 0509 0651 0715 0908 1121 6p 3 The deviations in } NI and OH are probably connected with disturbance by 2p*3p the lowest term of which in I is only four times the overall 3 separation of 2p above this configuration. . N last three examples departure from LS coupling is important * We wish here to acknowledge our indebtedness to the excellent compilation of energy levels by BACKER and GOUDSMIT (Atomic Energy States.value comparisons.)/( .gt. 1932) for most of the experimental data used in tiiis book in energy. Nil. In La II the configuration is high and lies in the midst of many possible perturbing configurations.8P) 150 np 2p z 2 C N Ge Sn I II M3 114 114 148 150 139 1843 m 2p* 2p* Si I I I La H Pbl 3p 2 4# 2 5p 2 Gp 2 6p 8 062 The departures in case of CI. W.). S. McGrawHill.198 in 3 11 THE RTJSSELLrSAtTHDERS CASE: ENERGY LEVELS is . SnI and Pbl there is 11 appreciable breakdown of LS coupling (see 3 ). &. This with the experimental values* to be compared Atom Theory Configuration 8 .1D)/(W . Similar remarks hold for S II. the terms in order of increasing energy are is 7 P. These configurations are considered in detail As F% 3 is 1 essentially positive. OIII are probably due to action of the configuration 2p %p above.gt. The same remark holds for Si I. In Gel. In the (3". so the good agreement here is probably accidental. 57 unless there ambiguity.
In the case of SbHI the 5s 2 6s *S and the &? 2 &PD are 2 2 2D interval. while ( 2D) is 507 which. while ( D)=08 which is very OH much smaller. Fz.n s). 20J where JFO =3 Fj( n P&.gt. (G . Evidently ( 2 S. where of course the is 0^(np. so the agreement is fortuitous (see 3 3 shown to agree well with the theory for intermediate coupling).*D)I(*D . Similarly in the ( 4P) is 143 and 1 14 from the 2 2 intervals. this is roughly half of ( 2 P) = 4500. 2 $ 2 D interval.57 FORMULAS AND EXPERIMENTAL COMPARISON 199 The firstorder formulas give 2D) = and 2 P) = 0. nP) + 3 ^o( w * P).S P) 150 114 150 . so the actual term ( ( intervals must be referred to perturbations or breakdown of Russell Saunders coupling. although not zero. is quite small relative to the others. as it should be. nP) &.gt. +0.2D)/( 2DP) = i 4 2 where P = (2 P + P). &i= This configuration for O I is discussed in 28 . The Configuration Theory I np 2p 4p 4 Te I In 01 there is is departure 8 probably perturbation by 2p 3p and in Tel the coupling 13 where Te I is great. roughly half of ( P) = 274. 2s 3s $ nearby and located so as to increase the $ . ( In Sb III 55 we find 2140 and 2400 (cm1 ) for the two values of 4P) inferred from the two intervals.F *( n P&. but the ratios are badly off: 358 and 0481 respectively. Sblll 5s 5p 2 and Oil 2s 2p 2 here the order of terms is right. ^ is located so as to decrease the 2 52&. The formulas data are are the same Atom as for p2 with 6P (* written in place of _F .gt.gt. There are only two cases. In 2 Oil.
In in accord with the formulas. (1927). where the configurations are high and surrounded by perturbing configura tions. Using means eliminates a theoretical ratio (PF)/(. N II and 2 probably because of perturbation by p 3 3 Here the ( D) and ( P) should be equal. 364 CADY. then below for P and then above for D. nor in Ytll. In Gel 4p 4d and Zrlll 5p 4d the means are in the theoretical order These show the singlettriplet alternation as the G s} but the ratios are 028 and 358 respectively instead of 0555.F~D) = . 322 (1933). Thus the theory predicts an alternation: singlet above triplet for S. . I 7 from which . 22. and find (S D)I(D P) = f for the interval ratio of the means. Nil and OIII. so comparison vertically tests the Lande interval rule and com 3 3 parison horizontally tests the theoretical equality of ( D) and ( P). it is This lowers the for Ca I (P F)j(FD) is negative the higher stages of ionization the behaviour is more and Sc II. Sci.* may eliminate G s by dealing with the arithmetic means of corresponding singlets and triplets. We the J The means do not even lie in this order in the known cases which are in . This phenomenon occurs quite generally in twoelectron configurations. ^ 112 (ip) C I 2p 3p 106 102 125 NH 2p3p 2p $p 321 m The 304 292 352 653 820 734 682 inferred from eaoh of the intervals in the table gives the value of triplet. 43. Gel 4p5d. this is fairly well borne out by the data: III. Phys. The arrangement of the levels is shown in Kg. Rev. evident that the configuration is strongly perturbed in the low stages of 3 1 ionization. * P mean enough that the ratio f RUSSELL and MEGGEKS. Papers Bur.200 THE RTTSSELLSAtHSTDERS CASE: ENERGY LEVELS 2 is 57 We expect that 6? always small enough that (? determines the sign of the expressions in the G*B. but here the intervals inside terms are great enough to indicate appreciable breakdown of BussellSaunders coupling. The means do not giving come in this order in 01. The configuration 4p 3d can be foUowedf in the long isoelectronic sequence Gal to MIX. The 2p4p configuration in these same elements shows the same degree of agreement with the theory* in^. Standards. as is shown especially by the occurrence of the P below the P. La II. C I.
and G z which give approximately the best fit of the six observed levels.FORMULAS AND EXPERIMENTAL COMPARISON The 3 201 intervals P is partially inverted so a detailed study of the s Lande would be without meaning. 2 .) Kt Only one example is known: La II 4/6^. I configurations in the isoelectronic sequence from Cal to MIX. The calculated terms are obtained by choosing values of FQ . 3 jD being partly inverted.F) is 1*05 instead of the theoretical 035 ( = 7/20). s indicates a reason Similarly in CI 2p M the relation between the is why the 3 P is inverted.lt. 55 s Ca Sc n .?)/(? . The order of the singlettriplet means agrees with theory but the ratio (D . P Jp isr ?p__ 5zI ag &. Tim viv CrV FeW CoVl NIK The Fig. 3 5 I 7 g o 3 2 j ". . ^ numbers. although the conclusion uncertain because there are large deviations from the interval rule. The interval rule is not satisfied. (Scales in thousands of wave ipM F .=&.gt. The theoretical relation given in the table imply the = it 3 ( which makes larger than clear 3 why the P intervals are so small since (*F) is enough D) to make 3 ( P) almost zero.
in which (m) is the mean of the s for the two 2 J7s. zero. indicated by ^L. n p} GF? = Gi(n p. but the graphical F As they are not we must draw a line on the graph so that the F method is accurate enough and gives a better idea of the nature of the fit.202 THE BUSSEIXSAUEDEBS CASE: ENERGY LEVELS 57 Here we have the first instance of a configuration in which a term of a particular kind occurs more than once so that the diagonal sum rule does not suffice to give complete formulas. In is DPF in Sc I 3d 4s 4p which is probably strongly perturbed by the order is Ytl and Zrll 4e5s 5p correct but with large depar z by 4d 5p.d) Gf^Gz (n p. tures from the ratio. The terms are 2 2 4PD. ri d) Gff = GJna. If the F& coefficients were all A F . Of course the parameters can portional to the coefficients of be chosen by some analytic process like least squares.F. as investigated . r n". the points should is lie on a straight line whose slope is F% and whose intercept Q ordinate differences between the points and the line are as closely pro as possible. convenient graphical way of doing this is to plot the observed term values as ordinates against the coefficient of 2 in the formulas as abscissas. The values of the parameters chosen so as to give the best agreement with the data for 2d* in the isoelectronic sequence Sc II to Ni IX. The formulas  give the energies of the means of the pairs of doublets. is n". and Of = Q^na. probably mainly because of perturbation Regarding the J^2 and jP4 as adjustable parameters we have here four term intervals to be expressed in terms of two parameters.d) The predicted order of the doublet means expressed in The order 3da 4jp.
7id)+2Fo(7id Q 9 n s). The S term is much too low in every case. 0*TII AAJrl Sell Tim V IV CrV Mn VI Fe VII CoVffi Ni IX YII 7 Fig. The interval rule and the relation 3 ( P) = 3 ( jF) are quite accurately fulfilled in the long isoelectronic sequence studied by Cady. 2 ionization as they should. Similarly La II 5d 2 seems to be strongly perturbed by 5d 6s. The accuracy with which the other terms of these configurations are represented by the theoretical jP4 (3d 2 1 I . 3 7 There is no obvious reason for the discrepancies in Yt II. Parameter values in the configuration d 2 . cannot be represented at all with possible values of F% and F^. 2 . * Ft^F^Jnd. loc.* are shown in Fig.FOBMULAS AND EXPERIMENTAL COMPABISON by Cady. the hydrogenic values being J 2 (3d 2 ) = 203 and = 1472 in cm".  G2 Here F =F (nd. left formulas in terms of these parameter values is shown in Kg. 203 They vary roughly linearly with the degree The values are something like 80 per cent. n ^)? G z =G 2(nd. . CADT. so it was ) out of account in determining the parameters. T larger than what is given by using hydrogenic radial functions for the oneelectron 3d states in 8 6 15a.n s). probably because of strong perturbation by 4d5s. of 7 . cit. The Zr III 4d2 configuration .
3d 2 4d {Scales in thousands of wave numbers. 4d* respectively. The best parameters are 2 J = 905 and 2 According to the formulas first 4 should equal 2 JP This two cases and not at all true in the third: f .?&. 3 . and (? are the same as those of *#. 1 Neglecting the %S which Ytl 4d 2 55 with the values much too low we may Ytl 434 32 fit Till 3d 2 4$ and TiH J as 7 2 ^4 1015 59 shown in Kg.lt.gt. 3 P. l 0U _/_ Til F^..D 15 \~  //&. NiH Zrl 3d 2 The configuration d2 is . . P. configurations overlap 2 and interact with 3d3 and off. .lt. roughly true in the 2 ( very poor.4 P J is only Tin Ytl 3964 4357 is Zrll P. In Zrll 4d 2 5s the $ is not so badly although the i?G 20j fc : &.) agreement in general J4 =55. G in d\ *D 2 9 J( J+2*F).204 THE RUSSELLSAUISDEBS CASE: ENERGY LEVELS observe that the separations of 1 2 . 4 These . We 2 2 ( P+ 2 4 P). is D 3 5 P. where effects of configuration interaction are discussed. _ Y3I 2 ScD Til VF CrV Mn\[ FeW CoTO 3d 2 7 Fig.4P) 6620 1877 5404 (*FfF) 4558 Further reference to these cases made in Chapter xv.
The five singlettriplet differences are represented by (? = 2230. Fig. 4 . f I9r 18 17 IB 15 14 13 Y 7 Fig. F = 6. I 4d* 5s 2 Configurations d s and d d. As before the 1 /S is much too low and was left out of account.  The best example of this configuration is Sell 3d4dl. .57 FORMULAS AISTD EXPEBIMENTAL COMPABISOK dd 205  8(7. The parameters used are F% = 107. (Scales in thousands of wave numbers.) 4 7 shows the relation of observed and calculated singlettriplet means.
D I 20534 20506 21467 21191 I= 16: G 19038 19323 H 23680 22598 25214 25216 The G parameters were fitted to the the values being 1 sentation of the data for the singlettriplet differences . This configuration is discussed in detail in iJGT. (?5 = 378 with the following repre .? 57 G 2 = 367 and Observed Calculated 4 = 35 in the manner shown in the table: iS~*S 3872 6368 tPtP 4275 4385 TD*D 4384 4492 iJajF 3935 3810 *G*G 4864 4760 Other known instances are Yt II 4d 5d. This configuration gives two by the diagonal sum rule: 2 D terms.3576.lt. cit.i was of use in the P 4/ a case in which knowledge of the theo analysis. Zr III 4d 5d and the agreement is La II 5d d where not as good. P (? 3 = 297. Zoc. .lt. so we can obtain only their mean It is interesting to note that 2 P and 2 H have the same firstorder energy.206 THE RUSSELLSAUNDERS CASE: ENERGY Y LEVELS &. 1042. D 3279 3397 F 6112 5837 G 4879 4987 H 9690 11330 Observed Calculated 4421 4638 This gives a beautiful example of the alternation in sign of the singlettriplet difference with increasing L. p. the singlettriplet differences are entirely in disagreement in La II. 78 . F%= 115. ^=1^0 + 10^+ 3^^(15^ + 10^3+ case is 6?5 ) {(*#)= The only known retical formulas La II 5&. * CONDON and SHOBTLEY. The triplet intervals do not follow the Lande rule sufficiently well for a comparison of the s. observed separations by least squares.F Observed Calculated = 21400.* The singlettriplet means are s well represented on taking .
57 FORMULAS AND EXPERIMENTAL COMPARISON /3 and// 207 The formulas for// are F4 + m6J 6: 4 . The intervals are given by G. The determined as . 5 7 The comparison ^ . F. known at present._ No case of //is 2 .? 6) G^ + 3 78(? 6 ) I = The formulas sions in the 3 !/S. Terms in the nlx configurations. ^6 = 0262. the secondorder perturbations are usually quite important. intervals in the triplets of La II 4/ are badly perturbed. with observation is shown in Fig.^ 4  286&. configuration of Let II.F 2 = 9333. so without the Pauli principle the number of different complete sets possible with x electrons in the nl shell would be Nf The exclusion principle however . effects a strong reduction in this number. 2 although the firstorder formulas agree with the data in many cases and explain some qualitative facts like alterna tion in sign of singlettriplet differences. for (? s S P. But one/ 2 is known: LaII4/ Using least squares the F parameters were = 2158. iD. 2 _ fo. / are obtained by omitting the expresand noting that the allowed terms are: 3 1 1 /. The number of different individual sets possible in the nl shell is JV/= 2 (2ZI1). 6. The upshot of all these comparisons is clearly that. since it requires that all individual sets in a complete set be different and that two complete sets containing the same individual sets in a different order not count as different.lt. is Therefore the number of states associated with the configuration nlx . These are commonly the type associated with the lowest levels of an atom (compare I 14 ). T. It is of interest to consider the configurations in all which of the electrons outside of closed shells belong to the same shell.286.
For the configurations dx and/x the calculation of the terms by the method of 2 becomes rather lengthy. 29. The small numerals tinder the term designation show the number of terms of the kind occurring in the configuration. and WHITE. 604 (1934). . 782 (1927). J I and has maximum in figurations increases with increase for larger decreases symmetrically value for x=*NJ2.gt. Therefore the complexity of these con a? to the middle of the shell and then xuptox^N^ x configurations s The RussellSaunders terms corresponding to the and p have been x considered already in the course of the preceding section. Phys. The fractions in parentheses give the values of a in the equations ($!/) = a z 21 f 1 Where two terms of a kind occur. * The term energies for d* are given by OSTROFSKY. TABLE I 7 RusseUSaunders terms and Lmd& factors for nl* configurations. &.208 THE BUSSELLSAUNBEBS CASE: ENERGY LEVELS *. the mean value of 21 f 1 and (SL) = . includes the s and p* configurations already discussed.lt. for completeness.f The values of (SL) as given by Goudsmit (loc. cit 4 7 ) for p and d electrons are also included. 790 (1927). 29. j &. Rev. Formulas for the term energies as expressions * in the F and G integrals have not been worked out. f RTJSSEUD. Rev.af for x for x a is given. . 46. . 67 x ff the binomial coefficient which gives the coefficient of z in (Hz) This number a is symmetric with regard to x=N /2 l since l I \ = I ^. ibid. but the kind of terms to x 7 be expected are given in Table I which. WILBER. GIBBS. Phys.
noted by Hund 3 * that the term of largest S and S and sets. in which case Thus a d shell this gives *$. 4dx and 5dx occur in the elements ZnI 3 the so YI to Cdl (the palla platinum group) respectively.lt. we can infer the value of 3&. value of the terms of highest multiplicity. Similarly of the sixteen terms 6 expected from 3d only one. and Q S in agreement with the table as x ranges from to 5. The largest m values. an 7 see that they remain fairly constant in the plotted against x in Fig. (21 f 1)..lt. This means that from the middle of the shell on the highest multiplicity diminishes by unity for each added electron and the associated L values run through the same sequence as in the It is first half of the shell.. an empirical fact.67 TEEMS IN THE nl* CONFIGURATIONS Sol to 209 Tlae configurations 3dx occur in the elements from called iron group. for the others we must take for ? ms negative and take the remaining w/s as large as possible. 6 first half of the shell. then reverse sign and increase rapidly in magnitude in We the second half of the shell. 124. It is easy to find the largest For x 21 f 1. For 6 example. satisfying the Pauli principle by taking different the terms of highest multiplicity have s = xl2. l2 = 11. 5D. in Pel. p. $. 2D Z F.. among these the term of largest L is lowest in energy. Hence m is clearly given l l by taking ma = m I. This interpretation of the trend of the observed (y SL) in the elements of the iron group in which the 3dx configurations occur. For x ^ 21 f 1 we can have ms positive for the first 21+ 1 individual sets and for these Smz == 0. . and G terms are known.J in each Linienspekiren. *F. The con x occur in the rare earths. (21 + 1) and the minus sign for x &. 14 . 8 and ML in the table of complete The result is that for this term the plus sign applying for x result affords &.gt. whose spectra are not yet analysed figurations 4/ in any detail. Even in the case of the iron group where quite elaborate dium group) and Lu I to Hg I (the analyses have been made the results are as yet far from complete. L m positive. These are .lt. it will be possible to have an individual set in which all s are &. It is easy to find an expression for the (y SL) of the term of largest L in these configurations by the method of sole occupant of the cell of largest M 47 since this term occurs as the . Using the formula just derived &. the normal configuration 3cZ gives rise to sixteen terms according to the table. but reference to Bacher and Goudsmit s tables shows that only the 5 D 3 ? Z F.gt. 5 is known in Mai.
Terminterval parameters in the 3d* configurations of the irongroup elements. giving more weight to the regions t. The triplet helium. PROBLEM Show that the term a doublet with of Mgiiest L value for nl x is a singlet with L =xl .Ja. but the result is rougher because the data are not as complete and the departures from RussellSaunders coupling are greater.lt. 6 7 . where I = 1 is large and consequently increasing the value of 3d A similar situation holds in the x palladium group where the 4d configurations occur.210 THE BTTSSELLSATnSTDE&S CASE: ENEEGY LEVELS (y$). They lie on a increase with atomic number. (a: . or (x^ 21 + 1). and in is we have seen that this simple approximation useful in correlating a large amount of empirical data on intervals between . Mg.2) if x is L=xl(x. Our 5 5 showed discussion of the relativistic theory of the oneelectron problem in how intimately connected is the spinorbit interaction energy effects. This is just smooth curve showing a steady what we should expect because with increased atomic number the radial function B(3d) will be drawn in toward the origin. The 67 element from the observed values so obtained are also plotted in the same figure.)= mately thus far by introducing the terms 2fc )LfSt { with 57 in the Hamiltonian. . 7. with other relativistic We have allowed for this interaction approxi &&.1) 2 if x is odd terms of even.
38. Phys. the Lande value of 2: These facts 1 1 (. GAUNT. Roy. v and v% being the velocities of the two electrons. Proe. in which a more refined discussion of the spin terms is necessary. Soc. Soc. The classical instance is that of the 3 3 3 3 and 4 3 D. according to Heisenberg.099 cm. 228. Zeits. Finally the last line is the direct interaction of the magnetic dipoles of the two electrons.) instead of have been the subject of a number of : papers* and are definitely related to the inadequacy of the usual approxima tion for spinorbit interaction. The spin contributions to the Hamiltonian. 153 (1929). The Heisenberg. In Chapter xi we shall see that is also quite suitable for discussion of a wider class of cases in which the spinorbit interaction energy becomes comparable with the electrostatic interaction of electrons not in closed shells. Rer. 499 (1926). Roy.^SSiforJS^for ^12 P In this expression C to be calculated simply for the Coulomb field of the contains terms which we have already considered in nucleus. Rev.77 levels of THE TRIPLET TEEMS OF HELIUM 211 a term. OPPEKHEIMEB. j fSi ( S. One is to adopt the model of the electron as a small magnet and to set magnetic interaction with the nucleus and mechanics. 383 (1930). 3 P 5 D terms are narrow and inverted. 35. may be written for the twoelectron problem as ((ri + e* o. The question has been approached in two ways. These triplet terms of helium. The other is to take the relativistic classical formula for the interaction of two moving charges and try to adapt it to quantum mechanics by methods suggested by Dirac s up the additional terms for other moving electrons by its classical theory for one electron. so the first line the theory for hydrogen. Trans.007 cm. and the departures from the Lande interval rule are so great that they were at first thought to be doublet terms. fiir Phys. But there are cases. 39. Thus for 2p*P the interval ratio is 1:14 1. Phys. BRETT. A122. particularly for light atoms. his first work being earlier approach is that originally adopted by than the relativistic theory of Dirac. The terms of the last three lines are given by purely classical considerations by associating * HEISENBEKG. Data are known for 2 P. The next two lines represent the interaction of each (r) is electron magnet with the field produced by the other electron. 461 (1930). 151 (1929). 142 .
and is beset with numerous difficulties. L^Si and L^S^ together If we 9 with terms in which mixed expressions like {r x x v 2 ) in L*S is found to be t Sl occur. The whole term on using the definition of ^(r^ in terms of the Coulomb field. The approach through Dirac netic s equations does not make use of the mag moment in the model. It starts by replacing the ordinary Coulomb interaction by the interaction law of classical electron theory which includes the magnetic interaction of the moving electrons as well as The velocities vjc and v2 /c are replaced by the matrix vectors p x and (3 2 of the Dirac theory and this term incorporated into a Hamiltonian which also includes Dirac s relativistic Hamiltonian written down for each of the two electrons.212 THE BTJSSBLLSAIJNDEBS CASE: ENERGY LEVELS 77 with each electron a magnetic moment eS[jJiC. is that made by who cases of 2 3 P obtains a quite satisfactory agreement with experiment in the of He I and Li II. The differences are akin to those discussed in 5 5 in relation to the $~levels of the oneelectron problem. rearrange the terms in the second two lines we see that they can be expressed in terms of the products L^Sly L^S^. The problem of spinorbit interaction in a particular spectrum is thus reduced to the calculation of the perturbation energy associated with these terms. visional details. . This shows in a rough way how part of the mutual interaction of electrons comes in to reduce the full effect of the nuclear field in the terms of the form L^Si and affords a slight justification for the use of U(r) in place of the Coulomb field for calculating spinorbit interaction in complex spectra. The most careful computation of the triplet structure Breit. But the whole situation is at present quite unsatisfactory and calls for more accurate treatment. so we shall not give further When the Hamiltonian so formed is reduced by approximate elimination of the small Dirac functions that go with negative values of the restmass term it is in close correspondence with the one obtained from the classical model. This procedure is entirely pro their electrostatic interaction.
In 1 we find that operators may be rigorously defined to characterize the resultant momenta of all the electrons in a given shell in the configuration. we may add the two J7s to obtain a resultant L and L and the two /S s to obtain a resultant 8 and 8 for the n 1 1 1 and n 2 1 2 electrons 3 by the formulas of 14 Then in terms of these states the matrices of 17 s l and $ s of the n P... configuration.* In this section we consider the meaning of vector coupling in antisym metric states. but this operator will not be the sum of two com muting angular momenta. Rev.CHAPTER VIII THE RUSSELLSAUNDERS CASE: EIGENFUNCTIONS In this chapter we discuss not only the calculation of eigenfunctions in LS coupling in terms of the zeroorder functions. In the antisymmetric state characterized by the quantum numbers riWm^w^. while 7 discusses the calculation from these eigenfunctions of the separate energies and Lande splittings in cases where detailed results for the 1. Phys. and will not have the allowed values determined 1 1 by the addition of a vector Z to a vector Z Hence if a group of equivalent electrons occurs in a configuration. 43.. . This enables us in 2 to introduce a characterization of LS coupling terms by parents and grandparents and in 3 to calculate the Lande intervals of a term from those of its ancestors. not trying to define the angular momentum of less than the whole group. whole group as a unit in our vector coupling. But if n P2 1 eigenstate of the operator Z^ofthe% ^electron. and 6 are devoted to calculations of eigenfunctions proper. . But 2 2 we can no longer define an operator iofthe^Pelectron. however. 40. n 2 l 2 m*m$ . 4. M M . If n P also differs from all the other nl s. It is. Phys. The situation is roughly m as follows. it is an equal). with Vector coupling in antisymmetric states. of what operator is m] the eigenvalue? all the m^s are s ofthefirstelectron (unless Clearly not the operator l differs from all the other nl*& in the configuration.and n 2 l z electrons would be given by 9 3 11 and 10 3 2. still sensible to define a resultant L for the two n 1 ?1 electrons. These ideas are given precision by * SHQRTLEY. Rev. and the extent to which the matrix methods of Chapter are available for use in connection with such states. 197 (1932). if T^PsTi ? since no operator will distinguish between the two electrons in an anti symmetric coupled state. but the question of the mean ing of quantum numbers referring to less than the whole atom for anti symmetric states. 627 (1933). 5. . two terms of the same character occur in a two 2D s of d?. we must be content to work with the . For a discussion from the point of view of second quantization see JOHNSON.
. 58 .f denote the antisymmetric states of this group by We The products X (Ai) Xn (An r ) (4) of functions of type (1) and functions of type (3) are functions of all N I+ U electrons for which the matrix elements of j have the values =N N = (APIA S 8(An A n).NT ) in a given configuration I. where Here $1 is (Af Agl^jA J A g).. THE RTTSSELLSATOTOERS CASE: EIGEKFUJSTCTIONS I8 the following consideration of the coupling of two inequivalent groups of We consider a group of I electrons (1 .. Here II is any configuration inequivalent to I.^ p for the states of a given 2 zXf) (2) term are supposed to be chosen so that the matrices (A^I^A St and (A^jA *) of L I = L l + L 2 + .f&. I9 but the sum of the angular momenta of the N electrons in configuration I. L1 vanishes.k^zxK)&.lt. are the indices in of the electrons in configura tion I. expressed as a product of oneelectron functions as in 2 6 5 has the same effect as the operator cf&. Nj) configurations related in this way will he said to be 4s. 3L . Q ) (X AniAi A*)..lt.. 9 . the matrix elements of L1 have the values . 4. . N states by (i) X^&UMIMD^W. . have quantum numbers A inequivalent.NI + N u ) a configuration II whose nl values are all different from any in I. where a. . Sj Nl (1 ) * The phases in Consider also a second group... La 4. Xgi(Ai) XOII (AH) iXoa (A i) XOTI (A H) = (A* A* U\Xi A n) S(&. 6s how to determine these linear combinations. (6) (7) 1 .Lb + 5 } &. N^ Q is restricted to be such a permutation that the electrons in QI and QI1 are ordered... functions of the type Such a state will be a linear combination* of products of the JVj oneelectron xI (Ai)= m*raf SamX)P &. not the sum of the angular momenta of electrons 1 .214 electrons.S have the values given by 3 3 7. we define L1 as that operator which when acting on a state of configuration I f II. We make corresponding definitions of n S and Sn For states formed by the exchange of electrons between groups in (4). Explicitly.. 5) (AiAglljIA jA g) ( 1 Let us now define a new operator L to represent. When acting on a state of a configuration which cannot be represented as I + 11.b ... Let us denote the allowed terms for this configuration by the quantum numbers y1 S1 L1 and the corresponding antisymmetric . ofNTI electrons in (JVj +1 9 N I + 2.. the set of electrons which the permutation Q of electrons N puts in place of electrons 1 . 1 ...gt..lt. + L and Nl = S: + 5*2 f . We shall for convenience call * We shall see in J f The symbol A J Two indicates that group T of electrons (1 . ...lt..3.gt.
Matrix components of L1 between states of two different configurations are of course all zero. The matrix components of L1 between states of the type (9) are seen from (6) to be given by Hence. state of type (8) gives (12) where (A*iAn J^AiAH) = (AAg J^AjAg).1s VECTOR COUPLING IN ANTISYMMETRIC STATES (6) follows (6) is 215 such a permutation an exchange. . and which vanishes otherwise. . . The expressions of 1C 3 matrix components of ./.. . the states T of (9) have all the properties of the states of 6 3 1 with respect to the angular momenta L1 L11 and again with respect to S1 Sn Therefore we can use the formulas of 14 3 to add L1 and JLn or . I II = JL I + n = J ? (11) I  11 . M\. Since the states in the summand of (9) are all orthogonal.lt. We may easily construct an antisymmetric 1 2 9 .FN let us similarly define F1 as that which behaves like Fa + Fb + . (13) and a is a state of a configuration which cannot be written III + IL* Similarly the action of F11 on this state gives in the form (U) P For example. when acting on a state of con operator figuration I + II. and is hence an allowed antisymmetric state of configura tion I f II. if configuration I is d* and II p 2. to obtain states where 5=S + 5II =S + S for the VW&IfilPJSPIPtSLMsMi). will accordingly hold for this system of states. . n . * rf . A similar statement holds for the corresponding operators referring to configuration II. For any quantity F = FI + F 2 + 4. iS1 and *S n or both. linear combination of these eigenstates: J (9) where the summation runs over all the Nl/NjlN^l exchanges Q. and g has the parity of Q. S 1 L1 Su . . Formula resultant of operation from the fact that the by L1 on its operand in the same as the result of operation by LQ^ on this operand. Then the action of F1 on a . 9 (8) thus an eigenstate of (S ) (L1 ) 2 S* L* with the quantum. L . Y is normalized. . &. a typical III is while a typical a is P 1 has of course no components between configurations differing in more than one electron. The is state X^A 1 ) X$n (An) s Q XT (Ai) Xn (An) . numbers 1 S 1 M\.. .
This by coupling in all possible ways the S means that we can obtain the allowed by 7 terms for any configuration by using Table I of allowed terms for groups of equivalent electrons. ft THE BUSSELLSAinSTDEBS CASE EiaElSTFUNOTIOKS : I8 Is a state of a configuration which cannot be written in the form From 1 these formulas 11 we F= F +F XQi(A connecting states of configurations I see that the general matrix component of + II and III 4. and (10) 9 . and III and IV must be figurations inequivalent. Here con I and II must be ^equivalent. and those F as we see that in evaluating these matrix components joining corresponding coupled states of type (11). Genealogical characterization of LScouplxag terms. and that these terms will be characterized the terms of the constituent groups. As pointed out in I 7 a term is not in general completely characterized by its configuration and L value since a given configuration may contain several terms of the same sort. . we have found that the matrix components of a quantity of type F between an antisymmetric state of configuration 1 4. we may treat F1 h F* where F1 commutes with Sn n and F^ with S\ Ll If F is (13). 2.IV may antisymmetric states of I and III states of II and IV in just the of electrons in the process of antisymmetrizing as in (9). the matrix components of 1 and 11 between states of type (11) F F be given by the formulas of 1 1 3 To summarize. Where a group contains three or more equivalent d or / electrons.II and an will . be reduced to those of FI between and of Fu between antisymmetric way we should if the uncoupled states of I + II and III f IV had been taken of type (4). If we divide the electrons of a configuration into two inequivalent groups as in the preceding we see that the allowed terms of the con paragraph. . figuration may be obtained as in 181 1 and L vectors of the groups.216 where IjIV. and commutes with the other.IV is mX ) Hence the matrix components of the type (9) F between two antisymmetric states of are From this. . We shall now investigate the allowed terms from a vectorcoupling standpoint with a view to obtaining where possible a more general characterization and an introduction of the important concept of parentage. a vector of type T ( 83 ) with respect to either L or S. without exchange antisymmetric state of III 4. we cannot distinguish between the terms .
The terms built on each of the parent levels have essentially the energies of a single valence electron moving in a central field due to the ion in a particular state. They are designated X ( in this way even when the number of terms P) d gives a pentad containing only three terms 2 PDF. *D d 3 ( D) p PDF. Large interactions between configurations are * e. each 2 2 is individually characterized by giving the terms of p and d from which ion. we obtain the terms sd s sdp sd(iD)p*PDF s s *&. the configuration sdp contains a doublet triad having as parent sd( lD) and a doublet and a quartet triad having sd(*D) as parent. For this spectrum the centralfield approximation which regards the electrostatic interaction as a small perturbation on each configuration is quite invalid.PDF s dd (2) f sd(TD}s*D 3 d ( 3D) s d C~D) d ZJSPDFG d ( SD) d *. Thus for the hypothetical configuration p 2 d 2 the allowed terms are 3 tf&. triads. since it in this group except by giving the actual eigenimpossible to divide such a group. the electrostatic interaction of the core is larger than the separation between configurations in the centralfield problem. is not as large as indicated.gt.5Pi&. and pentads respectively* (in general potyads). Hence the eigenfunctions which arise in the convenient theoretical designa tion by parentage must to a certain approximation be the actual eigen fanctions which diagonalize the electrostatic interaction. the it When one electron is added to an . . in Fig. and 3 J". Thus if we consider the addition of nonp. in the example above.g. and d electrons respectively to the sd configuration of an equivalent ion. ( P) d* 1 ( S) 3 P 3 ( 3 ( P) 8 P S ( P) i. and d electrons are called monads. The occurrence of these close groups of three or five terms was noticed empirically soon after the beginning of the analysis of complex spectra. P) *PDF (1) (iD)iSPDIG 3 ( P) *PDFGH Although there are arises. I 8 of the energylevel spectrum of 1. six each of 1 D 9 3 B. Thus. The groups of terms of the same multiplicity which arise from the addition of s.*. Z s *SPFG *SPDFG. of the low 2^ 3 configuration of II as limits. even when more than one term of a kind occurs. The reason for this is illustrated by the plot. This spectrum appears essen tially as the sum of three oneelectron spectra converging to the three terms . P s. .gt. terms of the ion are called the parents of the terms of the atom.gt.s occurring here.2s GENEALOGICAL CHABACTEEIZATIOlSr OF i^COTJPLTNG TERMS 217 more than once is occurring functions. p.
This shows aU observed levels except 2p 4 and 2s2p 5 *P (13. 3 2p fS) The energy levels of 2p 3 (*D) 2p 3 (*P) Fig.218 THE BUSSELLSAUNDERS CASE : EIGENF1JN". (76. .000 cm.CTIONS 28 among the low configurations plotted. Hydrogen levels are the perturbation of OII# 3 it is certain that the actual eigenstates of the p 3 levels are to a good approximation the parents of the plotted levels of O I. not only 40 30 2 D 7s 20 5 4: 3p 3 D &0  & 30 $0L. But whatever .1 ) indicated by broken lines. or triplet and quintet polyads. expected.000 cm. 1s. but between these and configurations high above the ionization potential which have other terms of II as parents for the agreement with the formulas of 5 7 of 2p 3 Bs 3 is no better or worse than the agreement of the II 2p parent.000110. . The electrostatic interaction of the valence electron with the ion causes only the small separation of the singlet and triplet. oxygen I.1 ). and the per turbations of this parent are caused by higher states of II.
. and Zr. different parents. 31.) (2) I8. such as those of Ti. 960 (1928).COUPLING TEEMS 219 In V. polyads we may expect an interaction between the similar terms arising from 3. In the first sum. II In accordance with the discussion at the end of we may evaluate each of these parts independently without troubling about the fact that the eigenfunction is antisymmetric.lt. in which case f(^)J^ will be diagonal with respect to it. This reduces the first sum known multiple of * GOUDSMIT and HUMPHBEYS. Phys. we may split the II. however. The parentage is not exact. This breaks the sum (1) into two parts.* With the we may easily obtain a formula for the intervals in the terms of a configuration I f II in terms of the intervals in the in7 equivalent configurations I and II separately. where the of configurations is not so exaggerated as in 1. (rz)L and S^ may then be assumed to commute with given by 11 38 U and S 1 11 . jj+If or & or S to a 3r*IP or SP.L or S. for as soon as the intervals within the polyads due to the electrostatic interaction of the valence electron with the ion becomes comparable with the separation of the tion. Q^fa) j&. in which case S^ will be 1 1 diagonal.gt. the levels of a overlapping given configuration will still be found to occur in groups (polyads) having approximately the relative locations of the terms of the parent configura many of the complex spectra. 1=1 (I) We have omitted the sum over y because each quantum number in y will in general either refer to the spins. If now the term ySL is derived by the addition of the term S L of configuration I and the term spinorbit interaction into S11 U1 of configuration II. in which case the factors are each if we correlate L&. Lande intervals for terms results of I 8 of coupled groups. From 3 2 we find that ( Y SL) = S (yLg(rt)L&L) (yS\S&8).28 GENEALOGICAL CHARACTERIZATION OF LS. Rev. one of which refers to I. or will not refer to the spins. the other to two parts lV:^ .
QS&IP)**^. consider the deter mination of the matrices of * S2 and LS in Pfcys. 39. 197 . L and S The direct method of obtaining eigenfunctions characterized by SLM S L 2 is to diagonalize the matrices of and S2 in the zeroorder nlmsml scheme. . if we wish states characterized by SLJM. Since such a diagonalization does not give states with phases chosen in any particular way. Calculation of eigenfimctions by direct diagonalization. the nlms (1932). it is necessary. In order to use the formulas of 14 in the way we have sketched.220 THE RUSSELLSAlHtfDEBS CASE EIGENFUNCTIONS : 38 The second sum is similarly reduced. for greater convenience. of L*S). to diagonalize also the matrix of JT2 (or. if a single ril electron is added to an ion. Dffi(ffl+i)+s^(s^+i) rtanr ^ (4) By this formula. 2 . M Because the process little is laborious and the phases arbitrary. m l scheme because JOHNSON. the values of for any configuration may be expressed in terms of those for configurations of the type nlx which were given in Table I 7 In particular. by SLM8ML by by SLJM are given directly in terms of states the formulas of 143 States characterized .* We wish now to show how to determine the eigenfunctions of states in LS coupling in terms of states in the zeroorder nlms scheme. Rev. We Z. . nevertheless. this gives the correct answer even the electrons are equivalent. this method has practical application. These considerations reduce the problem essentially to the deter mination of eigenfunctions in the 8 L scheme for configurations con 3 sisting wholly of equivalent electrons. . shall. m t States characterized characterized for configuration IfII are given in terms of those of con 8 figurations I and II by the general procedure of I this is discussed in detail by SLMSML 68 . it is however necessary that the relative in 8LM M phases of the states of a given term be such that the matrices of have the values given by 3 3 7. shall show in 6 8 . Formula (4) gives the values of f immediately for twoelectron configura tions nlril if we take ^ as and if we 4. . to obtain finally 2L(L+ .
b while A has a & This component has the value . (4b) N is the number of electrons and dividual sets with the * It is A is the number of pairs of same nlml9 each pair counted only once.M ).gt. (The sign is in all cases to be chosen positive or results negative according to the even. say a and b.gt. . A those in a. .wf). differs Sz We get nondiagonal elements of S2 only if A from A in two individual sets.lt. say that A has the sets a. . Because the simultaneous diagonalization of these three matrices is an excellent illustration of the process of matrix diagonalization described in we shall give detailed results for the configuration p 3 The matrix components of L 2 S*. (2) This property will be of use in Chapter xn.6 where a and Matrix of 6 run over . A b). 72. all stand at the same places in the lists.M ).w Pmf)8(mJl. with a! V corresponding to r to Matrix of L 2 We get nondiagonal elements of JL 2 only if A differs from A in two individual sets.mJ)i. (la)* (a\Sx \b) =8(*Zmf. (3a) The diagonal element a (3b) a&. scheme may be easily expressed in terms of the oneelectron components (cf 3 3 4 and 7 3 3) . In this way the following are obtained. This component has the value (A\S*\A )~ 4{(a\Sf \af)(b\8x \b )(a\8x \b )(b\8f \^)}^Jf. (a\Lx \b) (n a la m%mf\l (mf 1. and L*S in the nlm/n. m\) ffiV(l b m*&. . (4a) The diagonal element of S2 is (^15 ^)=^(Jflf^~JV where 2 ).)(l b + m\ + 1). mj . (A\L*\A )= 4{(a Lx \a of JL 2 )(b\Lx \b is )(a\Lx \b )(b\Lx \a )}8(M. T/ in to be noted that for any of these quantities (n a l m wij \n* I* mj mf) =(n* l a m m b \n V&. .or oddness of the permutation which changes the set A from its standard order to the order in which sets in 1 which match . ft (lb)* (lc)* 6 6 by the formulas of 6 7 and the relation 3 3 6. all the individual sets of A.4s CALCULATION BY DIRECT BIAGONAMZATION 221 our discussion in Chapter xn of transformations for configurations con taining almost closed shells will depend on the properties of these matrices.
(5a) (A\LS\A )={(a\lS\a )2 Z(a\La. } . namely (%) When either of the last two terms . it has (a\L*S\a ). does not vanish just the value (i. (a \L. D.e. This configuration leads to the five levels 4/S . C M ). A JB C D E (6b) . The part of a diagonal element which results from a closed shell is easily seen to Illustration. the matrices of S2 2 . a.M regard to one individual set. This method of calculation be illustrated in detail for the 2 case of the configuration ^J3 . the third term vanishes + except for one value of c. The nondiagonal elements are obviously not affected by the presence of closed shells. we see that the terms 2P and 2J9 have states in both box a and box /J. Only those sets of the configuration which . 2D. when the appropriate 6 or c exists in the set A).. be zero [using 3 7 5 in the case of (A \L?\A)]. the zeroorder scheme. and L S have the form the lines in the matrices indicate the separation between a and j3) A and JB. will The configuration p*. Hence we may infer that the eigenftmctions for 4 will not involve  m . where 6 and c run over all the individual sets common to A and A It is worth noting in connection with this formula that one obtains no value + The second term in the braces unless a.2 I. (mz 1) vanishes except for one value of b namely (m^ 1)~. The diagonal element of *Sis given by With these formulas it is rather easy to calculate the matrices of i 2 S2 and L Sin.\e)(e\Sa \a)}8(M. )(b\Sx \a ) ). a and we obtain (a \Lx \b If A differs from A in )(b[Lx \a )(a\Sx \b )}S(M.\b)(b\8ie a ". 2Pj.!. The zeroorder states for M= M J are given by 0) 1 I (10+ (!+. 1) i r i C (6a) D E If we make a plot such as 4 1 ? 2 while states has a state only in ]3. differs from A in regard to two individual sets. IfA 6. a are of the form (m/)". 2P.222 THE RUSSELLSAUNDEES CASE EIGENFUNOTIONS I f 48 Matrix ofL*S. are outside of closed shells need be considered in calculating these matrices. In this scheme. (5b) . (cf.** 7 2 for notation. We shall consider only states characterized by = J this will give us one state of each level.
2 and *S2 are concerned a and j3 are quite independent. (6f) . are diagonal by 11!.) is not uniquely determined for either pair of When the matrix (6c) of I. For formation which diagonalizes this matrix is found by the method of 7 2 : S . Consider the matrix of 2 For a. 2 the relation (cf. Sz Lz . the eigenvalues of S 2 which may occur are those corresponding to the two we have in addition to these the quartet eigenvalue ^f. namely f and f . A \\(A\*M)\\ (6e) (Because of the degeneracy this transformation doublets.CALCULATION BY DIRECT DIAGONAIJZATION 223 ABODE (60) ABODE l\(A\LS\B)\\ = p*. (6d) So far as the diagonalization of Z. trans doublets. 7 2 7) is transformed to this scheme in which S 2 .
for both the stepmatrices to P and D.. . The eigenvalues of Z. as required. with more useful phases. *!&.gt.L scheme may be * We have chosen the A phases so that 2 PW .224 it THE BUSSELLSAUNDEES CASE EIGENFTTNCTIONS : takes the form *. the values of M 3 and MI being indicated by obtained by the or j8. The  and . 2 is diagonal with respect to $. states are now in the SLMsAfz scheme.. TA nmltiplieation transformation from the zeroorder scheme. 7=6) of (6e) by (6h): to the SLMSM. /S= are now known to be those corresponding transformation which diagonalizes (6g) is given by whicli a. oc atiu fl p .. (of. 8 (6h) The new a. cc jina Q p have the * * proper relative * phases as 2 determined by the method of the next section. namely 2 and 6. and so that 2 Pf ^i* ^ an(l  are the proper linear combinations of these states as given by 143 In this way we can make full use of these matrices without having to rewrite them. .
gt. f.j. 2P.8 CALCTJLATION the matrix (6d) of L BY DIRECT DIAGONAUZATION scheme. p. 1.gt. is then given by the product of ^ & (6m) 11 D E * See footnote to (6j). The eigenvalues of this matrix are calculated from the formula LS=MJZ L 2 S*). as required. J. a l&. it 225 When S is transformed to this becomes (6k) which is diagonal with respect to L and 8. and for 2Pj. 224.*jZ&. and ^s respectively. The transformation to these states is given by (61) TAe transformation from (63) and (61): the zeroorder scheme to the SLJM scheme.. . which gives 1.
From the results of interaction in the zeroorder scheme A B CDS (7) When this matrix is transformed by (6m) to the SLJM scheme. We shall need to discuss only the transformation to the SLMS L states. 5.gt. Phys. so that the results of 14 may be used directly to obtain the SLJM states. &. ML = L. . . In this way M &=L S ~S. SL ) this M 9 found with the proper relative phases for all 3 states. hence the states of different terms have no particular phase relation. . it becomes (8) which agrees with the results of 5 7 The same eigenvalues would have been obtained by trans forming (7) to the SLM s M_i scheme by (6j). Calculation of eigenfunctions using angularmomentum opera tors. and the x operator ?~Sx iSy to give ^(SLM8 lML ) and so forth. In order to carry out the operations mentioned we shall need to know the and f on a state expressed in terms of the anti result of operating with zeroorder functions (m J m] m mf Since J5? = ? l + ) symmetric 2 + we have from the general relation is the whole of an term M &. 38. . (1) * GRAY and WELLS. . directly the electrostatic energies which were obtained in 5 by 7 6 and 8 6 we find for the matrix of electrostatic the diagonalsum role.lt. . . The first state is found purely from orthogonality considerations. 248 (1931). . Rev.* We shall now give a convenient method of computing SL eigenfunctions proposed by Gray and Wills. . . .226 THE BUSSELLSAFNDERS CASE EIGENEFNCTIONS : 7 It is Interesting now to verify".=$? &.lt. . Having found the eigenfunction *(SLMS ML for method makes use of the symmetric operator iLy to give the eigenfunction ^(SLMS L 1) by 3 3 3.
calculation. so that operation by P siirn gives just the sum of the states resulting when successive m^ are if one has occasion to apply it. When we apply s to we find With The this formula the result of operation by J? on any state is easily calculated. E F G (2+2.1+) . let us obtain in particular let us obtain one eigenfunction for each of the two 2D s to use Illustration classification of the 7 8 for the separation of the energies of these terms. Before beginning the calculation proper. result of operation by f is very similar. # .F] H i 2 J K L N M (2+2. (2) it commutes with the operator $$ of 3 6 6. s for m= s J. down to . of and f\ the configuration . J. the s values being suc cessively decreased by 1 in place of the m^ values.1+) 0) 0+) 0+) f 3 D (2+1+ 0+) 4 [ . to obtain two (orthogonal) eigenfunctions for D. (3)]: of Our problem is. .1+ f 2 I (2+1+1+) (2+0+ (1+ 1 0) 0+) 2 D then. s L in M M jfrfff A terms which have components in each partition is given below jjfefff 7 (cf. d3 As an illustration of this method of some of the eigenfunctions for the configuration d*. (5) Sfl = 152 . is just the changed to mj~ The operator . cf. 2 together with the zeroorder states of d? according to .USE OF ANGTJLAItMOMEKTIJM OPERATORS the result 227 Since S? is a symmetric operator.1+) (2. 2 & ft". 1 for m = J.2+) (2+1+ 1) (2+1. 1 2) : Jfcf j\f^ (2+2 1+ ) B C (2+2(2+1+ (2+ 1+ (2+ 1 0+) . 2. let us calculate the action and f on certain of the above states [omitting the factor 1 . The coefficients which m occur are limited to 1 and 0.
) 3&. The 2 state 4.. f 3 = D. 2 = V^[2J + 3^ +i . any state orthogonal to the four above is a 2 and there are two linearly independent such states.a *) configuration question. 3) = . The other states 8 of this partition are both s. . M M 2 D D at random and a second orthogonal to it [.gt.gt. .228 THE RUSSELLSAUNDEBS CASE EIGENFUNCTIONS : 58 Now the state *H.K + 3 is 2H] . i 2 =30~V . 6. J.2Q *. 2 J. JfJf) represent one of the antisymmetric eigenfunctions of a given term of group I. \&. Calculation of eigenfunctions from vectorcoupling formulas. 3: . Any other A check is continuously furnished configuration is handled in the same way. 3 is determined by its orthogonality to the above three states for ^ We have now four states = of the partition L =2. But from (5).4M + 4^T + VO]. *[Vftff 43JT (6b) G. 5 is just A.20]. Let us choose one \&.gt. I (a J 3 . 2 G. 4 is a linear combination of B and C orthogonal to H S The choice of its phase purely arbitrary..K+L :=i l + N _ ] * =84~ [5J + 3JT+L4Jf3zY2V60]. i 3) = V3 4 ( J. By operation with ^ on this we obtain 4J^ . J. 3 =20". We have now 4J.2M . This is supposed to be known in terms of the zeroN for the 1 = in a2 order functions $ 1 XI (/S i I I (J. The other 2H s are obtained in succession: (6a) 2 #. . J. 4= 10[V&B.. Let us first consider how we may obtain the eigenfunctions resulting from the coupling of the terms of two inequivalent groups of electrons as inl 8 Let .J. From (1) we find that Hence J 2 #.G . \.3xV + V 60]. This procedure may be continued to obtain any desired state. by the fact that the states must come out properly orthonormal.
gt. Note that we are not here following our convention of capital letters for antisymmetric functions. these antisymmetric functions are obtained by simply s for I f II.( Let T(S1 given by SII SMS the linear combination of the r s which is ) designate 14 3 for the coupling of S 1 and S 11 . The product of these two states will be a X known linear combination of the form A. Xx Xn of (1) is then just and Y of (2) just (3) which we write as in as T(mjm)o&.lt.B This is antisymmetrized as in easily seen that is 1 8 9 by application of the operator *5/ . .. SLM ML s ) = T(Si S^SMs )a(VL^LML \ (4) where the right side of this equation is to be interpreted according to (3).gt.gt. 0)=2". small letters for all others. f BABTLETT.(mjmf). Let us write the function Y purely symbolically as a product of a function referring to the S s by a function referring to the L s: 1 T(# If M\ Ml .D &. Phys. hence the (2) In other words.S*IPMY n) = T (# /S11 Jf1 Jf I1 ) I? in Ml If* }.. 1.and IP. (3) S11 and of U.lt. s for I and II by replacing the products of 3 let us see how to apply the formulas of 14 to the coupling of $* and Now &. group II the other.^ eigenfunctions for a configuration consisting of just two nonequivalent electrons are given by these considerations if group I is one of the The electrons. l)^ f +) ^ &. 1. Making the correlation T( T{ T( * 1.gt.68 USE OF VECTOBCOUPLTNG FOBMULAS 229 Similarly let n (/S^ 1^ Jf * Jf *) be one of the antisymmetric eigenfunctions of a term of the second group.*[T(+ )+T(f +)] I)=r{). Rev.^*!)^^ for configuration I I an antisymmetric zeroorder function antisymmetric function II. let Q(ZJ i11 i Jf L ) similarly refer to the coupling of Dare given by y and D1 * Then symbolically.gt. M o&. It rf ^a^a^. 38. the k$eoupling states ^(fflI^ S^Ifl &. Two nonequivalent electrons. 1623 (1931).l&.
The first of the 2 $ s is given merely by adding + or 0~ to the single state of p p 1 /S and antisymmetrizing: which result. Hence ) ( .0+) ~$( . 0) =6~*[^(l+ .gt. !}( 1.".230 If THE KUSSELLSAUNDEHS CASE : EIGEOTTOTOTIOlSrS 68 we consider in particular the configuration np rip.0+) i r/Fk/ H. 0. l)=2^[a&. The &L eigenfonctions 1.gt.(Jft. (7) For the important configurations Il we have L .1 0) 0(1 1 we must add S1 = 1 to S11 = ( to obtain 8 = T(5=i.(l.gt. ( f ^ For the other 2 i. [r(0. .1.o(0. let us find the eigenfunctions for the two 2 $ s 3 2 3 Z namely pp (*$) s S and pp $) s $.lt.". 1. //vx [ OTUT = Z J2_j.1+ 1+)] etc. (pp) Is. Let us consider the addition of an s electron to the configuration pp to obtain pps. /f\tKT {\4\~\ { v ifS] ^ y ) Addition of an electron to an ion.(l. characterize the two 2 $ s of this same configuration in another considering the addition of a nonequivalent p electron to p s as l 2 parent.r4\ (^".lt.gt. This state is We may way by 2 orthogonal to the other $.gt. 1.l ^ f j +)].  1) = o&. .(0. with the correlation  =0. 0) (4) are then the symbolic products of T and fi: =*3~*[$(1+ . In particular.1(10b) !.1+ 1. 1) a&.l)] 0)=2~*[o&. 0.0)a&.1)] 1) (6) 1. 1)] H( Q{ JQ( I.(0. Jfi)=&.gt. 0)] O( 2. 0) +cw( 1. M ) = 2~*[&. .1+) $(0* 0*) +$( . as required. (for allJft) t(L. etc.*[cp(l.+)] i : T(flf=J.) V2 r( .( M1 .lt. Jtfj.Q).gt. If j=0) =:3". etc.)T(0.. The states pp^S and $ are given by (7). Let us obtain the eigenfunctions for ps (*P)p *S and ps ( P)p S.( 2~*[&. 0) &.) A \ .(M (8) Hence from (5) .Jf s = i)=3^[V2r(l.M ) = a&.a /7 .= i)=3". .
1+) 4 $(1. Let us.lt. In symmetrized states are general. by application of by these states are antisymmetrized to obtain states still but not necessarily by any other definite 8 SLM M L&. For the case of two equivalent electrons. and 231 to Ifl= 1 & to L=Q as follows: Q(X=0. see that the states (13) are quite different from the s} n ff np respectively. is in fact the following }\^ ( ] Two equivalent electrons.!+)( . 2 (13a) The states of the second $ are given by (12) and (9): +${0. some of the anti linearly dependent this reduces the number of distinct eigenfonctions.1+ 0.1+) +0(0+ 00+) +$((T0 0+) O( .. S12 L12 n^m^m^.6s For the obtain USE OF VECTORCOUPLING FORMULAS =1 first wo must add # = I to Sn =  as In (II). however.. 0. ri^m^m^. for configurations containing more than two equivalent 8 electrons. J. First. this is less easy than the method of 5 which takes full cognizance of the exclusion principle from the start. If certain of the electrons are equivalent. second.) Then.1) &. it is easy to see the effect of the exclusion principle and to obtain the eigenfunctions by this method. This difference of arrangement must be taken into account in a comparison of the two sets of states. when we use the functions . quantum numbers the operator characterized cS/ ? (The subscripts here refer as usual to the definite electron which has the indicated by the superscripts. etc. SLMS L . according to the formulas of 143 . n". The symbolic product of this with (11) gives. (12) (9). 1)]. quantum numbers. (13b) The quantum numbers np. couple the s s and VB of .0)=rl8~*[2$(l+0+ l)2^(0+Ori0)+2&.&(! 0+ 1)].10+ 1+)] J.1+ 0. As noted in 46 we may look at the exclusion principle from the following point of view: We build up nonantisymmetric states characterized by quantum numbers n^m^m^..0) +(!.gt. M . in these zeroorder functions refer to the electrons np 9 n p.&(l+0+l)O(l+Or. Jfi =0)=3~ i [w(i. however. In this way we may obtain aE the eigenfunctions for any configuration by coupling vectors and then antisymmetrizing.0+ . two things happen. the antisymmetrized states are no longer normalized and some of them vanish these are forbidden.s. . while those of (10) refer to We but since there are only two possible states 2 S. they must be obtainable from (10) by a unitary transformation. l) 0(0.lt.0+ 0) +$( . This transformation states (10). .
the important result that we can (15).l) 2 = ( . It is applied to an antisymmetric twoelectron function (3 ) = n in the eigenfunctions for the con jtfiff which we obtain if we set n &. Thus we obtain from (7) figuration T(^ while if we set 2 *8. The are forbidden. 1D Z F.. By 14 3 7 interchange of electrons 1 and 2 merely ..1) 28 8 = ( . *(2Z). = V2$(n&n& SLMS ML ) F^n^n^ S L M8ML (17) similar result holds for states characterized by J and M. 0) =3~*[O(1+.1) 5+1 Hence multiplies $ r by ( ^ M ". SLM M TU allowed terms for nP are hence *S. 3 .lt.$(1~ . we may write if cases in Chapter vn.2*^^^ SLM ML FiWn&nHfc S L M8ML n 2Z2 SL s ) 2 ) ) S y. This state is literally the product of an orbital function ^ r (n 1 l l n 2 l^LMI) and a spin function tff^s^SMg).\/%. the antisymmetric symmetric states states are all distinct since they all refer to different L and hence S is L are as all allowed. 3 P. 0. by ( .1) (0+ 0) .. Since the states are Y(nZ wJ SLMsMJ^n&nJi SLMS ML ) (15) Since the operator jtf has the eigenvalue V2l when 6 = 2~*j/^f. . T nln L Hence we can obtain the eigenfunctions for nl 2 from those for nlril by setting n = n and dividing by V2 to normalize.232 THE BFSSELLSAUKDEBS CASE EIGENFUlSrCTIONS : 68 two equivalent electrons to obtain the state ^( nih n SLMS L ). A m we must set those multiply the rest components from forbidden by &. and . . nP m for nonequivalent electrons.1+)]. f S already either antisymmetric or symmetric according to whether is even or odd.gt. these states all vanish. r this becomes ). obtain the matrix component of a quantity l 2 between two allowed Because of the relation we have F=F +F by giving quantum numbers n^s^ to electron 1 and nzs2 l% This permits us to use formulas of Chapter for such in the same way as we found in I 8 that we could use them configurations states of to electron 2. states of nl2 equal to zero. iff we have found in special normalized. on interchanging electrons 1 and 2 in the second term. For the matrix allowed state of ril* and a state ofriln l we have component between an V8 L M8lfL t ) r SLMSML F ^Wn^n^ S L MsML f ) ) M ML F ^(n^ $ S L MSML . Hence if we use the formulas of Chapter to find matrix components between configura tions nl 2 and riln V by assigning definite quantum numbers to the electrons.1)* and &. ( 1 6) n~n in s /Sf. SL is an allowed term.
_ L\ 3^21(^5^) 9 \* I +1 . JfL = 2.". Since Q is diagonal with respect of it will only be necessary to use independent S L. 2 s of 5 8 6e.H / J Since of a 2 ( 1) and (2) are independent of Ifs and ML . can * UITOBD and SHOETLEY. Thus we wish D 3V2l( F2 .OF VECTORCOUPLING POBMUIAS 233 considerations of this sort have been given for more than two equi valent electrons. No Separation of the 2D s of d3 . .57 J4 2 ) (1) which has for its eigenvalues (2) This formula then gives the separate energies of the two 2 terms. L =2. 167 (1932). The eigen = J. in regard to just one individual set.l 2) 2 = t(*D). however. that part of the matrix of Q which refers to a given L. 2) =T( D). may now be obtained. Hence H1 a quantity of type Jf.* When two terms of a kind occur in a given configuration. 7. \. Phys. for s M M D write the eigenfonction for either of them as we * A find 3J? ot= r/ I + 7^2 + 63*42 = . (4) Equation (3) gives the eigenfunction for D. by finding the complete matrix of electrostatic interaction Q by the formulas of 8 if we know to a set of i/Scoupling eigenfunctions. . 42. the same linear combination D and b 2D obtains for any state of the term. 2 in terms of zeroorder states = J.2\H*\*D. we have seen that the diagonalsum rule will not determine their separate energies or Lande splittings. intervals for these terms. These terms may be separated. Since now consider the absolute Lande 7 2 2 T( D. 4. S 8LM8ML and if MM SLM M to separate the two 2 s of c 3 we need only use the secondorder matrix connecting the two 2D. so that it is probably not possible to apply matrix methods to calculations within groups of more than two equivalent electrons. we have from 3 3 Let us (*D.l. . This matrix is found to be . Rev. Since these states all belong to the each characterized by 8 same configuration and have the same s and L no two of them can differ M M M .5F4 . If we functions for these terms.
710 cm1 which .1 higher than any Q Z c/) J G~ D 5  _ OQ 3 03 &.450 cm. The configuration d3 has the peculiarity that the calculated electrostatic 2 and 2 are equal. J&. TH 3d 3 . so that we can 7 calculate (4) entirely in terms of the diagonal components 4 3. However. In this instance these energies are not at all energies for 2 equal.1 The only ob 2D is at 12. as the theory predicts. . The . Fig. J4 =54 (3^=17. Till 3d3 tn CC id CD ?I5^ D 12. tn 2 agrees excellently with our lower D.as the correct value of as 142 2 1 di 1 . o o 3 other level of the configuration.gt. interval cm 1 .886.F V193J1 () We tions shall now see how these calcula 31450 compare with the experimental 42700 27300 data.000 cm".644 1250 *F P It If the formulas were accurately followed. In this way we find that 59^435^4 4 + 8325. 2 from the following list of values of d calculated from the observed intervals (beginning with the widest) in the . see Fig.750).234 THE BUSSELLSATJNBEBS CASE EIGENFUNCTIONS : 78 have no matrix components connecting two of these states. I O &.81*0 892 Z 2 H D 889 810 1027 *P 2 1467. vnr 3 3d 4d zrn s fairly s The d* configuration. if we choose D H P . so that we cannot depend much on *H and P. we find for the energies of the two 2 s . In the 3$ of VIII. If we take F 89 cm. 2 s If we put these values in (2). 2 is pre The position of the second dicted 10. The fit intervals in this configuration also well. we calculate from (5) the lower 2 is 1294. which may account for its not being found. the formulas This is seen terms: *J *G 856.lt. 2 is pleasing to find the inverted.820 served and 31.lt. first instance of d? occurs in 20 which although completely mixed up with d 2s gives a fairly good 2 fit for the terms exclusive of the D s with ^2=845. while the observed value The interval for the higher D is calculated as 3 677 cm". these values would be all equal. all the terms except *F and one 2 are known.
2 8 satisfactorily. with 309 cm".300 and 42. Phys. the second figuration. . who finds that he can account for the discrep by 2 in the above approximation ancies of Fig. we obtain an ap 2 36 (3. s&. the second D extremely high and inverted. .800 1 higher than any other level of the con ! which has a spread of only 16. 732 (1933).F = 16. proximate fit of aH terms except P with P2 = 683. predicted 25. The intervals as usual agree only roughly.891). 2 4 P 2 ? is fairly P J J D . if these are correctly classified. which gives an average value for . The better agreement of *H over 2 2 s in neighbouring configurations. the intervals are 248 and 110 cm". fF fits the interval rule is fairly well.300 1 cm". In this configuration again.869 and 14. F= With these values the calculated 2 D s lie at 1 11. Hence we must infer that.750 and 27.been considered UFFOBD. the *H while that of the is not.900 cror1 as analysed Hence it is not surprising that this second 2D was not found.* 2 parison with the theory.78 SEPABATION OF THE 2D S OF jF s to d* 235 the fit exactly. These 1 constants give for the values of the two 2 17. . in which two 2D s are reported. respectively.$. first of these is is agreeably close to the cm". 1 compared with the observed interval of 147 cm". . The observed 2 s lie at 13. is strongly perturbed by is explained by the fact that * The D P P P whereas there is no nearby configuration which contains a 2 H term to perturb the *H of d*. . as standard.700 cm". Rev. . in detail 2 interaction between these configurations and the assignments have ". one of 3 very strongly perturbed. The values of the constants good energy which are obtained in this way are 1^ = 1171.317 1 cm".559 cmr 1 with separations of 734 and D 435 1 cm*". These separations are separations of 593 and 2 calculated using the J?. d is com pletely mixed up with These are all the instances of c 3 which are sufficiently analysed for com them is d?&. In general we have seen that the lower J) corre 2 is predicted sponds well with the one usually observed. 44.000).lt. 4 = 83 (3 = 23. Tor the 4d3 of Zrll. The make the other three terms *F. and if we use the given by this level (which 2 calculated D about an average for the configuration).". 1 the first of these is to be . 2 D found by White at 16.gt.
The nonvanishing matrix component connecting dividual set is states A and B which differ in regard to one in just the corresponding oneelectron matrix element con the nonidentical individual sets of and B. Since the electricdipole moment From P which anticommutes with the parity operator of 1 1 6 it follows that P has no matrix components between states of the same parity. . fur PKys. and enables the spectroscopist to the to characterize such levels as uniquely even or odd. 23. 2. In 1 we obtain some general results concerning the possible configuration changes in radiative processes In this chapter which are true for any coupling. the results of previous sections we may immediately obtain two is a quantity important selection rules. from a transition between a particular pair of configurations is treated in the next two sections. Zeits. Configuration selection rules.CHAPTER IX THE RUSSELLSAUNDERS CASE: LINE STRENGTHS we shall develop the theory of radiation as outlined in rv to obtain formulas for the strengths of the various spectral lines Chapter for atoms obeying RussellSaunders coupling. Hence all . & spectral lines due to electricdipole radiation arise from transitions between states of opposite parity. vanishing matrix components only between states which differ in regard to at most one individual set of quantum numbers. Science. In 5 we develop for quadrupole multiplets the for mulas giving relative strengths of the lines analogous to those for dipole multiplets in 1. see also RUSSELL. Prom the theory of necting A oneelectron spectra we know that this matrix component of vanishes unless AZ = 1. is a quantity of type Since considered in 6 6 it will have non P F . In 2 formulas for the relative strengths of lines in a multiplet are obtained as a special application of the results of il 3 The problem of the relative strengths of the different multiplets arising . 512 (1924). where AZ is the difference of the Z s in the two nonidentical P individual sets. Hence if the energy levels are accurately characterized by configuration assignments. known This rule was discovered by Laporte* and is usually as the Laporte rule. Its importance lies in the fact that it remains valid even in complicated cases where it is no longer possible to assign configurations uniquely to the energy levels. The symbol is attached quantum numbers of odd terms when it is desired to express the parity explicitly. 135 (1924). 51. the configuration change occurring in dipole * LAPOBTE.
the discussion of 1 1 ). the change in I being restricted to Such. 2. For example. commute . e. transitions are called oneelectron jumps. and that with considerable difficulty. But these quantities commute with the With regard 44 M parity operator &.I9 CONMGURATICm SELECTION BULES is 237 radiation 1. it follows at once that the matrix of P can contain no components connecting states of different 8. only one line connecting the singlet terms terms of helium has ever been observed. and quintet system. the depend J ) occurring on the right of 7 4 5 is ence on J of the factors (ySLJlPly S The line strengths We P L 3 given by formulas 11 8 if we correlate^ with from these formulas that the selection rule on S and j 2 with L. so that they have nonvanishing matrix components between states of the same parity. which is just the opposite of the only Laporte rule for dipole radiation. Since commutes with S. are given by formulas 7 4 5 if we write ySLJ for oy have the selection rule AJ = 1. We confine our attention at present to electricdipole radiation. Because of this. The restriction to oneelectron jumps also applies to them. The ensemble of all lines connected with transitions from one term r characterized by L and S to another characterized by L and S we shall call a multiplet. We wish now to consider the theory of the strengths of the lines of a multiplet. In passing we note that this is also true of the electricquadrupole and the magneticdipole radiations. This is then the first important selection with the triplet rule of the RmssellSaunders case: intersystem combinations are forbidden. namely AI/= 1. It follows as that L is the same on 7. spectroscopists find that they can conveniently divide the terms of most atoms into systems of different multiplicities. configurations with levels. SL J r ) \(yL\P\y L )\\ r . triplet system. and the operator 3 positional coordinates only (cf. Transitions are observed in which there is an apparent change in two of the nl values (twoelectron but this is to be connected with a breakdown in the association of jumps). a singlet system. The factors (ySL\P\y dependent of S of products of a function of the electronic spin coordinates only and a function of the positional coordinates only. Since P commutes with S. Line strengths in RussellSaunders mtxltiplets. to quadrupole and magnetic dipole radiation we observe from 9 that %t and are also quantities of type F. by just the nl of one electron. The lines connecting terms in different systems are in general missing or weak. Hence in general 3 occurring on the right of 11 8 will be in since the states W(ySLM s L ) may be expressed as a sum f SL ) M P acts on the we may write (I) S(ySLJ. y SL J ) =/( J. 0. since the corresponding moments also with the spin.0.g..
(4) ZS( 7 SLJ y for the case SLJ = (2J+l)L(L+l)\(yL\P\y is of these three quantities proportional to 2J+ 1.. Zeits.^ The sum of these expressions is 4*/(Jfl) (2a) given by 13 5 3 : f : r Ll)^ (3) that level level. ySLJ the total strength of the lines of the multiplet originating in the is proportional to the statistical weight (2J+ 1) of the initial Since the formulas for strengths of lines are symmetric between initial we may regard ySLJ as the final state in the preceding formulas.* fiir PJiys. OBKSTEIN and BUBGEB. and Dorgelo. Thus for result that the (5) any EussellSaunders multiplet we have derived the general sum of the strengths of the lines having a given initial level is to the statistical proportional statistical weight sum of the strengths by of the lines. y SLU } = axr ^^+x.1 For these we have . where the whole dependence on S. in which case they give at once the strengths for a multiplet L = L + 1 and the sum rule says that the sum of the strengths of the lines ending in the same final level ySL J is proportional to the statistical weight of that level. L)\*. * BITEGEB and DORGELO.238 THE RUSSELLSATJNDERS CASE : LINE STRENGTHS f 29 f(SLJ. ibid. 41 (1924). 23. 258 (1924). J. is. and that a given final level is proportional to the the weight of that final level This sum rule was discovered empirically Ornstein. Burger. and final states. and J is contained in the function SL J ). which may be evaluated from 7 4 5 and 11 3 8.. that the ) sum. The L = L + 1 has the value J corresponding sum SS(y5iJ /5i+l/0 = (2J+l)(L+l)(2i+3)I(yi:P:/i+l)2. First let us consider the multipiets for which L = L . 24. . : S( Y SLJ. For the multiplets in which L = Lwe have: (2b ) From 13 3 5 we learn. having (2J+1) of that initial level. 9 as before.
. that these should have strengths in the ratio 1:2.6013 . and Russell. 22.5206.a **P.a &. 170 (1924). Now that we have seen how the relative intensities of the lines in a multiplet follow from the general formulas of Chapter in. 8:615:432 Observed 828: 635 Calculated 10: (10:8:615 Observed 4823. of change in L. . In the 3 P.gt. let us consider the application to spectra and something of the historical development in this field. These formulas are symmetric in the 4 They bear a striking resemblance to formulas 7 5 which express the total strength of all components of a line. that the sum j rules are valid quite generally. with the results shown in the : ^ following table (the calculated relative intensities are obtained 4 4 plying the above strengths by the a factors of 7 ) : Multiplet by multi Wavelengths in A ( Relative intensity Cr: . The simplest result concerns the relative strengths of the lines Z S^*P% and 2 5^.4754 Doublets and combinations with 8 terms are the only multiplets in which the strengths are fully determined by the sum rules alone.2 Since there is but one level in the S state. This was studied* for ^Psr quintets. We consider in 5 15 the explanation of some departures from this result.5204 7:504:315 Observed Mn: Mn: 6021. ^^Pg. the sum rule tells us P.S 5208. Since the statistical weight of the whole term is find that the total strength of all the lines in the is (25+l)(2L+l). Zeits.6016. The complete intensity formulas (2) were derived by the aid of the corre spondence principle before quantum mechanics simultaneously by Kronig.29 LINE STRENGTHS IN BUSSELLSAUNDEBS MULTIPLETS 239 with the Finally we may sum these formulas over the various values of J associated initial term. M+1 P Generally the ratios of the strengths of the three lines 5+1 .y 8L) for the three initial = (2S+l)(2L+l)L(L+l)\(yL:P:y L)* (6) Mnds and final terms.Vi. sextets and octets in Or I and Mnl. This is actually the case for the yellow D lines of Nal and is quite generally true for the SP doublets of the alkalis. Experimentally it was found however. Sommerfeld and Honl. and quantum mechanically first by * DOEGELO. we multiplet given by S(ySL. fiir Phys. 25 * 1 are as (28 + 3): (25+1): (251).Wy .4783.3 5 triplets the sum rule predicts that the strengths of the lines are as 5: 3 1 and this was found to be experimentally the case in Zn and Cd.
Rev. fiir SOMMERFELD and HONL. values of the arguments L and L such tables are also included.* Before the complete formulas were obtained. Rev. are given here in Table I 9 . fiir Phys. as a class. 31. and of second order. 746 (1933). lines are called satellites. Phys. may be classified into those of first order. 885 (1925). These are called the principal lines of the multiplet. 44. t WHITE and ELIASON. On this point see an interesting study of conditions in the neon glow discharge by LADENBTJRG. 314 (1925). 19. 267 (1929). The satellites of second order are. Roy. but is hard to get rid of entirely. Zeits. in which the J change is opposite to the L change. 302 (1926). Proc. the strengths decreasing with decreasing J. 5. f SOMMERFELD and HEISENBERG. characteristic of them. p. 141. We have taken care to speak of the strengths of spectral lines rather than . Soc. Among the principal lines the strongest is that with the largest J of the initial level. KRONIG. Zeits. fiir Phys. Since in the theory of hyperfine structure and in jj coupling we need tables of this same function with halfintegral . (1)] for aU J and J consistent with L and S. 11. Ann. For practical work it is convenient to have tables showing the relative strengths of multiplet lines in the most important cases. Phys. . cit. Phys. 11. Among the difficulties that arise is the lack of a statistical equilibrium in the atoms of the source and a partial reabsorption of the light emitted in one part of the source by the atoms in another part of the source. DIRAC. 131 (1922). HARRISON. Am. These qualitative characteristics of the multiplet intensity formulas are naturally of great importance in helping to recognize the character of a multiplet when a spectrum is being analysed. Sitz. intensities in order to place on the experimentalist the burden of inferring the values of the strengths from his observed intensities. Soc. Acad. 13. Proc. Opt. 206 (1923).) and by White and Eliason. namely. in Among the satellites the strength is a maximum for intermediate values of J. 1925. Sommerfeld and Heisenberg found by the correspondence principle an important qualitative j". Alll. Akad. The other For multiplets in which L changes the satellites which J does not change. that the strongest lines are those in which the change in / is the same as that in L. These have been calculated by Russell (loc. der Preuss. These are essentially tables of relative values off(SLJ y SL J ) [cf. J. 243 (1933). der Phys. Zeits. 753 (1933). RUSSELL. see also SCHTJTZ.240 THE ETTSSELLSAUJSTDEBS CASE: LINE STRENGTHS 29 Dirae. The latter difficulty is  diminished by use of lowpressure sources. Many of the experimental data on intensities are not suitable for comparison with the theory because data are lacking with which to calculate strengths from observed * intensities. Nat. Sci. Important references are: DORGELO. The largest value is in each case set equal to 100 the others are sharply rounded off. 18. Mod. weaker than those of first order. jj .J The tables of White and Eliason a given L.
29 LIXB STRENGTHS 1% ETJSSELLSAT7NDEES MULTIPLETS TABLE P. tn 241 o 16 .
.242 THE BUSSBI&SAUNDEBS CASE: LINE STBENGTHS TABLE I 9 continued.
63 . 1.29 LINE STRENGTHS IN RUSSELLSAUNDERS MULTIPLETS TABLE 1 s 243 continued.
L:P:y Z/)J so our problem is reduced to the evaluation of these quan . are forbidden between terms built on different terms of configuration If the terms of configuration I are the same. .* Multiplet strengths in a transition array. If IP L as \( Y 8LJ\P\y SL J )\* is of SLJ 8L J On com . J. transitions I. Nat. Formulas 2 9 6 express the total strength of a multiplet in terms of 2 j(y. From the considerations of S 1 Ity* S 11 L 11 L )\*.e. treating F as a vector which commutes with L and S Hence this vanishes unless S IV = S 11 in which case it is the same function of L*L IV L. L 1 IPL ((y^l^PJV1 ^ 11)! 2 ) . . (1) reduces to 1 1 (y S* Ify&8lF LIP I 8 . Ann. 2 2 J For example. we then see that the total strengths of the multiplets are given by = (25+1) f(&IFL. in particular 1 8 16. Opt. SHOKTLEY. to reduce our the relative strengths of the multiplets in the transitions problem to that of from configuration II to configuration IV. Acad. VAN MILAAN. tities* configurations are expressible in the form If II and If IV the results of I 8 . in analogy with 2 9 6. Am. (I) According to 1 8 18 5 this vanishes unless y 1 ^ 1 L l sy 1 ^ 1 !/ 1 . 20. fur Phys. Proc. Soc. 427 (1926). 9 . If the two configurations are not If the two respectively. we may use expressible in this form. 81.244 THE BUSSELLSAUM3ERS CASE: LKE STRENGTHS may 29 refer For further comparisons between theory and experiment we to the work of Freriehs. HARBISON. these considerations are applicable to the transitions between d $ p and d s\ but not to the transitions between d z s z and d* s. 6 8 17) but may use the method of 4 9 . * . we see that we can evaluate this 11 1 :? (2) expression . . f JOHNSON. ibid. we shall call the totality of lines resulting from the transitions between two configura tions a transition array. 807 (1926). 389 (1928). Sci. paring 745 with 2 9 6. 591 (1934). der Phys. 38. 19. 11 3 1 u by means of I1 8. 17. Zeits. and of Harrison. of van Milaan. 916 (1933). we cannot proceed by matrix methods (except for twoelectron configurations. FBERICHS. If we sum this expression over the various values of L and L which are consistent with the given values of L 1 L 11 and i iv we obtain. (3) where the function /is defined by 2 9 1. Following Harrison. tions.J The quantity we must evaluate is \tf&&^SlFL\P\y*S L^S*IPL l )\*. 921 (1925). 34. ef. i. f We now consider the problem of finding the relative strengths of the iniiltiplets which result from transitions occurring between two configura 3.
109 (1929). It was apparently independently inferred from the experimental data by Russell and Meggers J in 1927 when they called attention to the Am. Sci. 2 9 I. f KBOOTG. For an allowed supermultiplet. 329 (1927). The maximum discrepancy of 6 per cent. We shall now discuss these formulas by means of illustrative examples. it of course contains a factor S($ IV S11 ). 33. multiplets in a supermultiplet are thus the same functions of asthe relative strengths of the lines in a multiplet are of S L /. J RUSSELL and MEGGEES. . For example. 261 (1925).n l~l)~ * v4PlJo ^=rrE(nl)R(n f ll}dr. (6) The functions /are given by 2 9 2 according to the definition strengths of the. 22. . Zeits. and &11 = i. 287 (1929).gt. of Standards. Papers Bur. y&IP^n the nl values ofthe jumping electron in the initial and final states. the relative strengths of the multiplets in the 7 $~&. 18. in which case it has the value last factor here is just the factor r The (nl\P\n l~l}^$(nl. Addition of an electron to an ion. HABEISOK and ENGWICHT. S(yiSiI?7rfS. 19.)J#!?ttTLO^ (5) which arises in connection with the 5 intensities in oneelectron spectra and which was evaluated in 6 3. Soc. Several carefully determined measurements of relative strengths of multiplets in supermultiplets have been made by Harrison* with good theoretical agreement. The set of all lines arising in transitions between two polyads ( 2 8 ) having the same parent configuration is known as a supermultiplet. J. For example. Itvanishes unless V = I 1. namely 50:70:90.39 MULTIPLET STRENGTHS IN A TEANSITIOH AERAY total strength of the multiplet 245 The last S here is the in transitions y iy S 1* LW ^YU &1 IfL between configuration IV and configuration II. for the above supermultiplet of titanium he finds the relative strengths 53:70:89. Ti I d* 4s (*F) 5s 5 F*d* 4s (*F) 4$ 5DFG 7 supermultiplet are the same as the relative strengths of the lines in a P transition. This relation for the relative strengths of the multiplets of a super multiplet was first obtained by Kronigf from the correspondence principle in 1925. ibid. In the first place we see that transitions between polyads based on different parent terms are forbidden. The relative strengths of the multiplets in a supermultiplet are given by 1^ 1 1 1 y ^ ^ represent the parent term of the ion. * HABEISON. fur Phys. I9 with this correlation. y^ L = nl and (3) if we let l . IZl L SL J These relative strengths are thus given by Table . The relative UIL. Opt. between these and the above values is probably little more than the experimental error.
when corrected for the initial levels actual distribution among by an assumption of a Boltzmann distribution at the most favourable temperature. have thus solved completely the problem of reducing to the radial integral (6) the strengths in a transition array in which the jumping electron We is not equivalent to any in the ion.gt.gt.gt. where If is the L value of the parent ion and 8 the multiplicity of the supermultiplet. 10:7:4.gt.lt.3d ( D)5s. e 7 6 6 .s&. D should be as strong as these.n P 2. For example. 7:5:3. P&. the theoretical relative intensities of these six multiplets for excitation at infinite temperature are given by Seward as 382:354:259:1380:777:754.&. Rev. It should be pointed out that this solves in particular the problem of transitions between twoelectron configurations * SEWABD.3) are 2: 6: 12: 10.3 ^ 4^3 2. namely 4 jF. as seen from the following table: p 2 . 5 multiplet. : The agreement is rection and quite good. WD 4.  i. the relative total strengths &. Pfcys. A comparison of the intensities of a quartet and a sextet super furnished by Seward* for the case of the quartet and sextet 6 5 6 5 supermultiplets of Mill 3d ( D)4p&. P&.lt. . 344 (1931). When these values are corrected by the actual 4 &. 37. are given by Seward as 381 400: 278: 1328: 740: 819.gt. in the tran 2 of the four supermultiplets sition airayjp 2 2?. considering the difficulty in temperature cor intensity measurements for lines of rather different frequencies originating in levels of different energy.lt. The total strength of a supermultiplet is obtained from (4) if we make the same correlation as we did in (3) shows that to obtain the relative strengths of the multiplets. 4 4 5 5 P~&. The multiplets J 6D. * l4r&. D. The measured intensities. let us consider the relative total strengths of the various super P Now multiplets in a transition array between two configurations formed by adding an electron to the same parent configuration.7z&.gt.1 2.gt.e.r factors of Mn I. The relative strengths of multiplet 4 is D are the same as the relative strengths of the lines in $.246 THE RTJSSELLSAOTDEBS CASE: LINE STRENGTHS 39 striking similarity between the visually estimated relative multiplet in tensities in a dd*dp triplet supermultiplet of Sell and the theoretical relative strengths of the lines in a 5 D&.gt.5 Experimental data on relative strengths of supermultiplets are almost non existent. This immediately the strengths of the different supermultiplets in a transition array are proportional to (2$f l)(2Ll + 1).
PP 3 Pn (10) (10) (30) (30) (30) (30) (50) (50) (50) (70) ^ s ^n (20) 120 \ 1(180) 60) (100) (20) (20) (60) (100) (100) The Jfile We sum rule. at most one can be composed of equivalent electrons. e. since such transition contain only two supermultiplets a singlet and a triplet. now derive a sum sidering in rule which applies in the case we have been con which the jumping electron is equivalent to none in the ion.gt. Invariant sums are shown in parentheses. may by formulas analogous each multiplet the sum of the strengths We . from 6 17 we . 2.MULTIPLET STRENGTHS IN A TRANSITION ARRAY neither of which 247 is composed of equivalent electrons. For of lines originating in a given level is proportional to its statistical weight 2 J + 1 . Thus. The signs of S* are indicated. except that all absolute strengths must be multiplied by . For ex arrays ample.. Relative strength of the lines in 2 ps*pp and ps*p in LS coupling. see that the above considerations are true for the unexcluded multiplets of this case also.g. 3 3 P but the ps^pp are the same as the relative strengths of the lines in have thrice the strength of the singlets. the unexcluded multiplets of ps*p* have the same relative 9 strengths as the corresponding multiplets of p$*ppl see Table 2 TABLE 2 9 . the relative strengths of the multiplets in either superniultiplet for $&. The line strengths in this triplets 3 9 array are given in Table 2 In transitions between twoelectron configura 8 tions.
and Lu S11 the 2 term of p (3) shows that the relative strengths of the multiplets in a group & .gt. illustration of the use of formulas (3) is still holds for More in As an and (4) for transition arrays which the jumping electron equivalent to one of the others.248 to 2 9 THE RUSSELLSATODERS CASE: LIKE STRENGTHS 3.gt. may during be eliminated.(we call any row or column of a transition array such as that of Table 2 9 a J file). such as d 2 here. SL r . Hence initial term only through its statistical weight array the total strength of the lines of the transition originating in (or terminating on) weight 2J+lqf that level. this sum rule J files in one direction in the transition array. proportional to the statistical This statement. general configurations. as to 2 sp^p The allowed . If we let S1 represent the term of d! 2 L IV S IV the term of sp. and# 2 and which are analogous to supermultiplets. 27 3 ( P) P) 45 3 ( S P&. of the lines of the array which originate in the term y1 U^nlS L. multiplets of the . We shall show in 411 that even if the jumping electron is equivalent to the other electrons in one of the configurations. These multiplets are indicated at the right of The obtained from relative total strengths of the different groups are to be (4) in terms of the known relative strengths of the multiplets in the transition . This sum has the value which depends on the (2S+ l)(2if 1). holds for any type of coupling. . It is convenient to consider together all . are the same (8).gt. t as the relative strengths of the lines in the multiplet 3 SL&. where S = If L = L^ and L = IP.d 2 p 2 are ^P^S) Is p (1?) IP +yfi (IS) 8=1 g 9 3 (sppp _^ (ap)3p p PP) *SP*p z (i) 3 P ^ 45 3 ( (P+Z) 3 ( (8) 8 ( P) 1SPD+ P) i^PD 9 P^ 3P) 3 P&.gt. we may consider the strengths in the case d 2 sp~*d*p*. which we shall see in Chapter xi any level is we shall call the Jfile sum rate . By (3) and (4) any group of electrons which remains intact the transition. 39 5 sum (5) over L to find the total strength. and the problem reduced to transitions between the electrons. 4. transitions for * remaining d 2 sp&. same multiplicity which are based on the same terms of d 2 sp. Each arrow in the above represents one such group.
2U. We We reduce the problem to a simpler one. and n I 1 in the other. in the zeroscopic stability in . the absolute squares of the matrix components of F connecting these two configurations. 23 for the last entry of (8). It is possible to determine these strengths from the principle of spectro &. The states of the zeroorder scheme are related to those of the 8 L scheme by a unitary transformation . the total absolute strengths of these groups in terms of the radial 44. By the results of 6 6 a non. these configurations when expressed in the S L scheme. by means of the formulas 9 11. We calculate first. and the relative total strengths of the different groups are given by the numbers in italics.gt.+ 1 = 3. 740 (1933). e. All of these 2 are expressed in terms of the quantities j(y$ L\P\y 8 which we are Z/) 3 seeking. Multiplet strengths obtained from spectroscopic stability. . l) J (1) where s is given by 3 6. 8LM M P SLM M which has nonvanishing components only between * if we had substituted we should have obtained integral (6).* 4. Substitution in (4) gives 45 for the total strength of the group.g. energies As shown in I 9 the only transitions possible are between configurations which differ in regard to but one electron. f CONDON and UFFOED. 2S f 1 = 5. which has quantum numbers n I in one configuration. Thus all the squared matrix components of P may be expressed as multiples of s 2 Now let us consider the squared matrix components of connecting 9 . f have obtained very simply the strengths of the multiplets for con figurations in which the jumping electron is not equivalent to any other electron in either configuration or is equivalent to one other electron in have also been able in many cases to only one of the configurations. order nlm/rit scheme.39 MULTIPLEX STRENGTHS IN A TRA^SITICOT ARRAY this 3 249 In way. Thus the relative strengths of the multiplets in a group are the same as the relative strengths of the lines in the multiplet in parentheses at the right of (8). There are no components connecting states which differ in regard to the quantum numbers of more than one component is simply ( electron.. Rev._p 3 much the same way as we determined the electrostatic from the diagonalsum rule. 2S11 +1 = 3. S(sp Pj9 P) = 9. But we have not been able to handle such transitions as p 2 s & 2 or p 2 s~*p% to name two of the simplest.vanishing matrix the corresponding matrix component of the oneelectron problem is given by the formula 6 s ) This . Phys. states of the same Ma in (4) the absolute strengths of the multiplets in the array sp~+p z .
250 and THE BUSSEIXSAUNDERS CASE: LINE STBENGTHS L Therefore we may apply the principle of spectroscopic stability 2 2 25 to the squared matrix components occurring in any box of which the . 0*). method determines only We shall illustrate the method by consideration of the configuration array p*+p*s n RussellSaunders coupling. specification only the If there are several multiplets of the same kind. (*S. Only one component occurs with lfg =Jf^ = f and ^=0.gt. L =l.(l+0+ s2 SLM M 3 Hence we infer that This result ML =M^0. M =M 8 may be checked from the component having M ~M s f s =% In the same ^ way we may pass to the part of the matrix associated with = J and find in the zeroorder scheme that the coefficients of s 2 in the squares of the nonvanishing matrix elements of P are given by desired for checking. In the zeroorder scheme this is the M transition (1+0+ of P is . M rows and columns are labelled by the same values schemes. the squared matrix component being. the method gives complete when there is but one multiplet of each kind occurring. for which the squared matrix component the formulas. In this way a set of equations is obtained which is usually sufficient to determine the quantities \(yS L\P\y SL )\* 9 from which we obtain the multiplet strengths by 2 9 6. 1). The table need not be extended to negative values of L unless this The corresponding portion of the table in the SLM 8 M is ML scheme. by 9 3 11. in which the numbers are the factors which multiply the corre sponding quantity of the type l(p**D\Plp*s*P)\* } is . Analogous to the limitation of the diagonalsum rule for energy. This enables us to equate the sum 8 and L in the two of the squared matrix com oM M ponents in a particular box in one scheme to the corresponding sum of the squares in the other scheme. the sum of the strengths. f 0)( ~l+)&. In the by S L scheme this is the transition 4 P f.
at the top. of the second. and where two or more nraltiplets of a kind occur. we obtain a which lead to results set of equations for the coefficient of s 2 in the value of multiplet strengths. In the same transition array. given in TABLE 3 9 .p s2 or p$ 3 P 2 4Z) 3 2 Z&. The terms of the first configuration are placed on the left. 4 &.gt. 2 3 P 120 45 15 ! ! i . of the boxes. Only allowed transitions are listed. \(p*SL\P\p*8SL )\*. 2 2 P 33 i&. the sum of the strengths is given. values in boxes of different multiplicities are to be directly compared. The total terms of this quantitj7 by formidas 2 9 6 are ? Relative multiplet strengths.gt.gt.49 MULTIPLET STRENGTHS FEOM SPECTROSCOPIO STABILITY 251 Applying the principle to each of the boxes.
5. In the process of squaring. of being capable of giving us only the amplitude of the electricmoment matrix. I are related to the matrix components D. Harvard College Observatory. Phys. as follows: = . 974 (1932). In 6 4 we were able to find the of the quadrupolemoment matrix components by building dependence on we M them up from the dipole matrix components of 9 3 1 1 here we may repeat the : process on L 3 by applying II to find the dependence of the matrix components and 8 in the SLJ scheme. This is of little use for cases of departures from RussellSaunders coupling as discussed in Chapter xr. G H. eSrtri? i)(a". since to effect a transformation of this matrix from LS coupling to an intermediate coupling we need to know the correct phases of the matrix elements in a definite scheme of states. Quadrupole multiplets. probably be published in the Astrophysical Journal f UJTFOBD.* The method of this section has the disadvantage. . In order to separate two like multiplets in cases not amenable to characteriza tion by parentage we must also go to the eigenfunctions. This gives us a set of formulas (Table 4 9 ) for 9 quadrupole multiplets analogous to 2 2 for dipole multiplets. the sign of the matrix component is lost. Such a calculation of the electricmoment matrix may be made if we know the eigenfunctions of the LS coupling states in terms of the zeroorder states.:** S S J&ftja S L) of * A very complete set of tables of relative multiplet strengths is being prepared by Mr Goldberg.e S J S [(a 8 Ljr.252 THE EUSSELLSAUNB BBS CASE: LINE STBENGTHS . lines in Let us now obtain the strengths of the as a quadrupole multiplet. After the matrix components are found the strengths of the quadrupole lines may be found by 7 4 7. 49 9 given in Table 3 together with the relative strengths of the multiplets in other simple transition arrays which cannot be solved by the formulas of 3 9 . so in Table 4 9 we give the sign in a separate column. he can find it from 3 components of r t where 92 = . did for the dipolemultiplet in 2 9 . E. F occurring in 7 4 7. 40. this will of the in 1935. If one wants to know one of the matrix the strengths by 4 dividing by the appropriate factor in 7 7 and attaching the sign here given to the positive square root of the quotient.f who calculated them by first * D } obtaining the eigenfunctions. Rev. not shared by that of 3 9 . just as we did in 7 8 to separate the energies of the two 2 s of d 3 Several of the arrays of 9 Table 3 are taken from a paper by Ufford.
fur Phys. TABLE 49 . of that level.j^L. RTJBINOWICZ. who showed that they obey the sum rule of Ornstein. 662 (1930). Zefts. Strengths of guadrupolemultiplet lines. namely. . There formulas. that the sum final) level is of the strengths of the lines in a multiplet from a given initial (or proportional to the statistical weight. 65. 2J+1. Q(J) and R(J) 9 are the factors used in IPS with the correlation j^J y j l ~^S.QUADEUPOLE MTJI/HPLBTS 9 253 The strengths of Table 4 were calculated by Rnbinowicz*.gt. is very little The relative line strengths in * experimental material available for testing these 2 5 quadrupole some of the 2 D&. Here P(J). Burger and Dorgelo.
fur Pliys. the theoretical relative strengths.D five levels of the 6 D term. They are and $d*4s*G+3dF. 62 6 6 ^ the being due to disturbance by another line. probably accidental in view of the lack of photometric measure ? ments. and the ratio. The 6 g . we s interpretation of the nebuconsider in 5 11 because these lines are combinations between terms of different multiplicity and so existence to the departure from RussellSaunders coupling. rule the strengths we take 1). . For the eye former there are five lines having the same initial level and ending on the 3rf 5 4s 26 $&. In the table give for each line the observed relative strengths (intensity divided by a6 ). Zeits. we as good. The difficulty is that multiplets violating the Laporte rule may arise because the atoms are disturbed by electric fields in the source.gt. t MJERBTLL. owe their There are two good examples of quadrupole multiplets in the Fell spectrum found by Merrillf in the spectrum of the star ^Carinae. latter should be constant in * For the other multiplet the agreement is not nearly The any one row as these lines have a common PBOKOFJEW. are proportional to (2J+ numbers proportional values are 1) for the final level. This is surprisingly good agreement. If Merrill s intensities divided by to . J. 67. By the sum. Astrophys. 405 (1928). 387 (1929). . observed to theoretical.3d 6 4s 6. The intensity data are merely estimates from plates taken in Chile by Moore and Sanford. In fact the most interesting developments in this field grew out of Bowen This Hum lines as quadrupole lines. is in the spectra of nebulae or rarefied stellar atmospheres where the mutual disturbance of neighbouring atoms is negligible. 57. The place where quadrupole lines are of importance . Q (2J+ ? the quotient should be constant.254 THE BUSSELLSAOTTDERS CASE LINE STRENGTHS : doublets in the alkalis have been measured : by Prokofjew* and found to be 3 2 in accordance with theory. in which case the line strengths are given by other formulas (3 17 especially 3 17 5).
consider the absolute values of the quadrupole strengths. .gt. if the temperature were infinite. divided by 12 which would be equal to the sum from 4 (? divided by 8. jbo a temperature of 1600 K. one of the matrix components (nlms l\ \n for ms = H. as in 6 5 5. and S(^l. H clear that for a oneelectron spectrum H = 0. otherwise the parity selection this rule would be violated. by direct integration. G. or P from 6 4 6. The methods developed in the preceding two sections could be taken over with lines. corresponds. which is all we need. Jo (I) which obviously tribution. It is 3 . to express the numerical coefficient in the 4 quadrupole transition probability in atomic units. We now proper generalizations to treat the corresponding problems for quadrupole Such developments have not been carried out in detail because the possibility of experimental verification seems too remote. which is directly analogous to the work of 6 5 and 9 s The problem is to express the coefficients. U. and I in terms of s 2 table of strengths of this section we can find G. since we know that this is also equal to (?i?Z+?f \nf I I* +%V +%) in the nljm scheme.5s initial level. so by appropriate choices D. which is 275. 3 and I.J and m^l we have m f 8l ) in the nlmsmi scheme. QFADRUPOLE MULTIPLETS 255 The sum of the observed strengths from ^Gfij. and F and the coefficient of 4 4 Q in 6 6a can all be found in terms of s 2 Then by combining 7 7 with the D y .l)V(2Z+l)(2Z3) Combining these with the table of strengths we have the means of expressing in absolute measure all the strengths of oneelectron doublet lines. The work is a little tedious but straightforward. The same matrix component can be expressed in terms of E. The observed ratio. H of the formulas for line strengths in terms of the radial integral &. This will measure the secondorder moment of the charge dis l may be done by calculating. Then. may write . It is convenient. if we measure a with the Rydberg constant as unit. is 44. In 7 8. J3) in atomic units. e2 a 4 we . We confine atten tion to the case of oneelectron spectra. if we assume a MaxwellBoltzmann distribution of the atoms. The values of G and I found in way are g  4 (21 .= efr2 R(nl)R(n l )dr.
gt. As of of Z the calculation should be . A128. where the terms are well separated.3 8 /2 13 . 11. Experimental values were obtained by the anomalous dispersion method by Prokofjew. . 216 (1932). using the table of strengths. &. Stevenson* has calculated the transition doublet for the alkali probabilities from the normal 8 level to the lowest D metals using Hartree wave functions. 387 (1929). we shall calculate A(A. Soc. 57.gt. To exemplify the formulas just presented. For These are in the ratio of the statistical weights as the sum rule demands.Is doublet in hydrogen.3 8 /2 13 . . this line we have cr = f so the spontaneous emission transition pro is bability of either line From Table 5 5 the closely analogous dipole transition probability .256 THE BTTSSELLSAHNDERS CASE : LESTE STRENGTHS 59 The numerical coefficient is about onemillionth. j This was pointed out by KUBINOWICZ and BIATOST.) for the 3^&. Ergebnisse der exakten Naturwissenschaften. l*j) = 3. f PROKOFJEW. l*j) = 2. made using the relativistic radial functions is 5 5 but our result shows the trend in order of magnitude.gt. fur Phys. although for 2=92 the ratio probability . S(3dj&. 591 (1930). this is possible and the s *d series is easily obtained in absorption. . 8 1 is a consequence of this trend quadrupole transitions are sometimes of appreciable intensity in Xray spectra. is A(3p*la)= 164 x 10 secwhich is about 027 x 10 6 times as great. Zeits. Roy. S(3c%&. For the higher values only 1 : 32. 2 In hydrogenic ions of nuclear charge Z we have and r ocZr 1 so the dipole transition probability varies as Z* while the quadrapole transition Q In all actual atoms the quadrupole transition probability varies as Z remains smaller than the dipole. of that for dipole radiation 5 (6 o).rccZ .gt. Proc.S first D~*S Rb 27 29 quadrupole Cs 06 line to dipoie line are Na Observed Calculated * 11 K 15 35 25 STEVENSON. First we find that the radial integral 2 = I Jo hence I 2 = 3 7 /2 19 from which.lt. In view of the great ratio of dipole to quadrupole intensity it out of the question to observe quadrupole lines in the hydrogen spectrum.f His values have to be divided by four because of a difference in the theoretical formulas for quad 6 rupole and dipole dispersion 4 The final values of 10 times the ratio of the spontaneous transition probability for the that for the first P&. and also to gain a better appreciation of the order of magnitude of quadrupole transition pro babilities. In the alkalis.
although approximate. The diagonal element for the state A = a1 aN is given by (A \H*\A) = S (n*Fj*m*\H*\n? I*? mf) 45 ). when the electrostatic interaction is absent. H &. The general solution is possible for a great SLJM many more scheme. coupling scheme. scheme in which the fs have been combined to form resultant J and M. it still does not in general furnish a complete set for more than two electrons. In the pre cases if one uses the scheme one must.CHAPTER X jj COUPLING The most would direct method of solution of the firstorder perturbation problem consist of the diagonalization of the matrix of electrostatic plus spinorbit energy for a given configuration in the zeroorder scheme. Since the i= spinorbit interaction HI= f (r^L^S.coupling scheme and 1 the spinorbit interaction. will 1. considering this interaction. character. then. the problem and the impossibility of obtaining the general solution for complicated configurations. 1 is so highly degenerate as to be diagonal in any scheme Although the set nilij i it is most convenient to consider the particular specified by (cf. That procedure one might call impossible for all but the very simplest con figurations because of the high order of the resulting secular equations. It may CS 17 . In this way we shall know the character of the general solution at both extremes. The ^". . be interesting to consider the less important case in which the electro static interaction is weak compared to the spinorbit. but in order to utilize this special cases. (I) We ^H i i is a quantity of type F. except in Because of the complexity of ceding three chapters we have considered the important case in which the spinorbit interaction is weak compared to the electrostatic in this chapter it .gt. it is diagonal in the zeroorder scheme in which riljm are taken as the electronic quantum numbers. it is desirable to obtain as much information as possible of an elementary. wish to determine the firstorder energies which result from the spinorbit interaction. . This. which depends only on the values of 71*1* j*. is the natural scheme to use when . obtain the transformation to it. The scheme characterized by the set of nH^ and J is known as the jj M be here noted that although this designation utilizes more quantum numbers than the i~coupling scheme.
gt. There are two states with Jfef = 0.3. M 3 M similar way the levels for the other values of j. 0. P1? P These 1 . (. the resultant levels cannot be obtained in this electrons.J).258 fj COUPLING The process of finding the allowed levels iajj coupling is similar to that in 6 coupling.=I. depending in the same way on 4 1. 2. way if there are equivalent For the configuration np\ (3) becomes modified as follows: (4) . Just as in L$ coupling. = i / = i (m.gt. and since this is the highest = occurring for j  j = . etc. consider the configuration npn p.m ) may have the values (J. For example.They namely SQ Si. Hence we infer the existence of the levels wpin pi. 0. J=l. The one state with J". / are determined in the following table. the level J = 1 has a state Jf =0 and there must in addition = 1 is taken care of by be a level with J=0. In the body of the table are given of each column are given the resulting J values. 1. 1&. ($. .2. m ).2&.J). I7 for this configuration. (ra.i. while at the foot (3) J values check with those obtained in 2 1 3 3 ^gj A. could equally well have been obtained by the usual vectorcoupling picture: j = f and j = f can combine to give a resultant J = 3. and ( i). In a LS . Here j and / may take on the values J and f If . J). there must be a level J= 1. For the first of these states M=l.
Rev. and hence for the whole configuration. and determine its eigenvalues. . namely 1 SQ 3 P .2? *A2I 10 . calculate that degenerate spinorbit levels. Phys.gt. for each J.0 The spinorbit energies for these states as calculated from (2) are (16) * it. We part of the matrix of electrostatic energy which refers to each column. But the electrostatic energy is diagonal with respect to J and independent of M . i&. Because of the symmetry which obtains. in 1 10 3 and 1 10 4.lt./ = : U iU 2C W (6)1 I * (8)} (1)1 (6) * * (The numbers in parentheses at the right denote the degeneracies of the energy levels. We therefore need the diagonal elements of the electrostatic energy )e/r&. was zero. which follows from the theorem 7 7 given in 3 about the centre of gravity of a term.) Thus we see that p* is split by the spinorbit interaction into three equally spaced energy levels.gt. This is a general property of the spinorbit interaction.i. the half of these tables for will usually give one all the information desired.gt. . 862 (1931). these eigenvalues can be determined by the diagonalsum rule from the diagonal matrix elements. 38. 172 . while pp is split into four energy levels whose spacing depends on the relative values of and n p In each case np the centre of gravity of the configuration remains at zero.j i&. by the diagonalsum rule the sum of the eigenvalues of 1 must have this same value. H H 2.*.kp (8) (5) (8) P a : J = !.. than once per column.3 (1) LSTGLIS. with a degeneracy of 2 J + so that there will occur one eigenvalue 1 Hence unless a given J occurs more .* We shall now determine the effect of the addition of an electrostatic inter action which is sufficiently weak to be considered as a perturbation upon the must then.THE jyCOtTPUNG SCHEME ASTD SPINORBIT INTERACTION 259 These J values agree with those previously found. lf&. The addition of a weak electrostatic interaction. In 3 we calculated the elements of 1 in the LSJM scheme and found that their sum for diagonal each term.
nT) and Gk (ril. i .lt.n*B?nf).=.Gz 0: 2: F . It serves merely to raise the whole configuration and may be considered as a constant inde 2 pendent of coupling.0.J=3: F + F2 &.*! T(n*V^*. 2) ^ (2) = S &&.? . =f. I 10 these levels are compared schematically with those of Chapter vn for this configuration in LS coupling. with giving Table I 10 as calculated by Inglis. jj COUPUKO 2 10 From 7 S 7 this element becomes (A\Q\A) ^ = S r/fe*Z^*)&^^^^ l. p. I 10 grow into each other in this of the same J value cannot in general cross when one . f We f 9 m r ) For example. The / values occur in the same order on each side. of the quantities T(riljm n l j in terms of the ) Fk (ril. for s. Each of the ^ s of (2) must now be expressed by 45 8 in terms of the ^(nlm/n^ in which case we obtain a sum of terms of the type 8 6 1 which have already been evaluated. shall content ourselves . In the case of np we have 0: In Fig.260 in the nljm scheme. (3) 0: In the approximation we are considering FQ need not be small since it occurs uniformly in all diagonal elements and all energies.n l of 8 6 15. and d electrons. in 3 11 that the That two levels two sides of Fig.gt. for the configuration nprip the found from 1 10 3 and Table I 10 to be npn pi / t electrostatic energies are . and as the parameters are continuously varied we shall see order.
T(nljm. n lj m ).TABLE ll &. . Che numbers given are to be used as coefficients for the integrals at the top of the column. which is omitted from the table for convenience. nT).gt.. To eack of these T s is to be added F (nl.
2p2yj. All terms for which not more than 2J+1 electrons have the same nlj value are allowed. (D) Weak electrostatic interaction.* The limits (weighted by 2Jfl) energies In the two rule. Zeits. The exclusion fashion than in LS principle operates in jj coupling in a slightly different coupling. the j values of the electrons. VOF XEUMAI^ and WIQXEB. (C) Xo electrostatic interaction. and are de If a weak electrostatic interaction is generate with respect to J and The energy M . . However. applied. not all the levels of s vectorially are allowed unless all the a given term as given by coupling thej nlfs are different. The subscripts denote the configuration 2p 3 by 2p2p. Phys. levels which result from the spinorbit interaction are characterized for a given configuration by a set of j values. For example if. We shaE use a notation in which we represent the three possible terms of and 2p. these energy levels are split into levels characterized by J values.Q . 467 (1929). but we can in general obtain more of them by coupling vectors than we could there. (A) No spin orbit interactioxx.262 parameter is ii COUPLING 21 varied has been electrostatic sums of the shown by Ton Neumann and Wigner. Limiting eases for j? . Eigenfonctions. Let us for convenience call the set of states characterized by a given set of J values a (jjcoupling) term/ in analogy with the terms in LS coupling. as in I 8 we . * & * 5 2 S * (A) (B) 5 (D) (O 2 10 Fig. (B) Weak spinorbit interaction. 30. are equal as required by the diagonalsum o $ . 3. couple the terms of two configurations to get terms of a * new configuration. i . the superscripts the number of electrons of the same nlj values. The eigenfimctions for Jj coupling may be found by any of the methods used in Chapter vin.
on line strengths. we see from the relations where the matrix component at the right individual electrons hare definite = T(Z?nZf JJf) = 2^KZ^ 7i2y.Fj f 1*2 1 lT J JT) = (jj \F\ff) 2 (1) connecting the states of nl and a consideration similar to that which gave 6 8 17 that nlriV. for use in the nest section considered in detail in 6 . and is hence amenable quantum to the use of the formulas of Chapter m.p(0)ttpj(i). This is less Js stringent than the L5coupliBg require ment that no allowed J value occurs in both configurations.3 10 all ECGB^FUNOTIONS the 263 obtained by coupling the allowed J1 ^ and J^ s will be allowed and the eigenfunctions may be found as in 6 8 provided that no nlj Yalue occurs in both I and II. JM) = HtflnAJj n J J ) Y(nZf ril J } f M M ^W^M JM M J )l j(nj n&ft )] that j f) = i . 9 . the type nfj These are given in Table 2 10 Thus are levels of . TABLE 2 W . all J values are allowed if j1 ^^2 8 i=j* the states resulting from the coupling are as in 6 either anti symmetric or symmetric according to whether J is even or odd. we see that the three allowed np\np^ w . The use of vectorcoupling formulas 2 for obtaining matrix elements between two states of the configuration i is 12 Let us here consider. Allowed J values /or groups of nljequivalent electrons. f and f. Hence only the even J values are allowed ifj=f. If j= /. Here in parentheses are given the J values of the groups of nZJequivalent electrons. and at the end the resultant J values. Thus we may find the values for any term if we know the allowed / values for terms of ril . we see from is between states in which the numbers. If j /. the matrix components (nljnW JM\I\nlj*n of J = . In coupling two equivalent electrons. I and wp (2)^(4).
/) . whichever occurs. we may use the 3 are formulas 11 88 to evaluate the quantities Kn^PfnljJlPln^nTj J which are needed in this 7 4 5 to give ) (1) the strengths of the corresponding 1 lines. if none of the electrons in the ion has quantum numbers * n lj * BABTLETT. Phy. If one of the configurations is composed of equivalent electrons. to transitions between the levels resulting from the addition of electrons of More quantum numbers nlj and n Vj* to any ion in a state of resultant angular momentum J1 nlj or .p in jj coupling.l)^J ( Mh J ( ^&..gt. the order of the quantum numbers must be reversed by the use of the relation 143 7: is significant.lt. formula (2) is applicable. L never. ( 3) In this way we find 1 (jj IFiff) = StfJ Ch/s!* .* Line strengtlis in jj coupling may be found by methods similar to those of Chapter ix for L8 coupling.so". 35 f 229 (1930). and from 3 104 that when j^j1 either J ) or Sfjj 1 JJ1// ). }  s(fj*W J jW H K^XZ . Line strengths. Their main application is in the raregas spectra (Chapter xm) where only the strengths for twoelectron configurations needed. (2) =/(j f)! Hence the relative strengths of the lines in the *multiplet* connecting the terms fj and j1/ are the same as those in L8 coupling for the multiplet SL~*SL f with the correlation 5^j 1 L^j. . Rev. as in 2*1. halfintegral. 2 The total strengths of the multiplets are given as in 395 by (3) 9 S^V) = (2f+ !)/(& which reduces all 8l j ) \(^:P:nT)\^ the intensities to the single matrix element 3 6.264 In tlie last term here.iX^O i tt* !) (*) 0V/) 4. If the jumping electron has different nlj from the other electron in both configurations. We shall first briefly consider transitions between the two twoelectron configurations n^Pnl and riWnT. if we write J for j .!^?) ) . These relative strengths of the calculations are illustrated 10 by Table 3 of the ps^pp andp#&. we see from 3 1@ 2 that the allowed lines when j =j 1 have twice the strength of the corresponding lines for nonequivalent electrons. They are thus given by Table I 9 for halfintegral L. In way we obtain. and = . has the same intensity as lines in S^jJ^j S^jJ^fJ 2 ) for nonequivalent electrons. say that wi^n1?. 1 1 generally. L *j except that j is always.
1 x i.i if 1 I.i 2 f.i 2 I. The signs of S PP i.* 4.i 1. STRENGTHS p *jp 265 Relative strengths of the lines in p and p s~*pz in jj coupling.* 1 (90) (150) (10) (10) (30) (30) (30) (30) (50) (30) (50) (70) I. Invariant sums are shown in parentheses.0 (30) (90) I.4 8 (20) ps 100 kl80) (100) (20) (20) (60) (100) (100) .4 .! 1 M 1 i.LESTE TABOJ 3 10 .! 2 M 3 4. are indicated.
of Matrix ol spinorbit interaction for configurations consisting first coupled groups. the actual levels of all atoms lie between these limits. In Chapter xn we shall see how to calculate the same energy matrix in the jjcoupliiig scheme which is particularly suitable for the considerations of the raregas spectra in Chapter xm. . although many are very close to RussellSaunders coupling. or JtScoupIing electrostatic energy predominates. hence the least value of JJ/J which occurs for the con figuration is usually the most convenient to consider. in which the spinorbit energy predominates. If we make the correlation i Jr*S J+J V . since every level will state. and a feWj particularly heavy atoms closed shelly are close to jjcoupling. however not In 3 8 we saw how we could obtain the diagonal elements of this matrix for configuration I f II in terms of the diagonal elements for the inequivalent configurations I and II separately. the dependence on J (and If) of the matrix elements (3) * JOHNSOST. . Such a calculation is restricted to the diagonal elements. 1628 (1931). which 1. In this scheme the electrostatic energy is completely known from Chapter vn) and the The total energy spinorbit interaction is diagonal with respect to J and diagonal {the diagonal elements being is M . Rev. 38.* Our action task is to obtain the complete matrix of the spinorbit inter A~ (1) for the SLJM scheme of a configuration. will be considered in Chapter xv. Phys. and those containing almost line strengths In this chapter we shall obtain the firstorder energies and in in the general which the two interactions may be of any relative order of magnitude by calculating the complete energy matrix for states in the SiJJl scheme. have such a These calculations all neglect tie interactions between configurations.CHAPTER XI INTERMEDIATE COUPLING We have calculated tie firstorder limiting cases: the RussellSaunders. independent of Jf. Practically. energy levels and line strengths in two Hmit in which the s and the jjcoupling Emit.
The above procedure is justified by the fact. be used to reduce the first sum to a known multiple of yi S S tflfl&t) L&iLi)(&. since the matrix for a oneelectron configuration is known from 4 5 6: A comparison of this with 12 3 2 shows that (nK(r) LM)(ns:S:ns) = tnl %\ (6) which gives the value of the quantity (5) for a single electron. say I. Formulas 1I 8 may then. Since the matrix elements of spinorbit interaction for configuration I are known multiples of (5). over group I and II inde 3 pendently. L J) S ln if (Ul*\L )(Si&\S ). which 1 follows from I 8 . with the correlation 3 8 3. These considerations completely solve the problem of finding the matrix of spinorbit interaction for a twoelectron configuration.J1 JyPrf ) LfSt \y* S*1 i (y 2 & 1 J1 if1 ) * /J (3 1 ) equals the factor given by 12 f*i I S2 times 1 E S (/ & &\&rd L^/ & L 1 ^y". /(T 2 iixLnr***!1 S (S\S \S) = (SIS \S) = (8:8^181)= (SiS :Sl) = p (8) * For a given configuration.and S 1 L 1 S fU JD n and not on the structure of the inequivalent configurations I and II. S correlation (2).lS L I y ^SL L f J1 ) f (yi&Li y^^nz/n S^. (1) L J) is the coefficient of (4) in (3) as given by 123 2 with the and 2L(L+1) V. x (5) The second sum may be correspondingly reduced. Thus for a twoelectron configuration the element S (nWn*P SLJlftffa) LfSilnWvW S L JM) =g(8LJ.yi&lSfriSi). that the matrix component (3) is a linear combination of the components (3 ) and (3 13 ) which depends only on S1 L1 S11 17*. S where g(8LJ. 1 although (3 ) has a value different from zero. this effectively expresses the matrix elements for configuration I f II in terms of those for I and II separately. since no state characterized by S* L 1 may be allowed. to write that 1 V. .I 11 is SPINOBBIT INTEBAOHON MATRIX FOE COUPLED GROUPS 267 given by i 12 3 2 in terms of the quantities ".lt. (4) be broken into two sums. & Li\Sg/i S i ) (41) nas in general a sense only symbolic. this ).IXL1)} .* Twoelectron configurations.yWjyi y^Sf njyn s As in 3 8 1. yiyn S S (yl&IfyZSZIflLigfa) L may i : 7 1 ".
m o o o o V3 V2 o 2 V3 V2 0020 o V5 V 10 2 o 5 V 2 Pi V5 Vio o . Natrkm of spinorbit interadim.. 2 p x i 2 V5 o 20 5 8jD at  VlOa V 3a VlOa V6^ 4^  2V2a 2a S &.gt.268 INTEBMEDIATE COUPLING TABLE l u .^2 4 V2 2 2V2 .
A . j. Voa 4V2/S 4V5a  V5 ** 2a *J. 1 *F&. SV^ 2V5/3 6oc 2a 2oc V7a 6a 2V /  2V21jS Vsjs 3a 21 8 J A 0.gt.SPINOBBIT INTERACTION MATBIX FOE COUPLED GROUPS TABLE I 11 269 continued. V.
gt. where it sets (outside of closed shells) of A. configurations. SrL=Jin this order.gt. It follows from 6 8 15 that these formulas hold for the allowed elements even if the two electrons are equivalent. .4 H*\A )= H*t&. In these matrices the l l phases of the eigenstates in the configuration n l n*P are such that = 2 f 2 5= S1 f S*. say that a occurs in A while a! occurs in A The value of this scheme is obtained from . if we know scheme (Chapter vm) and the matrix of spinorbit interaction the eigenstates for the in the zero SLJM may readily be transformed to the SLJM scheme spinorbit interaction in the zeroorder The matrix of the 66 s (cf. j&. of n^PnH1 are According to this convention. One obtains a nondiagonal element only between states differing in regard to one individual set. this matrix in the usual way. From these formulas we may easily calculate the matrix of Hl in the zerothe SLJM scheme it is diagonal with respect to if. 2. the phases of a given term 2 {i)21^ ^^! times those of the corresponding terms of More complex configurations may be calculated in a similar fashion.w(*\LS\a ). 3 =S&. For configurations containing more than two equivalent electrons we cannot obtain completely the matrix of spinorbit interaction by the method of the preceding section. Thus in Table I 11 is included the configuration p*s. 4 1 for notation and sign convention). L Sf L.gt. In this matrix the phases of the eigenstates are such that an 3 z 8 eigenstate of p s is obtained from those of p with phases given by 4 6j by S s l^+L =l. Matrix of spinorbit interaction obtained from the eigenfunctions. This matrix was obtained in the way we have sketched from that given for 3 which is calculated in the next section. (la) The diagonal element has the value where a runs over aE the order scheme. But order scheme. We shall always adding S^f S use such a system of phases when adding an electron to an ion or in general in coupling two groups. component is (. with the vectors added in this order by the formulas of I 4 s We shall always use this system of phases for twoelectron 5 J= . When transformed to becomes diagonal also with respect to J and inde pendent of If. In this way the configurations in Table matrices of spinorbit interaction for the twoelectron I 11 may be readily calculated.270 INTEBMBDIATE COUPLING 5 I 11 are the factors given by 10*2 with jS 1 ^  5 2 = f 3 $== I.
we obtain the matrix given in Table 3. if* 7 By adding the electrostatic energies of 5 to the spinorbit matrices of Table 1 U and solving the resulting secular equations.911 MATRIX OF SPINORBIT INTERACTION 8 271 Illustration: in 4 6m for M = J.gt. x) in Fig. we find for the energy 5 levels of si in any coupling the values: Here = &. The SLJM states for j? 3 were obtained In the zeroorder scheme 48 6a the matrix of 1 has the H value A A B CDS B C D E When this is transformed to the ln . as ordinate. Phys.gt. I from to oo. SLJM scheme by 48 6m. 35. 33.lt. fx. 1342 (1950).In order to keep are f x and x~&.2) to jp is an the configuration sp.gt. the ordinates from going to infinity we plot instead ===.oQ. Apart from .?! while . 297 (1929). Illustrations of the transition from LS to jj coupling. The complete transition from LS coupling f (fl 1 &. For = the energies in these units are + 1 and 1.gt.F . I FQ and hence does not need here to be considered further. 3 * HOUSTON. .As the whole transition by making a plot of JGl against x.. Eev. in coupling ( ffj is plotted additive constant which does not influence the intervals between the levels &. while for Q^O. and in order to confine the abscissas to a finite range. we see that the ratio e/6^ of the energy value to G^ is a function only of x = f/ Gl . Phys. At the left end. we plot this against 11 In this way we show the true interval ratios for all x ^j(1 4. 11 for Fig. CONDON and SHOBTLEY. they 3 Hence we cannot show */#! approaches infinity. Eev. e/G^ is effectively plotted against }/&. The configuration p*.
272
INTERMEDIATE COUPLING
311
at the right end /f is effectively plotted against 1  (&lt;?!/) chosen to make the total splitting the same at the two ends.
T^ factor  is
5
6
7
8 3
I S S
7
S
5
4
3
2
11 Fig. I
.
The configuration sp in intermediate coupling.
./
2
3
4
5
6
7
$
3
I
3
3
7
6
5
#
3
2
/
I
2
3
4
5
6
7
&
11 = Fig. 2 . Interval ratios for sp. (x K/#i *)
In order to see how well the observed si configurations fit these 11 and 3 11 for sp and sd respectively formulas, we have drawn in Figs. 2
curves which show the theoretical value of ( 3 L
as ordinate against
 3 L_1 )/( 3 il4 1
.
3
LJ) plotted
(^i^i)/^
3
^!) as abscissa. These curves
3 11
ILLTTSTBATIOXS OF TRANSITION
FROM LS TO
jj
COIJTIX&G
273
are in fact straight lines: if abscissa by a,
we represent
I
.
the ordinate
by o and the
0=
I
The plotted points
represent these ratios for the observed si configurations. It is seen that in genera! they follow the theoretical formulas rather well. While there is no essential requirement that Gl be positive, and there are
many sd configurations in which the singlet is
below the triplet as
if
G
2
were
"Q
./
2
3
4
5
6
7
8
U Fig. 3 . Interval ratios for ad.
(x =
K/&lt;?,
.)
negative, the interval ratios for these cases do not obey the above formulas at all accurately; they are probably all to be explained as in I 15 by a strong
perturbation of the singlet by another configuration. No plot is made for sf configurations, since there are just a few known, all close to the Russeli
Saunders limit.*
* Formulas which make an approximate allowance for the terms in the Hamiltoiiian which express the interaction of the spin of one electron with the orbit of the other have calculated for * I by use of grouptheoretical methods by WOLFE [Phys. Rev, 41, 443 (1032)]. We may derive Wolfe s formulas very simply in the following way. For a twoelectron 7 configuration this interaction is assumed to have the form. (of. 7 I)
"been
(1)
The second
factor here has no elements connecting different configurations.
By
writing
(2)
LSELt
2
(J"
Si,
 JL2  S2 }] minus that of the spinorbit interaction we see that its matrix is that of L*S [= J with ^(r ) and hence & set equal to unity: both of these are known in LS coupling. This matrix must be multiplied by that of w(rl9 rx ) for the configuration under consideration. If in we replace the mutual distance r lt by r we have a function p(rlf rt ) merely of the *K**i* magnitudes of the radii. The matrix of this for a configuration in which the I values of the two
*"t)
&gt;t
cs
18
274
ESTERMEDIATE COUPLING
i?*
3
U
V, J.W.tf
1^
1
\
SP 7.
"!
XGJ
rs = A  ^.F*  It 4V aai ps _ jus *2b j. 4b zrj2 ^0 J^z f S
C
s&gt;
7
_
*
,
*
*
4.
&gt;j
If /JF 2 is expanded as a power series in /jP 2 keeping Just the first power, these results agree with those obtained in Chapter vn for LS coupling. If
s
c
j
Is
expanded in terms of ?V, the
.
results agree
with those of Chapter x
for jj coupling. See Fig. I 10 The complete transition is plotted in Fig. 4 11 as a function of x = e superpose on this figure the observed levels of Ge 1 4p 2 3 Sn 1 5j? 2 and Pb 1 6p 2 placed at such values of x that 3 X the mean
K ^V
"^
,
,
P
,
of
IK and SP!,,
and the mean of
^and
Sn I
9180
8
Pfit the theory
Pb I
9215
exactly. This
corresponds to the parameter values
Ge
I
F2
i
10169
8801
20973
7294
1583
X
elections are different constant value
is
0173
0457
diagonal in the zeroorder scheme, the diagonal elements having the
"
Hence
just
TI
in
any scheme
this
matrix
(2).
is
with
0,J,
times the matrix of HcssellSaunders ease. For si, the matrix of  1, I  1, for lL 3
t ,
To
is
s
this approximation, the
v ^ times the unit matrix, and the whole matrix of JEf is Lande interval rule still holds in the
Hs

TJ
written for
z
.
When
Tl
times the matrix of L (which is diagonal with elements TJ 3 lj ^ _i) minus the matrix of spinorbit interaction of Table I 11 we include this matrix, we obtain the energies
z
S
cannot compare these formulas satisfactorily with experiment because we have now as many parameters as energy levels. These considerations can readily be extended to other configurations. * The secular equations for this configuration were first calculated by GorBSMJT, Phvs. Rev. 3 35, 1325 (1930), and those for p later by INGLIS, Phys. Rev. 38, 862 (1931), by the following pro cedure: Since all the matrix elements of the Hamiitonian are linear functions of the JP s, G\ and f s, the secular equation for a J value occurring n times will be homogeneous of ?i til degree in the J^s, GTs, t?s, and , the energy variable. For small J*s, the roots of these equations are linear functions of the F*s, G^s, and f s, known from the electrostatic energies and Lande splittings of Chapter vn. IFor smaE electrostatic interaction the roots are linear functions of these same para meters known from the considerations of Chapter x. Knowing these roots for limiting values of the parameters serves in simple cases to determine all the coefficients in the secular equations. Since this procedure does not give the energy matrix, it is not possible in this way to determine the eigenstates in intermediate coupling in terms of those for pure coupling for use in Zeeman effect or intensity calculations. In simple cases, the weakfield Zeeman effect is given by addition of terms in Jf* to the secular equations.
We
3n
ILLUSTRATIONS OF TKANSITIO^ FEOM LS TO
jj
COUPUKG
atom
275
gets
It is seen that the coupling gets progressivelj closer to jj as the heavier. The separation between the two levels of J = 2 and the
between the two levels of
are seen to agree
J"
= 0, which are absolutely predicted by the theory,
the observed data.
separation
weE with
X.
*
I/K
11 Fig. 4
.
The
configuration ^p
2
in intermediate coupling. (^ = J/JFa .)
One
eigenlevel of
3
j?
is
2
Pi
,
with energy 3jF
,
one
is
2
D
5
with energy
4
2
%FQ
6jF 23 the other three levels are linear combinations of
$
,
P f 2D
,
t
with energies given by the roots of the secular equation
3
4
2LF2
2
f
(90 J
 C 2  ^jP2 C 2 = 0.
)
,
These energies are plotted in Fig. 5 11 as a function of x = /jF 2 together 3 which are seen with the observed levels for As I 4p 3 Sb I 5p 3 and Bi I to depart progressively from RussellSaunders coupling. The values of x for these configurations were determined by making all the levels fit as
,
,
6j&gt;
5
well as possible.
The parameter values
are
The configuration jp 4 is similarly discussed in Chapter sm.
1
82
276
ZN TEEMEBIATE
311
For more complex configurations the formulas become more complicated and the number of parameters necessary to determine the intervals greater than two, so that it is no longer possible to plot the complete transition in two dimensions. Xo comparisons with experiment have been made for such configurations. The secular equations are readily obtained from the electro 11 static energies of Chapter vn and the spinorbit matrices of Table I .*
2
3
4
5
6
7
8
$
I
3
8
7
6
*S
4
3
2
x
11 Fig. 5 .
*
i/x
The configuration p
in intermediate coupling*
(%= JJ/^a
)
At this point we can merely call attention to a recent paper by Bacher and Goudsmit f which makes a good start on the problem of calculating the absolute energy of a state of an atom from the experimentally known
5
energy states of
its ions.
It
is
unfortunately too late for us to treat this
important paper in detail.
[Phys. Rev. 45, 412 (1934)] lias shown that in the addition of an * electron to tie atom may be easily calculated from those of the ion by vector mode], and that in tJiis case the spin of the parent term is always an exact quantum number. By the procedure of l u , the spinorbit interaction for such an atom is easily obtained in terms of that of the parent ion. MEBBELL [Phys. Rev. 46, 487 (1934)], combining these calculations, has made an interesting comparison with experiment of the energy levels based on certain definite terms of the d k ion in a number of configurations of the type d*n* *
ion, the electrostatic energies for
*
VAX VLECK
an
the
Dime
f BACKER and GOTIDSMIT, Phys, Rev. 48, 948 (1934).
4 11
4.
LIKE STRENGTHS
ENT
ESTERMEDIATE COUPLING
277
Line strengths in intermediate coupling. The strength of a line from a level a J to a level b J is given in any coupling 4 by formula 7 5 in terms of the quantity (aJ\P\bJ }. If the expansion of the state aJ is known in terms of a set of states T(aJ) and the expansion of b J is known in terms of the set Y( J ), we need to know the values of only
(aJ:P:/8J
(
:
)
P:
)
transform
to obtain the strength of the line in question. Since the factors like the components of a matrix of an observable ( 9 3 1 2)
5
/
/
).
(1)
The matrix components on the right of this equation must be taken between states having the same phases as those for which the transformation co efficients are calculated. Hence we cannot immediately replace these matrix
components by the square root of the
line strengths as given by Chapter IX. However it is convenient to replace these components by quantities which we shall write as S*(oc J, /?*/ ), and which are understood to be the square root
of the line strength taken
f
or
according
to the sign
of the matrix component
f
lpJ
).
Hence we write
,
bJ
)
= S (aJ\*J) S*(oc J, @J
a/?
f
f
)(fiJ
\bJ
).
(2)
In
this
way we can
magnitude of the S
s?
use directly the results obtained in Chapter ix for the and need only learn to choose the proper phases.
S*.
Phases in the matrix
configuration I f IV
(
Let us consider, as in
y
W! yIVIVIV SLJ:P:^S^U
expressed
3 9 , the transitions from configuration I f II to and ask the phase of
&gt;y^$L
SLJ
).
This element
is
by
11 8 with
3
S+L=J in terms of
which
3 1 1 8.
in turn expressed by 1 1 3 8 with JLx f IV or Ll f JLn = L in terms of (yivj^iVpynjrjij jj^ eac 1 case jfaQ proper sign of the coefficient is given by
is
B
In the same way, we find the relative strengths of the lines in a multifrom 2 9 2 and then the relative strengths of the multiplets in a group plet 9 having the same parent terms by a reapplication of 2 2 with SL J, SL J*
?
replaced
by UU^L, I^L^L This expresses the strengths of all lines in the in terms of S(yIv v LIV y^S^U1 }. group get the proper phases for the S^ s if on each application of 2 9 2 we carry the factor where ( I) 2 is
.
^
J
We
(1)
written in these formulas and also in the second formula of 2 9 2b, when J(J+l) S(S+l)iL(L i 1) is negative. This amounts to carrying in
Table
I9
satellites
a minus sign for second order satellites when L+L 1, and! for all and those principal lines for which S(S Jr l)&gt;J(J+l) + L(L4l)
when
278
OTEBMEDIATE COUPLING
411
In this way we find the phase of S^ for a given line in terms of the phase of rv I S&(y S *IF y^S^L^) correctly for eigenstates with the phases we agreed
9
to use in
I 11
in calculating the
For
transitions in
energy matrix. which the relative multiplet
intensities
cannot be
obtained by the method sketched above, we must calculate the matrix (ySLlPvy SL ) directly from the eigenfimctions used for the expression of the energy matrix. We assume that the states of a term have the proper
relative phases as given
f
8 by the calculation of 5 Then (ySL\P\y
.
SL may
)
be obtained by finding the matrix element (ySLMs 3IL \P\y SL J}Is 3IL ) or (ySL J3r\P\y SL J JI ) for any one component of the multiplet, since the
values for
all
components
expressed in terms of from the zeroorder eigenfimctions by the formulas of electron components (cf. 4 9 1 and 3 9 6)
(n
I
may by the (ySL\Ply SL
f
f
formulas of Chapter ra be readily This matrix element is obtained ).
66
and the one
m 8 rn^erln
I 1
m 8 wj) = s
l)(iij)}.
(3)
The procedure
for finding intensities in intermediate coupling is thus the
following: Put the calculated eigenvalues of the energies into the energy matrix to find the transformations from the i$coupling states in the usual
way. Find the matrix of Si for states with the same phases as those used in obtaining the energy matrix. Multiply the two transformation matrices and
the S^ matrix according to (2). There are at present practically no data suitable for comparison with the theory, so we shall not carry through a detailed calculation.
Sum
rules.
Concerning the line strengths in a transition array, we can make certain general predictions in the form of sum rules which are independent of the coupling of the configurations.
The most general of these is the Jgroup sum rule** We call the array of lines connecting all levels of a given J in one configuration with all f levels of a given J in another configuration a J group. If neither of the configurations is perturbed by outside configurations, it follows immediately from 4 U 2 and the principle of spectroscopic stability (2 2 25) that in any
transition array the sum of the strengths of the lines in a J group is independent the of coupling. If several configurations are perturbing, we must
enlarge
to include all perturbing initial levels levels before the above statement becomes true,
*
/ group
and
all
perturbing final
HARBISON and Joiosoy, Phys. Rev. 38, 757
(1931).
4U
LINE STRENGTHS IN INTERMEDIATE COUPLING
rule of importance
is
279
is
The next sum
the
Jfile
sum
rule* which
an
extension of that proved in 3 9 for LS coupling. In a transition array, the set of lines connecting a single given level of one configuration with all levels of the other configuration we shall call the J file referring to
a transition array like d^p^zdfid, the of the different files referring to the levels of d*p were propor strengths tional to 2J+ 1, and the strengths of the different files referring to d*d were proportional to 2Jf 1, in LS coupling. We shall here show that this
that level.
in
is
is
We
saw
3 9 that for
true for
any intermediate
coupling.
In
this case the
jumping electron
not equivalent to any of the electrons in the ion in either configuration, and the Jfile sum rule holds for both rows and columns. For such an
t
5 4 array as d p*=?d in which the jumping electron is equivalent to other electrons in one of the configurations, the strengths of the different files
referring to
d5
are.,
in
any coupling, proportional
c?
to 2*7+1, but this
is
not
true of the
files
referring to
shall
4
p.
the strengths of the Jfile$
In general, we
prove that for any coupling,
&gt;.
referring to the level of the
\
i
i
configuration are proportional to 2
jincLl
)
provided that the jumping electron
configuration.
is
not equivalent to any other in the
.
.
In
this statement, the
\
{
,
!
jumping electron
In case
it is
may be equivalent
not equivalent to ^
to others in the
final
configuration. &
j
another in
either configuration,
the
sum
rule holds for the files referring
to both configurations. That this sum rule holds in any coupling for the files referring to ps and to pp in ps^=?pp and for the files referring to 2 in ps^p* follows from
j&gt;
an examination of Table 2 9 or Table 3 10 In these tables, we see that the sums of the S*s in all columns headed by the same J value are the same, while the sum of the products of the S^s in any two columns headed by the same J value is zero. Therefore, since the S^ s transform like the matrix elements of an observable, it follows from 2226 that these sums are invariant under any transformations of initial and final states which do not mix up
.
the
J
values.
tables,
A similar statement applies to the rows but not to the rows of ps^p2
.
of p s *^pp in these
In order to prove in general the sum rule as we have stated it, we shall apply considerations similar to these to the whole electricmoment matrix for the transition array in the zeroorder nlm^ scheme. Let us consider
the transition array connecting the configurations A and /z. We suppose Z= 1 or 0), A contains nlk and that in the nl and nT shells (where Z
* SHOBTLEY, Phys. Rev. 47, 295, 419 (1935).
280
ft
INTERMEDIATE COUPLING
4n
In addition A and ft have the same numbers of electrons in ail other shells. For a nonvanishing matrix element of P in the zeroorder scheme, the quantum numbers in these other shells cannot When they do not differ the element has the same value differ in A and
contains
iJ^n V.
p.
V which we now consider. First we calculate the sum of the squares of the elements of P connecting k~ l n l k The the state O(wijw& wzf m?,...,m*?w?) of nl to all states of nl must be all different if the state is to be numbers in k sets of
as in the
amy
nlk
^nlk ~ n
l
f
t
f
.
quantum
...,
&gt;
allowed. This state will combine with the states
0)Y(tnTOf,
,
0*X),
W(mlm}, rojmf
...
,
&gt;
,
...
,
mjwif,
1
*
mX),
have
...
,
of wZ^nT.
CWT(i}mJ, and For combinations between
6
rojrW
mX)
(4)
WT we must
m8 = m*
,
the matrix ml ml or m 1. From 6 8 we see that the square of 2 cal is just (nZwi*wifPwTma7nJ) cpand element of P connecting its quantum numbers. The culated for the one electron which changes is given by to (i) Y for all total strength of transitions from
&lt;*&gt;Y
*
mX
J

031
oo
s is just k times The total strength of all transitions from O to all the tMs and is independent of the quantum numbers in We shall now show that for two states a and & of nlk the sum of
&lt;t.
T
9
&gt;
&lt;1&gt;
,
in the transition array is zero, the scalar products of the elements of 6 are a and referring to i.e., that the two files of the matrix of 5 do not combine with the same states and orthogonal. The states
P
P
&lt;t&gt;
ff
&gt;
of nlk
^nT unless
*
they agree in k
a
1
of their sets of
.
has mfm\ say that 1 sets, the files referring to them are obviously orthogonal. If they in k do agree in all but the f^ set, they combine simultaneously only with the of (4). The sum of the scalar products of the elements con states (i)
&lt;!&gt;
a
where t & hasmf mf
If
a
quantum numbers and 6 do not agree
&lt;D
T
necting them with the
states of
(i)
T is
),
E (nZmfmpjPlnTmX) (nTmXJPNmf **?
and
&lt;!&gt;
this,
r
= tj2&
by
13 3 1 3
is
seen to vanish unless
mf
mi
a
,
mfmf,
i.e.,
unless
Hence
in the
nlmsm scheme, the sum of the absolute squares of the
l
k having a common state of nl is independent of that state, and the files of matrix elements from two states of nlk have 2 vanishing scalar product. A simple extension of 2 26 shows these properties
matrix elements of
P
to be invariant under unitary transformations. Hence if we return to the complete configurations A and \L in a scheme characterized by / and
M
in terms of the oneelectron component (nl\P\n r) of the strengths of the files. fur Phys. 13 B necessarily inaccurate. 461 (1934).1. it holds with respect /z in the perturbed case. by noting that two files of the same J group are orthogonal since they refer to different quantum numbers of the ion (the valence electron must have quantum numbers 3 by showing directly from 1I 8 that ns^). and v separately.) Such a strengths in this array should be the same as has been made by Shortley (foe. In the same paper is reported an attempt to calculate the detailed strength pattern for this array by the method we &. 88. (We shall see in S that the strengths in the neon array 2y 3p those in pp&. 3j&. in jj coupling.4n values. This rule says that for these arrays the individual J groups may be broken up in one direction into invariant files.l ). and J = (2J + 1) ) \(p\P\8)\*E(p. (6) This proves the /file sum rule as stated. These statements are proved (using 2 226). using the parameters of Table I for 2p was not satisfactory because a small change in the parameters has a very and the parameters used were large effect on the calculated strengths. then if the sum rule holds with respect to the J files referring to the With regard to cases of configuration interaction. levels of to these In. cit.gt. not equivalent to any electron can obtain yet another rule which is The direction is such that all the Ines in the file have a level of xs in common. J. and J. we may be called the J groupfile sum rule. *). and their strengths are shown in parentheses. and gives the absolute values.gt. .) with agreement within comparison the experimental error. LINE STRENGTHS IN INTERMEDIATE COUPLING 281 we may say that the lines haying the initial state XJM have the 2 strength sum &{(nZ:P:^T)J H(l r) and hence that the J file referring to the level AJ has the strength ? k(W+l)\(n&PWl )\*E(l. The J files strength of each allowed Jgroup file is the same as that of the referring to the levels of a 3? which cross it in the array. Zeits. The best experimental data with which to compare these sum rules are the anomalousdispersion determinations by Ladenburg and Levy* of the 13 5 5 2p 3s. the still more special case of transitions a s *=?& p in which the valence A in the transitions to files electron Jumps from s to p or p to s and in the ion in either configuration.. This calculation have outlined. f 9 we may say that if a pure configuration A combines with two perturbing configurations \L and v.p&. These /group files in Tables 2 9 and 3 10 are set off by solid and broken limes. (7) for / = /+ 1.gt. * LADE*BUBG and LEVY.
1247 (1929). 217 (1934). MJENZEL and PAYSTS. III.gt. Menzel and Payne. We shall Emit A^ ourselves to the The most famous of the nebulium lines. t STEVENSON. . Astrophys. They were often called nebulium lines because it was thought that they might be due to a new element not yet known on the earth a repetition of the history of helium s discovery on the sun before it was found terrestrially. 19. 1 (1928). . p 3 tffeHllm&. s BOWEN. INTERMEDIATE COUPLING The forbidden Maes of astrophysical interest. Roy. Proc. e j o11 For a long time several prominent lines in the spectra of some nebulae remained unclassified. Phys. Rev.f Calcula have been made by Stevenson and by Condon. Acad. therefore. * . Bowen* finally showed that they are due to transitions in oxygen and nitrogen in various stages of ionization. 298 (1932). Sci.282 5. 34.. Proc. J. Astrophys. Nat. called Nl T and J\ 2 were identified by Bowen as the transitions 5 p 2 configuration. The most systematic study of astrophysical data for identifications of such lines following Bowen is that of Boyce. As we have seen in the preceding sections. 67. f BOYCE. 79. A137. To the first order of the perturbation C = 210cm. 581 (1933). be electricdipole that they are partly quadrapole and partly magnetic dipole in character. Soc. We shall see figuration. 6 11 in transitions are made possible by the slight de~ g 3^ t 3 partures from EussellSaunders coupling.. They cannot. CONDON. the eigenfunc. breakdown of coupling is expressed by the transformations: We spinorbit interaction are given in Table I 11 . 5 and 3 ^ P The  com 6U Bowen  s iden tification of the . are what make the nebular lines possible. evaluate the parameter f from the intervals in the 3 term.for b and d The matrix components of the 00 theory .. The atoms involved have p* p* and p^ for their normal configuration and the lines arise from transitions between different levels belonging to the normal con s radiation. obtaining 1 III. BABTLETT. J. These intersystem indicated in Fig. P are given by These values though small. usually 1 bination of those for will be designated figure.* An earlier calculation by Bartlett is based on approximations not tions of the transition probabilities sufficiently exact to / ^o &o be of interest. n called 10 is a hnear ii j v tion of the level  . actual levels ^^ N i and ^ The by the letters on the left in the the approximate RussellSaunders labels being given at the right.
is 3 only about 10~ as strong as the HABTEEE and BLACK. in atomic units.lt. A139. one of which is due to purely quadrupole and the other to purely magneticdipole radiation.gt. the quad transition probability giving only 01 per cent. Proe. rupole term in the whole amount. The calculated transition probability is The &. but not being an intersystem combination (A&= 0) it does not depend on the partial breakdown of coupling. J? 2 ) 3 1) = 15 X lO^see. Roy. The calcula tions give A(O A(C magneticdipole * . On the other hand G Q+B2 cannot occur &. P is interesting.5U THE FORBIDDEN LINES OF ASTEOPHYSICAL INTEBBST 283 By means of tie results of Chapter vni the RnssellSaunders eigenfunctions are expressible in terms of those of the zeroorder scheme. using the eigenfunction of Hartree and Black. We therefore have two lines close together. with magneticdipole radiation because of the dipole selection rule on J. .* is 124 so using the formulas of Chapter iv connecting line strength with transition probability we find for the absolute value of the transition : The value of this probability for the two lines B2 = 0018 sec1 ) A2 The lines are T : A(^4 a spj) . (Quadrupole) (Magnetic dipole) . Soc. Likewise 3 P1 cannot be a quadrupole line as 01 change in J is of vanishing strength for this type of radiation. Being a line for which A J = 2 it is entirely of quadrupole character. 311 (1933). . of the 2 is The rise to line (7 &. = 0006 sec1 . From the latter the matrix components of quadrupole moment and magneticdipole moment may be computed.1 1 sec".way the following results were obtained for the line strengths: Line Magnetic dipole Quadmpole Here s 2 is the integral s2 = e *3C Jo r 2 E*(2p)dr.4 called an auroral line since in OI this transition gives the green line of the aurora and the night sky. The line CQ*DQ is forbidden in all approximations by the general exclusion of 0^0 transitions in J.7 triplet C 3 &. .gt.gt. P = 0102 indicating that the quadrupole line line. almost entirely due to magneticdipole radiation. In this ".
which contains the and the same 77 other electrons. We shall consider in particular the four transformations nljm *? \\ 33 JM *=? SLJM and incidentally the transformation nlmsmi 2=^ SLMS L In preparation for Chapter xnr on configurations containing almost closed shells we shall establish a correlation in each scheme between states of a given configuration containing an almost closed shell and those of a corresponding simpler configuration. 451 (1933). * Let us consider a configuration which contains. J$? To this configura we shall correlate a simpler configuration e same closed shells. however. outside of closed shells. of little interest. M transformation matrices^ 1. although TJ formally there is no restriction placed on their magnitude. a shell &* which is complete except for e missing electrons.coupling scheme of I 10 characterized by the electronic j values and resultant JM. which we l the 8 L scheme. Here e and q are considered to be small integers. Bev. Pnys. and in addition other electrons. jm 8LM M and SLJM respectively. This case is. missing electrons have the negatives of the f of * S? S and whose i\ and ml values of the e electrons in shell s other electrons have the same quantum numbers as m SiiOETLEY.CHAPTER XII TRANSFORMATIONS IN THE THEORY OF COMPLEX SPECTRA* We wish In this chapter to consider. and the ^". considerations of this chapter can all be readily extended to configurations containing more than one almost closed shell. 185 (1932). Configurations containing almost closed shells. There are five representations scheme and shall designate as the two zeroorder schemes. 40. In the nZwywj scheme we shall correlate to a given state of & with quantum e numbers listed in the standard order of 56 that state of 3% whose . 5. and determine the relation between the corresponding* . t The . ibid. electrons present in shell &*. This configura tion we shall designate as configuration ^. the transformations between the various schemes of states of interest in the of importance the theory of atomic spectra. tie two LSGoiipling schemes characterized by 3 mm i . since such configurations occur 5 c 5 4 mainly for elements near the tion right of the periodic table. more in detail than heretofore. 43.
In the nljm scheme we shall correlate to a given state of JS? with quantum numbers listed in the standard order of 5 6 that state of 3t whose missing . and whose rj other electrons have the same as those of J? taken when in standard order with the quantum numbers Here I is the azimuthal quantum number for the shell y phase ( which in contains p electrons with j=l + % and q electrons with = .lt. With this correlation we shaU show in 2 12 that the matrices of L S2 L2 and L*S are the same for the two configurations. are the same . We configurations in 2.lt.be LS coupling. states of ^. . is in shell SP* the second term vanishes.. will transform them to in l coupling thus have the same binations of the correlated 8LM8ML or SLJM values for the two LS coupling will ". M values. for the two configurations. have the same j values but the negatives of the m values of the e electrons in shell of 3?. will is In order to show that the same matrix it rilmfMi states of J? and 9k to L8 coupling. .) &.eKO&.(p + q=* ).. If a. Hence the transformation from LS J? and St. The transformation to LS coupling. If neither a nor b is in shell &*5 the value is obviously 3? and 91.+*). With j 2 this correlation we shall show in 3 12 that the matrix of/ is the same for the two configurations. 8 Formulas for the elements of these matrices were given in 4 Let us denote f by A# 9 A ^ 3 . the matrices of transform the correlated only necessary to show that . . the correlated states having the same values. . In order Matrix of IA The 2 to obtain a value for the first term a and a! must be of the form (w. two M same matrix tions. but not 6.I 12 CONFIGURATIONS CO^TAIOTNG ALMOST CLOSBB SHELLS 285 those of oSf with the phase shell taken when the quantum numbers are listed in standard order w where w is the sum of the m values of the electrons in ( & y l) .gt.$? 7 i)&. but the electronic j values of 3? are those missing in the corre lated states of ^. These correlated states have the same values. coupling to jj coupling is the same for the correlated states of This transformation will be given explicitly for a number of twoelectron shall . Hence the allowed states in jj coupling have the same electrons &. 6 12 . is given by of general nondiagonal element 8 the same for 4 3a. It is clear that this gives a onetoone correlation between all states of the M s and configurations. and hence that the .. Corresponding states in jj coupling will be the same linear combinations of the correlated jm states. zeroorder states of JSf and by A M A m . the correlated L 2 S2 and LS . ^ 9 i.. The allowed states in LS configura and corresponding states s the same linear com mm states. l .lt. JM show in 5 12 that with these correlations between zeroorder states of JS? and 0k the transformation from the msm scheme to the Jm scheme is the same for the two configurations.
r+1 . the sum of the m values in shell Sf differs by =*= are essentially equal dividua! set lying between and 01 we must consider the phases in greater detail. & r .TOl + l)x x A & . the third into a.)(.J) =0 and/fp^j) ~/(l r }) =0.. while this element is missing. . If A much the same as for L 2 and S2 element is 8 given by 4 5b.. Then the sum for group a has tlie siam for .j). putting the first section into group a 9 the second into /?. In a similar ^(Agt) and ^(A m ).. Jlatrix of L*S. . A in two electrons. . the matrix and for j? have the If a and a! are in shell from If . The first term is the same for A m and A # as also are the parts of the second and third terms arising from shells other than SP.. %.gt. But /(ft) =/( . then the following sum has the same value for groups a and mi )8 (the individual integers are denoted by m L ): S[Z(Z+l)mf] + S[^Z+l)HXz]&. Consider the sections as defined by section points p^... x f This may be proved as follows: The division into groups a and ft may he made by splitting the I. (mjf (.lt... The parts of those terms which arise from shell SP are the same if calculated for A s as for the group $ missing electrons of A M The equivalence of the calculation for the missing electrons to the calculation for the electrons present In _4 m is a direct consequence of the following ...Jj52 .lt. . results in a second difference in sign The diagonal element of 2 is given by 48 3b.1 ) is present in JSP so far as shell A m and A m is Concerned A s and^ difier by an odd permutation. etc.. . A SP&. In this case A& and A& will nave the forms: . might have the following electrons :  X X Here x indicates tie presence. the calculation is and A differ in one electron.the absence. all sets except those noted explicitly are the same for Ay and A#.) z .* 8 Equation 4 2 shows that in and (wi . .gt. How one in A m and A m This ever.** j&. pz . Hence the sums for a and f3 are equal. l from the different choices of phase for which makes these two elements just equal. m wMe Professor Bennett of Brown University. where /(p}=(Zf ^) 2 . such that the section contains the numbers p t f. is the same for not be discussed in detail..gt. wav one demonstrates the equality in case a and 6 are both in shell ?.. Pt ff .i ..286 TRANSFORMATIONS IN THE THEOBY OF COMPLEX SPEGTEA ( 2 12 M _ i). This do not differ in order. . has tlie value/(^2 ) +/(p 8 ) f/(p 4 ) + the value /(ft) */( ft) +/(ps ) +/&. interesting relation: If one takes the integers (or I and arranges them into two groups a and /?..The value of the sum (1) when z runs over the numbers of thissectionis /( pt ) rf(p t ^.. * For example shell & of A s and A Ay .. of a given individual set.P4) + * ft One of these expressions ends with the term f(pr ) 9 the other with/(pr+1 ). . This proof was suggested to us by series &.. The converse is true if 2 Z introduces one difference of sign between (A&\L \A&) and (A a\L \A a).f is (1) taken over only those m/s for which m l I is also TMs The 2 completes the proof that the matrix of L calculation for S 2 is very similar and differs will ? and 91. x A a .. If theinthis case the elements for * (wi. where the second sum in the group. halfodd integers) Z... Pt+i i. I into r sections.
one difference in sign of the matrix elements is intro duced by the different l values for A M and A m For J$? the second. In the next section we shall specialize to the particular transformation of interest to us.lt. +l)+ are present. The transformation between zeroorder states. One (m I). say that A contains a and 6 where A contains a! and b This element has the value 1 m . the diagonalization method is however much simpler than for LS coupling.nbl ) )(ja ma \Jx \j bmb ) element of J \ is 3 given by 3 4. however.b Now with the correlation given in which is I 12 it is easily seen. 4 2 and the discussion under 4 5b). ". 5 is to the q occurring in the correlation factor ). third terms vanish unless b = (m l).m + . third terms vanish unless b = ( l )~.m^. The transformation from the nljm scheme to the jjJM scheme may be obtained by any of the methods sketched for LS coupling in Chapter vxn. The diagonal 2 is (A J*\A] = &M* + W S {/(. for 31 they will have the form . and the trans formation is diagonal with respect to the j values of aE electrons in addition to If.{(a\L*S a ) . 4 3).Sis obviously the same for J5? and 9t with our correlation. Hence in this case they m (A#\LS\A #)=(a\LS\a ) (A *\LS\A a) = .1)+.gt.Now if neither b nor c is in $?. l ^ c = (fln. since only one matrix. in exact analogy to those of 2 in S the sml scheme (cf. The transformation to jj coupling.4 S (a Jx \b)*. a&. second. by an argument the direct analogue of that given above for JL2 in the 6?% scheme 2 (noting that J is diagonal with respect to the number of electrons in shell ff* s w with j = l  matrix of J^ 4. and the relation between these trans formations for J? and ? with certain general correlations.c = (wij)+ respectively are present. For the ^ Am ^ .e. THE TRANSFORMATION TO LS COUPLING 287 .(m) a 2 } . that of J 2 need be diagonalized. 3.2(aSa )} = (Ajf\L*S A ^} 8 8 (cf. f for the The diagonal element (2 8 oc) of I&. The elements of the matrix ofjF2 in the jm scheme may be written down . that the the same for the two configurations and hence that the transformation to jj coupling is the same. where (a\Jx \b) = S(nala .f + 1) . ( l ( and then differ by the same per m . must both be in 3$. z may easily verify that A# and mutation. We shall in this section consider in general the transformation connecting two systems of zeroorder states.2 12 form (wij). . It has nonelements only between states which differ in regard to two in diagonal dividual sets of quantum numbers. This completes the proof of the equality of the Decoupling transformations for J? and 5?. Similar considerations hold other two possibilities. i.
Y this state to the (2) The transformation of following calculation.e. a* of quantum numbers is defined by ? &. by . &. 3 6 ).. Q{^.288 TRANSFORMATIONS IS Let us consider an sets of oneelectron T THEORY OE COMPLEX SPECTRA 4 12 A eleetr0n configuration for which there are n possible us denote these 1... quantum numbers.. arranged in the order a1 2 &.. w. vanishes. (2) .1 =2s C^.^).^!* 1 ^ * JOT 1 example. ..lt. state a1 a 3 The transformation y ..2 =2 0~.. 2=2*& k 3= . 2. in some standard order.. A =3 and =8. In the second scheme let l../?*&.2. * / \ * (3) ]&&.a 1 . v ...ot = j/&(ai)fc(a) .lt... *). a 2 1 J? connectmg the state ^ / jS . by the numbers 5 and the corresponding states by ^(I). /4=3pl..^ In the first zeroorder scheme let individual sets..^(^^... t n for the quantum numbers.... and ^(/l)* ^(/^)j 9 ^00 f r t&6 states.*.. 5= / for the jm scheme by l=2*i.. . i.n...a*)= where we use the notation S ff . a 2 .lt..lt. 2..lt. .. MO?) *) y axe JVmimbeisof theset a 1...3=3pl+. is The transformation between these two oneelectron systems given by The a2 ? zeroorder antisymmetric function belonging to the complete set a1 . .gt. Wa. 3 iff(n).^ with the (quantum numbers in standard order) is given. the possible sets of quantum numbers being given. . Here a &.lt... .* S ^(^) CjPlai) = S If S #(^)(^^) for jB s are equal the antisymmetiic factor $/... by just coefficient / this determinant: CJ^JP..^(2) us use the notation x . for the configuration 2s Sj) .&... primed scheme is given by the From and (1) . irrespective of the order of the /?X to within a sign which is just correct to give us a determinant of the two of the transformation coefficients. while a given set of /fs this factor is the same... T( ai*&.. for the M/n z scheme. then. (cf..lt.
. . 2. cs . the determinant (4) and hence the transformation co efficient (5) splits up into a product of factors each referring to a single shell.... (6) Because of this property.. . in considering the relation between these coefficients for JS? and 9t we may restrict ourselves purely to the shell SP so long as the J2? other quantum numbers are the same for the correlated states of and St. if the configuration consists of in other shells^ we may split off a and N on shell ?: M M electrons 1 (I . and con shall suppose that there are altogether sider the relation of these components for the configuration consisting of e m electrons in this shell. y ? 3 (7) This operator is seen to be unitary. Let us define a linear operator Z by the relations . ... We states in the shell &*. We shall denote a given eelectron state by 2 1 am ~ ) a ) and the corresponding (m e)eleetron state by T(ax a2 YCoc a where the a s and a s together make up the set 1. . . (8) : The relation between Z and Z is given by the following t calculation . . M) in shell SP factor giving the dependence at\ / am. cm ~e = am~~ furnish just the Laplace expansion *9 . In the primed scheme we shall define a corresponding operator f Z by ).a  S D since the terms for c 1 = a1 . For example. since the states on the right form a normalized orthogonal system.4 12 THE TBANSFOBMATION BETWEEN ZEROORDER STATES 289 Since the transformation (I) lias no components connecting sets belonging to different shells. m. . . This correlation is to be independent of the system of zeroorder states used in the description. electrons to that consisting of Let us seek an invariant correlation between an eelectron state m (m e) electron state whose e missing electrons have the and the same quantum numbers.
yf3\ wMle the otter terms l 2 T(x a .lt.. section. operation. and since in our correlations all electrons except those in she! ff have the same quantum numbers for 3? and we need only I 12 .e electrons in shell 5^ in St.. A linear correlation such as is obtained directly by omitting the bar on the right side of (7) is invariant only under real orthogonal transformations of the zeroorder states* .. numbers. TMs shows is electron states is invariant under a unitary transforma that the transformation coefficient connecting two eessentially the complex conjugate of that connecting the whose missing electrons have the same quantum and gives the exact phase relation between these coefficients.* may now calculate the relation between the transformation co We efficients: since a transformation coefficient tion.290 TBANSFOEMATIOKS Es THE THEQBY OF COMPLEX SPECTRA 412 *". we obtain an invariantively correlated (m e)eleetron state. & } show that this transformation is the same for the and the m . a ). We take the complex conjugate because by (7) Z acting on a state gives a TMs shows the operator Z state in the dual space. electrons in shell ? in ? linear a linear correlation. 4^6). We shall now show that this transformation is the same for configurations Sf and ^. Of transformations of the type considered in the previous we are most interested in that from the m/rii scheme to the jm scheme.m/ pressed in terms of the any state may (7) be exthat we see by comparison with to be invariant to within a constant factor. since taking the complex conjugate is an invariant. with the correlations of to the shells Eecause the transformation factors according (cf... m j &. (m }eleetron states 5. whereas we want a state in the same space. Since \I.". an electron state and then take the complex If we apply this operator to conjugate. vanish. Hie transformation nlm/n^nljm. but not (c^F^c^F unless c is real).
. of listing and ( 6 3* * quantum numbers (5 it is seen that ( 1) 2 = ( I) 5 *.lt. Our correlation requires that they have the negatives of the m8 . from the standard order 0". Hence. J seen that the element m)= .. The coefficient we would like to compare with this (2) is (TOj^V.ml} and m values missing on the left. This jjJM^SLJM is is seen to imply that the trans the same. 4 8) (ms mz Z+m) = ( (ms mj[l it is m ( 8 m^Z+J 7WjZ m). the situation is as 192 .mfm?.gt.m^m values of those missing m from the closed shell is / __ ^ \jfjtf (+ix4fl w (4) ( When we make the correlations of for the I 12 which include a phase factor l) M* mm s l scheme and a factor ( that the G.j&.. of We have found a correlation between the zeroorder states such that the transformations and 3$ jjJM^nljm. the transformation 412 1 is given by 45 8. . and by using the relations (cf. returning to (1).^a* . and is entirely real. j^x1 *2 .m.wfZ4J^^ where p + q = e.... If we denote the msmj states by &. But this is easily accomplished. (JPJP .gt..TION nlmsm^nljm 291 ifs(nljm). More explicitly..1} (3) is ( ms m) 3 times the element (2). Since M = M + ML B .(nlm/rii) and the jm states by correlating these schemes respectively with the primed and unprimed schemes above.. (3) is seen to be also. 4 12 IO becomes 1 . it is seen that the ratio of the transformation coefficient for the almost closed shell to that of the electron configuration whose electrons have the negatives of the s .. Let the coefficient on the right of (1) be (wJw. ae ) with j = Z .TMsvalueistx&. Now from a comparison of the two determinants of type 4125 which give the values of these two 5 coefficients. ^". we may say the same for the two configurations. The transforinationjj/Jf^^iJJf.. m/nrjm transformation is l)(*HX+0 for the jm scheme. The determinant of this transformation ( for an I shell is easily shown to be l) .beinsertedin4 J 12 10.^wiJmHJ + i:^^ If ( 3) (2) is in standard order. . where q is the number of electrons in l)2 =( 1 ) Yfa 1 oc 2 . (1) The states on the right side of this equation have just the quantum numbers which are missing on the left. at*).1. am~*) = (  l^^C^jS 2 .5 12 THE TBAKSFOBMA.. formation nljm^nlm/fi^ and nlmsm^SLJM are the same for the two configurations. Moreover. v iJ^wetfi).
is there is an arbitrary phase. Xow 2 writing simply the values of j the elements of this matrix are given with the abbreviations If we omit these quantum numbers. l . . n l JM. by the quantum numbers SLJM (this state is not uniquely determined for two reasons first. For example. and since their eigenvalues are known. 2 SLJM or jjJM define a The procedure we shall follow is that of calculating the matrices of X2 and S in the jjcoupling scheme and then diagonalizing them to obtain the L8 coupling. and the second electron the numbers n I j with resultant J y are given by formulas quantum 12 3 2 and 103 2. =If ff 2i1JL 2 The first two terms have known diagonal matrices. with the jl9 j29 j respectively of 10 3 . IJ. The matrix of the third term is diagonal with respect to nl. thesaine linear combination of the correlated mm s l states of ^ is a state of 31 characterized statement holds for a jj obtained in this farJS?. no twoelectron configuration or its equivalent can have more than four states of the same J and Jf.and ^". A similar states of 3k of 5f* The transformation between the LS. second. J. the set SLJM of quantum numbers not in general complete for more than two electrons so there may be two independent states characterized by the same SLJM) is a certain linear combination of the wyn/ states. this diagonalization is a very simple procedure.292 TRANSFORMATIONS IN follows: THEORY OF COMPLEX SPECTRA 8 12 A given state of the configuration J2? characterized. to be desirable to find a direct method which will enable this transformation to be calculated with greater ease. M ddoi ds dhas 19.f. jL . We shall define our phases by correlating. then.j . vector addition. Since these matrices will split into steps of at most fourth order. s f . for no two of the three transformations are diagonal in common with respect to more than If. JM state except that the missing j s of M are those s by this same SLJM. It seems.coupling way is the same as the corresponding transformation Xow to obtain this SLjj transformation by the combination of the other is in general a very tedious process involving the multiplication of three matrices of high order. in the process of first electron has the 9 9 . this being in general the only case in which the quantum numbers unique state (to within a phase). The following accomplishes this result for twoelectron configurations. j. while pp or p 5 p has altogether 10 states of Jf =0. 9 M . The matrices of JL2 and S* in a nonantisymmetric scheme in which the transformation to quantum numbers n 1. s.j. On the other hand the three and resulting transformation is diagonal with respect to both J and splits in general into steps of a relatively low order. and j 9 to = + .
S In (1) closely related to the above: LT by 5X if we replace and . unless ot = /? and j=/ the antisymmetric 5 Now ) ( )! *(*. / = and both states are allowed. and . diagonal ^". similarly we may replace 2 by (2w + l)/2w by Ij2w by l/2w and 1/2^ by + l/2ti/.) = & J ~ Jlf 2 it is easily seen that for nonequivalent electrons ( (ajjSjVIfHaj^ Consideration of the matrix element (ajoc/ a ^^) ( 3) Jif va7* aj* /If) = (jj \v\ JT) ( 4) j cases. if t. a^^J we have (cf. either antisymmetric or sym ^(JiJD is and excluded states.) The matrices of 2S1S2 and of 2 1 2 and 2S1 JL 2 are given by formulas &. 3*2) j". (I) either the upper or lower undotted sign is to be taken (In the first formula with either the upper or lower dotted sign. we have simply 2 These formulas. 293 . For an allowed state metric. .gt.Ifiw by + l/2w. In terms of these nonantisymmetric matrix components. j&. Jl)f 2wJ^". (jj \v\j . enable us to calculate the matrices of L and S2 for antisymmetric states in $ coupling using the nonantisymmetric values (1).6 12 THE TBANSFORMATIOS. if j = /. Second. / =J OT .gt. JS = n V and let all differences in quantum numbers Then be indicated by primes. 52 if we replace (2^ + we may replace l)/2u&. corresponding to allowed if jV j . the components as between antisymmetric states may be obtained by considerations such those of 3 10 . is a symmetric observable. Let a = id.jjJM^SLJM. First. if j for equivalent electrons must be divided into three tt m ^j (2) applies to both states. .&& Y(oy jSJ JM) 2^(*i Ji J2 with respect to njh and Wgig.lt. )=V2tfi M jj) 0V/) (5b) Third. then. subscripts merely denoting the electrons.
in this case the phases of the jjcoupling states would not be determined. TABLE I 12 . The phases in LS coupling are arbitrarily chosen. 612 twoelectron configurations up 12 On the left of to dd gives the set of transformation matrices in Table I the matrices are given the values of j and/ for the jj coupling states the J value is shown at the top in the RusseUSaundeis notation.294 TRANSFORMATIONS IN THE THEORY OF COMPLEX SPECTRA The diagonalization of these matrices for all .% S 77?e Transformation from jj Coupling to L5 Coupling The jjcoupMng states here have phases in accord with those used in deriving (I). since this matrix has a simple diagonal form in jj coupling. These trans formations could be used to obtain the matrix of spinorbit interaction in LS coupling. . f a a G. The transformation to jj coupling can alternatively be obtained by diagonal11 izing the matrix (Table I } of spinorbit interaction in coupling. The trans formations are independent of M. This would LS possibly be useful for a configuration containing more than two equivalent electrons if the matrix of spinorbit interaction is nondegenerate.
. By writing down all fying the exclusion principle. actual calculations by the methods given have usually become very laborious for configurations containing more than a very few electrons.. It will usually be most convenient to cha racterize such a state by giving the missing sets and the y others. The electrostatic energy in LS coupling. Bev. or calculated with no more labour than for those configurations. 43. But there is a class of multielectron configurations occurring near the right side of the table which are given unexpectedly simple pro perties by the Pauli principle. Denote the rest of the sets occurring in A outside of closed shells by a 1 a 2 . * we obtain possible combinations of missing sets satis all possible zeroorder states of the SHOKTLEY. denote the individual sets of the closed shell SP by a a . The transformations for such configurations were shown in Chapter xn to be immediately obtainable from the transformations for the correlated simpler configurations.CHAPTER XIII CONFIGURATIONS CONTAINING ALMOST CLOSED SHELLS. For a given state A in a zeroorder 2 1 scheme. . PfayB. There is little hope of improving this situation for multielectron configurations which actually are very complicated.missing* sets..* The electrostatic energy matrix for configuration M is in general quite from that for 3? and must be separately calculated.. . Phys.. The missing sets must satisfy the Pauli principle no two of them can be different . Configuration 3t consists of a closed shell minus c electrons. and any number of completely closed shells. configuration . identical. In this chapter we shall give calculations which will enable the matrices to an arrangement of the energylevel and intensity be either obtained directly from those for the corresponding simpler configurations.... am are the sets occurring in A and a\ . 632 (1933).. 1. em where a6* 1 . ? . JOHSSOS. 40. such as those which occur for atoms near the middle of the periodic table. a* are the ". Rev. XRAYS While most of the considerations up to this point have held in general for configurations containing any number of electrons.. . 185 (1932)... a a ~\ . These are the configurations containing almost closed * * shells which were shown in I 12 to have essentially the same allowed states as the simpler configurations obtained by replacing the holes in the almost closed shell by electrons.. 1 . a ?.... ij other electrons.
We may write S .9". Third. for each closed is in a closed shell. there are terms closed shell and the other is one of the q electrons of group a. e) times 9*11. Second. given by the diagonalsum rule in terms to a discussion of the diagonal element for the state A. terms.. The summation in may con veniently be divided into several parts. there are the terms in the summation in which the sums of these terms are sets are contained in completely closed shells. (2) .S t.] .S S + [J(oa*)Jf(tfa*)l. both of the individual First.. % Consider first the sum (A). Since most of the electrostatic energies of interest are of the zeroorder diagonal elements. 6 6 in which one set is in a given by 9 I2 and 9 13. Since these elements have the simple form given by 7 4. there are terms in which one set SP. These terms 6 are given in simplest form by 9 I I. we TMs proceed directly diagonal element is 6 96 2 given by 9 2. the sum in range 1 to terms. the second TJ. these we wish to reduce to summations over the more convenient [For example. Finaly. and has the value S [J(afa?)K(afQ?)] (A) 2 (1) The inconvenience here is caused by the long summations over the range e f I to wi. These terms are given.296 CONFIGURATIONS CONTATSTNG ALMOST CLOSED SHELLS I 13 The electrostatic energy matrix has nondiagonal elements between states of the same configuration only when these differ in regard to two individual 6 sets. if shell P contains nine d electrons. while if the range were 1 to (A) runs over 36 terms. involving no summation over the electrons of shell they cause no particular difficulty . the of closed diagonal element consists of terms in which both sets are outside all shells. for configuration M. the other in terms already considered are the same for (in shell. The by remainder of the diagonal elements of the configuration. that in (JJL) over e the first sum would contain no.
in group a). Of the three sums to which we have reduced (A). J(ai a^)=^J(a^a ).ai ].V F T//j irti\ /TY/fi i\1 O(\  f [J(oaO. has a simple sum over pairs of electrons chosen from e. first 6 given by 9 I1 and depends only on the con Since the term (v) is already in its simplest form. We shall use a notation of the type (0+ 1~). As an illustration 5 we shall sketch the calculation of the electrostatic energies for in which the np n p. the 6 first is a sum over the closed shell SP and is given by 9 12. we find for that part of (A\Q\A) which may vary within the configuration the value ". The second is 6 11 with nl = n l Only the given by e times an expression of the form f . In using the diagonalsum rule to obtain from these the iScoupling energies and 8 values of the state A are given by we must remember that the quantum numbers M L M the negatives of the values for the missing electrons plus the values for group a. we may calculate the diagonal elements using the of the missing electrons of shell /* exactly as for a simple configuration except that we reverse the sign of the interac tion of a missing electron with an electron in another shell (i.=E S 3 =1 ]term is S S [J(a*aO of which the figuration.e. from the np first entry gives the quantum numbers of the electron missing electron n p.THE ELECTROSTATIC ENERGY IX LS COUPLING 297 { where we have used the relations J(a i ai )^K(a&. 1 2) M M (5) . The double shell.gt. and Kiata^^K^tfaf). and this The term (ft) TO of 7? (1) becomes similarly &. third term depends on the particular state A of the configuration.^(a*^)] (fO w Hence.gt. the second the quantum numbers of the zeroorder states then has B values of the L and entry table giving the 7 the form (cf. aside from common terms.
the electrostatic energies for the twj configurations. d 9 p have the same electrostatic energies. using the above results.. all vanish. every other singlet has the same (?/s energy as the corresponding triplet. m m f . l 1 amdafed toll are the same. from a the same integral as for p $ In the first 3 generalization of the above shells. striking characteristics with reference to these The following formulas show certain &k *s.. if we like. by the usual diagonalsum procedure TMs is one of the important almostelosedstieli configurations which is correlated to a (nonequivalent) twoelectron configuration. hence in a table such as (5) we obtain Gk *s only for states having 8 none of the triplets have G*& in their electrostatic energy expressions. since J(i. TMs follows from 86 18 if we note that the ?.j) vanishes unless m^=m^ 3 ~ 0. and for odd f I + l coefficients of with even Jc vanish. at coefficient.298 COXFIGBATIOSS CONTAINING ALMOST CLOSED SHELLS this I 13 From we obtain. If we consider the 8 shel of !OT ~% as having one missing electron the result follows immediately 3 from 8 s 16. e. These H facts reduce our calculation for such cases to a determination of the co efficients of the G%s for the singlets. and Second. namely that with k=L. 5 p d m Z i 8 8 l9 m\. TMs may be inferred. For each singlet. TMs peculiarity was not noticed experi a nonvanisMng of lf most only one Since for even Gk has V coefficients Gk s with odd k mentally because for such configurations the spinorbit interaction usually as large or larger than the electrostatic. I^uthermore K(i.m* m* energies involving Fk s for Z II will be just the negatives of those for IF.j) depends on only the absolute values of 3 1 the terms in the electrostatic Hence. a mz ) by the state ( . e. scheme to include two or more almostclosed The procedure is essentially the same as the above with the additional direction that. is .g. that the separations for p*s and d g s are given by ds. this means.one assigns the usual (not the reversed) sign to the integral connecting electrons missing from two different shells. m ~l s Jim the same singlettriplet separaplace the configuration l as Is. ~~ m ~i double entry table of the type (5) for lm l V may be obtained from that for r 1 ! by replacing the state (wi^mj ms l ms m^. Z ** r. Third. With regard to such twoelectronlike configurations we may make seTeral general state ments.g.
3F4 3 P=F e . ". . Since are the same for Jg? and 3t. is the We shall show here that the matrix of spinorbit interaction in any coupling scheme with the correlations of Chapter xri same for configurations ? and ^.) .I 13 THE ELECTKOSTATIC ENERGY IN LS COUPLING 299 electrostatic energies for several configurations correlated to twononequivalentelectron configurations follow: The *F=F 2P2 *P=F ~2F2 +9CK?3 D= P + 7P2 D = F f 7F2 8 *&.4F2  P4 P4 tfsPolOPj.SPa 3 P = . except for reversal.For configurations of the type l .126^4 + 10^0 .5F3 . (This m &. j&. energies 9 2. it will suffice to show that all transformations one scheme.F + 15F2 ip = ~F@ hl5F2 3 D= ~F I2F2 =F ?=~F . . Hence d7 j? 4 and/ have exactly the reversing 2 and / 7 respectively.7=P .of the sign of the spinorbit coupling parameter nl re with the correlations of Chapter xn.?=P *&.7Pa + 84F 4  S D=F JD=P ~ 6F2 f99F4 ip=p 7Pf + 84F4 s^= F 14F2 126F4 *S= P 14Pa .lt. Tlie spinorbit interaction. l . m~~ e from 86 16 if we note that the double entry may be obtained from that for l merely by 7 the signs of all m/s and m/s.gt.lt. ferring to the almost dosed shdl P.6F2 f99F4 8 X P= F P= P 24FS 66F4 24Pa 66^ + 700! containing purely an almost closed shell we may say at once that the electrostatic energies are the same as for the correlated configuration l This follows table of the type (5) for l m . . Its value is given by 1 2. If this is written the (m tni is given as a sum over shell minus a sum over the e missing electrons our as a sum over the whole theorem is proved.lt. We may also show that electrostatic energies of d3 m ~ s has the same electrostatic as I s for any e. The simplest scheme to consider this relation is satisfied for any is the nljm scheme in which the spinorbit interaction is diagonal and in 10 of s. since the sum over the whole shell vanishes.4Fa  . in which the coefficient dependent of the electrons of shell &.
with the positions of the centres of gravity of the 1 terms given in above the lowest term of the configuration: cm".? arfe taken as the same linear combinations of the correlated zeroorder states. For example. e.g. The matrix of spinorbit interaction for IOT ~ is just the negative of that for the correlated states of I .*. 888 (1931). the raregas ions Sell.". and KrII consists of an inverted doublet. from the fact that 300 2 13 for M a whole closed shell. while the HEDSENBESG. Since there is only one spinorbit para meter if only one shell is involved. with the level of lowest j value highest. Fig. . der Piys. f Not observed. is the case for the F*s if the two fields configurations do not fit ~ the multiplets which are normal in l will be inverted in lm while those m ~^. the ratios of the term splittings are the same for the configurations I and Im~~ . for example. This constancy would imply that the electrostatic parameters all increased in constant ratio. The constancy of the ratios is striking in view of the fact that the individual the firstorder theory particularly well (see 5 7 ). We have shown in I 13 that the electrostatic energies of the two corre which contain electrons in only one shell sponding configurations I and outside of closed sheik. the spinorbit matrices in LS coupling are the same except for the sign of the spinorbit parameter referring to shell SP Pure almostciosedsheli configurations. An.. This means that in RiissellSaimders coupling. Ann.) Hence if the iiScoiiplmg states of 3t and &. the lowest configuration (p ) of all y are both hydrogenlike with different effective nuclear charges.CONFIGURATIONS CONTAINING ALMOST CLOSED SHELLS 7 L = J1S = Q in 4 2 vanisMng may be inferred. This is illustrated by Fig.lt. are given by the same formulas. 1^". This is a fact well known to inverted in I will be normal in J empirical 5 7 spectroscopists (cf.* who gave two examples of related configurations of this type which show an almost constant ratio between the term separations. We cannot infer from this argument that the whole matrix of spinthis IOT/2 From orbit interaction is zero because for example in * LS coupling. Such.". except for this inversion. 5 11 for the case figuration of j?3 . argument we see that to the first order the terms of the con have no splitting. These are repeated here. This was first shown by Heisenberg. 6 ). 3. 10.
35. argon. included in the systems n yfiril.* The separa which = 4203). 9 corrected a slight numerical error in his comparison. I . 13 Fig. Phys. is Tel 5p 3 determined by making P 1. the observed 1S All levels of which are plotted in Fig. D2 and between the ^ . 1325 (1930).gt. I 13 as a function of x = K/^2 ^ ^e same manner as for p 4 . The raregas spectra.. linear combinations of different The from secular equations for the configuration jp 4 are immediately obtained The energies are those given in 3 11 for p 2 by reversing the sign of . predicted by instead of complete. of the spectra of atoms con The simplest and most completely analyzed and isoelectronic ions.PUBE AIiMOSTCLOSEDSHELL CONMGUBATIONS correlated states have the 301 have same SLJM same or SLM8ML values. (x= 4. distribution of configurations is concerned. The only available experimental data are for 3 plotted at mean of 1 tions x = 0685 J= and between those of J = 2 are absolutely the theory. . inversion of the triplet which occurs for x I levels of &. We have comparison was originally made by GQUDSMIT. Fig.. 2 in 4 11 . .. they different phases since they are the correlated zeroorder states. This configuration shows slightly the partial.gt. 2 . . plotted in Fig. That the upper group approaches as limit the P^ level of the ion and the lower the 2 Pj level shows that the interaction which causes * TMs Rev. this 3. 4 Theeoiifigurationj&... taining almost closed shells are those of the rare gases The best known and most typical of these spectra is that of Ne I. with increasing n into 2 two groups of levels. makes these spectra greatly resemble oneelectron spectra so far as the known levels of the rare where n = 2. ininteimediatecoupliiig. The configurations of each series rapidly divide. gases are for neon. the (J 2 =1227 and the mean of *SQ and 3 P^ fit exactly.
302 COKJ1GUBATIONS CONTAINING. while the interaction of the valence electron and the electrostatic inter spinorbit action between this electron and the p core rapidly diminish with increasing 13 n. ^ H _ n &* IS ^ ^ 4$ 20 3f &.ALMOST CLOSED SHELLS 413 this splitting is the spinorbit interaction of the almost closed shell. The quantum number which distinguishes levels belonging rigorously to one parent level from those belonging to the other is the J value of the p 5 group. 2 . I known Alt /evete included in the 13 Fig.1 Each line a group of observed levels not resolved* on this scale. This is a large and practically constant interaction for all configurations. which is also the j value of the missing electron. J". This gives the higher configuration members to the resolution of Fig. 2 the appearance of doublets. The energy levels of represents in general neon I.) . (Scale in thousands of cm.gt. Adding an s electron .
The quantum numbers of the parent levels.gt. 5 5 group contains two levels for p s six for p p. I &.000 for xenon. l 3. . i. i. the 9 s . so for corresponding configurations the division into two groups becomes sharper down the series of gases. The numbers here indicate / for p 5 p is given by values. however. for the j value of the valence electron is in general not a good quantum shall consider the exact characterization of these states in number. $&. cf s are completely analysed up to complete up to Ip. etc.0 2.gt. * .0 2.* We the succeeding sections. The states are not. 1400 for argon. become asymptotically exact quantum numbers.. in Fig. The fine structure of the parts of the doublet increases less rapidly than this. J=0.gt. Only structure. and 10. S for xenon. For s 5 j3 are J&.2..e. the / a very good quantum number. we have 2. 1. 8^ i 1. 2 but with all n values increased by 1 for argon.gt. 2 13 3 the upper group of levels (those having the limit p^) while the lower contains two levels for p^ s and four levels for 5 p. Similarly the jj coupling parentage 1. .1 2. schematically as follows p 5 $? &. for neon.gt. A plot for the heavier rare gases would present essentially the same 13 appearance as to the absolute location of configurations as Fig. value of the p group is 12 a glance at the transformations of Table I will show that assignment of L and S values is impossible.1. the characterization 5 by parentage is almost exact. 5 Wd. 21. in pure jj coupling.21. the parent doublet splitting increases rapidly.11  f &.gt. and eight for p*d Xel. adding it to This parentage may be shown states..12 Ul. 5400 for krypton. Hence . How 3 1 ever. . two : states. because the interactions of the valence electron eventually become very small compared with the separations of the levels of the ion. the configuration p^s is completely known up to 11$.4 1S (of j THE BABEGAS SPECTRA 303 the = f) to the J =  J = f level gives level of 5 j) gives two 2. For krypton and xenon even the lowest as we go THs is typical of the coupling near the limit of any series in any atom. 2 13 as doublets without j&. 1fM J+2.gt.gt. For those configurations which appear in Fig. in particular the J values of these levels.0.Z + l f &. J=l. while the two levels of the lowest p 5 f have been found. p^ d. Since this is the case.1. of 1. It is about 800 cm". while for pH with I &. 2 for krypton.
5. the theory predicts that the electrostatic splitting of pis/ be twice that of p\8. ibid. 3 as a fimc tionofxK/01 \ 1S Fig.l s are for the same as those of all 3 11 for Z s if we reverse the sign of this category Hence in G l &. For configurations very close to jj coupling.304 CONFIGURATIONS CONTAINING ALMOST CLOSED SHELLS occur In two wellseparated groups. The 9 configurations /*$ and d s. 35. 3 13 The experimental ratios for the higher . Phys. This is true of all the rare gases and raregaslike ions. CosDoy and SHOETLEY. 1337 (1930). The transition from LS 13 to jj coupling for p*s is plotted in Fig. as seen at the right series of Fig. Rev. We see in Fig. l. members of neon are 10s Us 143 218 1 216 195 LUPORTE Mid INGOS. 35. so that the parentage 413 p 5 p". 2 13 that the pVs limit. . where they appear as two double levels.* The secular equations for .s may be quite accurately assigned. 1342 (1930).gt. 3 . and observed cases come under we have LS coupling a singlet above an inverted triplet. 4 /A (x= to the jj coupling of neon are all close The 5 configuration ? ^ in intermediate coupling.
2. . These configurations tend to lie closer to jj coupling.3i ). we find ( iJ/+1 )/( iJ. For argon. the agreement of the Mgher series members the observed ratios are good. } 1 but a glance at Fig. . two levels of J= 1 fit the theory exactly.) 1 ^ a pair of linearly related interval ratios to compare with the theory. 4 . The agreement is again seen to be in general good. Interval ratios for d*8. 1 ^". which is on the left in this plot.J!^1 ) Just as for I s (cf. i M m tliat 2Z+1 0== is + JG P. I/I 7 8 3 ! 9 8 7 6 5 4 3 2 / 13 Fig. I". 8 13 shows a perturbation as large as 8cm". If we take as ordinate 8 1 8 8 and as abscissa (3i. we can find for 1 ". which is (1+ l)jl for jj coupling (abscissa 0). 3 11 }. The intervals in c? s are 13 compared with the theory in this way in Fig. 4 .j 141 The ordinate here 1 the ratio of the splitting of ^ to the splitting of 9 Zj^J ^. which has a zero spitting for 2p 10* j in 1 TMs term lies very close to place of an expected splitting of about 8 13 7d on which we shall see in 7 that there is indication of perturbation 2j? cm". than to L8 coupling. 5 2p fe 7s 8s 9# 129 119 424 M3 All other observed p*s configurations have larger values of 1/x and are 13 = and the mean of the plotted in Fig.513 THE COXFIGUBATIONS p^s AND d*s 305 The agreement Is good up to 10$. The agreement is In general good. 3 at that x for which the levels J 0. (x=fW7a .3i )/(3^i. to be quite is not unexpected.
* The configuration pp contains 1 level with / = 3 3 with J = 2. . Just as our consideration of one configuration at a time is an approximation in which we neglect the interaction between configurations. it is necessary to obtain the matrix of the Hamil tonian in the jj coupling scheme. Hence the diagonalization of the Hamiltonian for this configuration involves the solution of a linear.l.. as we propose to do. a quadratic. 4 with J = I . good as we go up the series of quantum number which distinguishes levels belonging to one from those belonging to the other is the J value of the jp 5 group (i. so we have no observed instances of/ 13 &.: T~ nJ \ l C In the parentheses are given the j values first of the j? 5 core and then of the added p electron.e. This latter approximation is 13 Fig. and 2 with J = 0. 6. the solution of these equations is rather complicated. and a quartic equation. be made. These equations contain as parameters six radial integrals. d are introduced as a convenient abbre viation for the four possible combinations of j values. Pfcys. The letters a. parent Since the the j value of the missing electron). so we may use an approximation in which we also neglect interaction between the groups of levels of the same configuration which have different levels of the ionic doublet as parents.i): jr + K c (fcf): r+K W d (i. States labelled by a and b belong to the lower doublet level. a cubic.f): &. with the m ff* elements n pP np np o & (. the the transformation of Table I 12 found injj coupling to have the value * SHOBTUEY. .306 COSrMGTJRATIOXS CONTACTING ALMOST CLOSED SHELLS is 5 13 Unfortunately the spectra of the latter rare earths not known. states labelled by c and d to the higher doublet level of the ion. expected (cf. 6. is much more complicated. c. The configuration j?5 p in the rare gases. however. in order to split the secular equation according to parentage. 44. is diagonal elements are given in With diagonal in LS coupling. to obtain the values of these parameters from the observed energies and then check the selfconsistency of the equations. These elements are independent of the values of the states. The matrix of diagonal spinorbit interaction is seen from I 10 and 2 13 to be mjj coupling. Given the values of these parameters. 2 ) to be increasingly configurations in the rare gases. A simplification valid in many cases can. 666 (1933).lt. Rev. M J and The matrix this matrix is of electrostatic interaction I 13 .
6 13 THE CONFIGFBATION P & p IN THE BABE GASES 3* 3a j 307 Jt  2o 2d 2c 26 Ic la (2) Ic It* Oa (ki In the notation here used the J value is given as an arable numeral followed by a letter which specifies the electronic j values according to the scheme ( 1 ) } . we obtain the ing to the parent j values as following equations for the energy levels: Upper l&mis (2c) J fl + =s j + r c (3) Lower Umis The six ously to the unprimed levels of this group belong in our approximation rigor quantum numbers assigned to them. . levels are linear combinations of those for the corresponding unarbitrarily denote the higher of the two levels by of and We the lower by 6 since the level a would lie above the level b if the electrostatic interaction vanished. The matrices are independent of the value of If. Adding the spinorbit interaction (1) and spitting these matrices accord indicated by the broken lines. The eigenstates for the primed prinied levels.
00 ^b 30 Zb". O The configuration p 5 p However. =f= WOrL a Oa . Hence we prefer to determine this parameter. . 1 . meters less sensitive to configurations. 5 . which is Xow the value just f the ions only to an accuracy of one cm". from the data for each configuration. our approximation is good be obtainable from the splitting of the parent But this splitting is known from the spectra of doublet. Sp 13 Fig. and then to check it against the doublet splitting of the ion later. 6 13 should in all cases in which of one of the parameters. From the values of the parameters we could then predict absolute positions Od On =g= aocl : */c p. The six linear expressions in (3) should determine the six parameters. This leaves the separations 2n 26 and la 16 to be absolutely predicted. in order to make the values of the para the small perturbations which must exist both between the two parts of one configuration and between neighbouring of the other four levels. along with the rest.308 CONMGUBATIONS COOTAINESTG ALMOST CLOSED SHELLS ._. 3 \ 6p in neon...[nujr L . we prefer to fit by least squares the eight quantities obtained by adding to the above six levels the means of 2a* and 26 and of la and 16 .
for krypton and xenon. . Fig. the magnitude of this interaction may be found by using the interaction elements ofthe matrices (2) according to the secondorder perturbation theory.". In this way the largest interaction was found to have approximately the value represented by the length of the short black bar drawn underneath each configuration. This gives an idea of the agree ment to be expected in the comparison. are approximately correct. In these figures the empirical value for 16 has been taken as the zero for each configuration. 5 13 for neon. and Fig. 6 for argon.6 13 THE CONFIGURATION p*p IS THE BABE GASES results of such a calculation are 7 13 309 The shown 13 in Fig. 6p Tp 8p The configuration p*p in argon. If the parameters we have obtained The AffGON I _ m/o too _ 5p 13 Fig. a break in the wavenumber scale indicates the separation between the two groups of levels. . The first scales are in 1 cm". 6 . inter question one asks concerns the validity of the neglect of action between the two groups of levels.
so far as work is concerned. r . 5 13 ). fur Phys. purely accidental that the electrostatic interaction .la 26* woo  L S 3 O ib Iff _ Ib Ib 3 ^ u *l KttrPTQM 1S Fig. The 2j9 5 3p is taken from the work of Inglis and Ginsburg. To the same approximation the separation between these two levels represents just the doublet splitting of the np electron in the central field due to the core. 43. 534 (1933). 194 (1933). Neon I (c/. between Ic and Id Tanishes identically and hence that these levels are to our approximation 100 per cent./c T . Rev. 3. 6p I 3 I (v.* who solved the complete secular equation in LS coupling using the levels of J = 0. 83. pure. 47. 295 (1935). 2.COQOr . Fig. 7 . PBTE. In regard to this configuration see also ROZEXTAL. We may call this f ( Ja\Ja 2 )\ the purity of the levels Jo! and Jb It is. and * iNGiisaud GIXSBUBG. corrected by SHOBTLEY.ld) I s 4p np in XENON I Sp 6p s The configuration j3 5 y krypton and xenon. ./c /c_ ". one can readily coefficients in the find the (JaiJa }f^ (^){J61/a f ) ( JalJb j+^JbKJblJb ).310 CO^FIGUBATIO^S CONTACTING. ibid. Zeits.ALMOST CLOSED SHELLS expansion 6 13 Having obtained the values of the parameters.
Argon I (c/. the last of the series which is completely known. TABLE 3p I 13 . effect. 1 and the coefficients in (4) are given The values of the parameters (in ) Table I 13 The significance to be attached to these values must be judged by 13 the value comparison with Fig. the interaction is much smaller and the agreement corre The 2j? spondingly better. by . .below 7p (Id) and the lower group of lip falls close to the upper group of Sp as indicated in the figure.6 13 THE CONFIGURATION p s p IN THE BARE GASES mean 5 311 the of the four levels with. leaving op is the first of the series to which our approximation is at all inter applicable. Bp (Oa) 1 falls about 200cm. 1 521 obtained from the parentdoublet splitting of 782 cm". 5 The value of is to be compared with 2p Ip 5 is cm. 13 Fig. There is definite evidence of The 5/group overlapping Bp does not have a pronounced perturbation on 8j&. parameters.gt. . These levels agree to within the rather large maximum action between the groups. TABLE 2 13 Argon I Sp 5 np. . the reason is that the lower 8p group interact strongly exactly overlaps the upper 7p and is therefore expected to with it. otherwise the /= 1 to obtain the J= 1 levels to be absolutely predicted. 6 ). Xeon 1 5p 5 2j? np. 6p lp found to agree not at all.". For 2p s 6p.. The pp configurations of argon remain rather well separated from each other up to 3p 5 Sp. .
this figure with the others that the highest J=l of 7p might more exactly to 6p than the Id assigned to it. 7 ). In xenon only the &p 5 6p is complete. If we make this re belong a decidedly arrangement. It is definitely perturbed by which overlaps as indicated. due to the lower Even group mainly rather than to the 5f levels plotted. . Xenon I 5p 5 ftp The constants for these spectra have the values given in Table 3 13 % for krypton is to be compared with the 3581 obtained from the ion. TABLE 3 13 Jn/p$on 1 4j) np 5 . b. the lowest p*p s of krypton and xenon are amenable to treatment 5 with our approximation. The 6p shows definite evidence of outside perturbation which is undoubtedly of 7p which lies at only 6200 on the Bp scale. Krypton I and Xenon I (c/. The doublet . This in the first plot agrees very the lower poorly with the calculations. e.gt. G 13 The constants The value of is to be compared with the 954 obtained from the ionic doublet splitting of 1431 cm1 . . The diagonal elements of spinorbit interaction for p 5 d injj coupling Ti are p nd (i) 5 ** d (j!i): where we have introduced a notation a. The 2p 5 5jp agrees to within the error of the approximation. d similar to that used for p 5 p. we obtain the plot on the right. For krypton the 2p 5p and 6p are completely known. splitting for the xenon ion is not known. 13 Fig. Here the parameter p which is the same as the former accomplishes the . The 5 configuration p d in the rare gases.312 CONFIGUEATIONS C0XTAIOTKG ALMOST CLOSED SHELLS 13 are given in Table 2 . one suspects 7j&. Although one cannot make a rigorous group on assignment of these overlapping levels to configurations. 7. which shows comparing better agreement.
states characterized by a and spitting of the configuration c and d in the upper.+ + (2c) =F f & L ^^G s Lower lends 36 1 . 3a 35  . b lying in the lower group.1 Vio Js  1V21F.7 1S THE CONFIGITBATION p*d IS THE BABE GASES 313 into two groups. Id Justasinthecaseof^wefi the following formulas to express the twelve belonging to different parents. (2) 2d la. levels in terms of six parameters: Upper levels (3c)=F + J. those characterized by 13 to the electrostatic energies of I jj coupling gives Transforming the matrices 4a 2F.
Since 13 These all the long series of configurations plotted in Fig. which should be just This further perturbation may be attributed to the fact that the lower part 5 of 9d lies 100 cm. .below the lower of s of neon these are known completely from 3d through we obtain further perturbation on the upper group of Id is shown by the abnormally the 7^electron doublet splitting. tions to be absolutely predicted. 1 comparison with the observed 782 cm". 13 The constants used in these calculations are given by Table 4 . This requires that Me very close in order appreciably to affect each other. Since there can be no spinorbit perturbation corresponding to the inter action which splits the configuration into two groups. Neon I 2p*nd. which are agree within the accuracy of the calculation except clearlv perturbed. The perturbations which occur 1 in . That there is upper group of Bd lies only 26 cm. 8 6d and Id. and la 16 fitting the six parameters to these nine 2a 2b\ la lfr separa the 3a 36 quantities by least squares. 2 we see that our approximation should be applicable to . From the p d 5 13 Fig. TABLE 413 . seem to be small except when two configurations of the same series overlap. I. large 2cM separation. should from the values here given predict a doublet splitting of 7804 02 cm". . in estimating the mutual perturbation of two configurations we should compare the distance of the nearest levels not to the overall configuration size but to the much smaller spread of each group of levels.314 CONMCUBATIONS CO^TAIKKG ALMOST CLOSED SHELLS : 713 V take the six levels given by linear expressions and the means f of 3a 36 2a 2b . all lOi. Thus the present theory accounts very satisfactorily for the observed structure of these raregas configurations.1 above the upper of Id and perhaps to the 2_? 10s which 1 lies about 20 cm". This leaves We 3 . The value We of t p is to be compared with the 521 obtained from the ionic doublet splitting. above Id. . The most of this perturbation is due to the fact that the 1 Id. 3d 4d 5d 6d Id two configurations Sd $d lOd .
THE CONFIGURATION P*d IN THE RARE GASES 315 .
the spectroscopy of these radiations requires a special experimental technique. The neon array 2p5 3p+2p 5 3s is Xray spectra. are the same as for the corresponding configurations J? and J2 . From the theo arising retical standpoint there is no sharp distinction between optical spectra and Xray spectra. CONFIGURATIONS CONTAINING ALMOST CLOSED SHELLS 8 13 Line strengths.. Owing to their great wavenumber.* confine ourselves to the theoretical problems involved.gt. corresponding to configurations in which an elec tron is missing from one of the inner closed shells of the normal atom. The transformation to any other scheme is the ^ same for the two cases. This is fully treated for example in Siegbahn s Spektroskopie der EontgenstraMen.g. Since all quantum numbers except those of the almost closed shell and %. 5 5 p has the relative strengths given by Table 2 M for p$+pp* We may obtain the relative strengths in any of 3 the array 9 j&.316 8. Thus to a first approxima tion such interactions may be neglected and the spectra interpreted as due to isolated atoms.gt.p by Table the rare gas transition arrays by using the matrices of S^ injj coupling and the transformations of the eigenfunctions to the jj coupling scheme as cal or culated from the observed energy levels. or a compound containing it the target in an electron tube so that it is struck by a beam of electrons which have energies corre sponding to some tens of kilo volts. The characteristic Xray spectrum of an element is obtained usually by making that element. discussed briefly at the end of 4 11 . e. whereas in ordinary Xray spectra the energies are a thousand times greater. But experimentally they have been quite effectively separated because of the great experimental * Second edition. To see this we note that in the nlm^ scheme the quantum numbers in the almost closed shell cannot change since one of the other electrons definitely jumps. We may say immediately that the line strengths in any coupling scheme. We These highfrequency radiations arise from transitions between highly excited states of an atom. 1931. It turns out that the interaction energy between the atoms in a solid is of the order of a Bydberg unit or less. the two merge in a natural way. Practically all Xray spectroscopy is done with the emitting matter in the solid state. for transitions between two configurations 3t and 3$ having the same almost 7 closed shell. Under this excitation the atoms emit ? 9. Thus. * . &. radiation of wavelengths in the general range one to ten Angstrom units. Julius Springer. Of course the term Xray spectra is a practical category from a classification by experimental technique. hence the transition arrays have the same strengths in any coupling scheme. the strengths in this are the same for the correlated states of scheme must be the same.
9 1S difficulties XRAY SPECTBA 317 of working In the soft Xray region and the extreme ultraviolet. Let us consider one of the heavier elements. is Similarly if an electron is removed from the 2# shell we is obtain a level not as high as the If an electron K level which called the LI level. will . does not matter in the first approximation). . and consider in turn elements of lower atomic number. The relation of the conventional Xray level notation to the usual spectroscopic notation is given here. . on the outside. foil scheme of levels as here presented is only present in contain normally all of these closed shells. The table ends with Y and Pm since the 5f and 6d shells do not get filled in the known elements. This level (really a group of levels quite close together if the structure due to the outer electrons not in closed shells could be observed) is called the K level. For remove T example in Mo (42) the scheme of the table extends to A nl as the 4d shell is only halffilled with this element (see I 14 ). the scheme of Xray levels becomes Of course the for one cannot simpler through the absence of the later entries in the table. If we remove an electron from the (just where. an electron from a closed shell that does not exist in the atom. removed from the 2p shell we are left with a p 5 configura tion plus closed shells. . where the merging takes place. Evidently removal of just one electron in this way from any one closed shell will give rise to a doublet term. This gives rise to an inverted 2 P term. that is in the order of the energy levels of the central 3 field best suited for the starting Is shell and put it on the outside point of the perturbation theory.. To ignore the structure of the Xray levels due to the outer electrons not in closed shells is formally the same as supposing that all electrons present are in closed shells except for the one shell whose openness is indicated by the above terminology. If we start those atoms which with uranium^ where this scheme of levels is folly developed. the nature of the term being the same as in alkali spectra but with the doublets inverted. Its normal configuration be l 2 2s 2 2p 6 3s 2 3p 6 3d1 4^ 2 Here the shells have been written down in order of the firmness with which their electrons are bound to the nucleus. the energy of the resulting configuration will be very high.
physical treat as being outside Z7(r) TJ/ . It is jumps from the L shell to the sometimes convenient to focus attention on the electron or hole in transition from the K level to the m level. are supposed to arise from transitions in a level scheme associated c with removal of two electrons from the inner closed shells. Suppose our central field approximation is based on the potential function U(r) and that we define the effective nuclear charge Z(r) at distance r by the equation electrons. that is. on the which we denote by ZJr): .318 COXFIGUKATIO^S CONTAINING ALMOST CLOSED SHELLS transitions 9 13 The Xray Hues are produced by between these I. We cannot have an absorption line in normal atoms corresponding to a jump of the hole from the L shell to the shell since in normal atoms there is no hole in the L shell. The absorption spectrum is thus directly affected by the external structure of the atoms and the way in which this is influenced and chemical state by the useful in discussing K in the absorbing substance. sometimes called non diagram lines* because there is no place for them in this simple level scheme. The theory of the Xray energy levels. K^ K K missing and to say that in the transition from the level to the level the hole jumps from the K shell to the L shell. in a transition from the level to the L level an electron shell. levels. together with the selection roles AZ= AJ = 0. (1) The force on an electron at distance r is then _3U__[Z(r)rZ fo (r)]e* ( ^ force 2) electron at distance The quantity in brackets is the effective nuclear charge for the r. The behaviour of a hole is just opposite to that of an electron the normal state of the atom corresponds to the K m : the hole being in the outermost far as possible in inner shells. In normal atoms the holes are oa the outside so the Xray absorption spectrum is produced by the transition of one of these outer holes to an inside shell. This level scheme. gives an adequate description of the main features of theobserved spectra. Z(r)e* LL_. that is. Inaddition there are observed weaker lines some of which receive their interpretation as quadrupole transitions in this level scheme. Other lines. shell. to all of the electrons being as is also The shift of emphasis from electron to hole Xray absorption spectra. Thus the line is produced by the In this transition an electron jumps from the 2p shell to the la shell. The K series of lines in an Xray spectrum is produced by transitions from the JK level to various lower levels. Such details we do not neglecting structure due to outer thus that of a oneelectron spectrum. 1. is the scope of the theory of atomic spectra.
then eaoh electron has an energy given by that formula on writing quantum numbers. as discovered by Moseley. Let us consider first the levels. 5th edition. as a rough approximation. with slope close to I . are dealing with a state of the atom in which the radial probability distribution has a strong maximum at r = 6. It represents the fact that the inner electrons in the proper f move in a region where their average potential energy is increased by the presence of the outer electrons. 9 13 . .913 XRAY SPECTRA * 319 radius of We know that Zf (r)+Zas r^0 and Z (r)*l for r greater than the f the atom.. corresponding to the first known empirical regularity in Xray spectra. which level highest as it corresponds to removal of the most tightly puts the K bound electron. The formula for the K level is. The departures from the Moseley law are put strongly in evidence by plotting Vp Z against Z to remove the main linear trend. that the of the electron will be If we energy close to that of an electron in the r (r) ft MZ Coulomb field (6) (4) as this has the field Z7(r). the curve is strikingly linear. oseley found that the square roots of the line frequencies are approximately a linear function K M of Z. writing Zf (b) for Z and subtracting the constant term e 2 Z (b). If the square root of the frequencies in Rydberg units be plotted against Z. The energies in crease roughly as the square of Z. in Rydberg units. (Note that BA Z f (b) is negative this adds to the energy and hence decreases the absolute value of the negative numerical value of the energy of each electron. The account of it we have Just given is incomplete in that it does not say how b is to be chosen. Atomban nnd SpeidraUinien.* It of such a theory of the Xray levels is largely due to the facts surprisingly well. Accordingly the Xray levels should be given by this formula with the opposite sign. Such a plot is given in Fig.*) Consequently the atom s energy is increased by the amount of one of these * energy levels when the corresponding electron is removed. If we subtract the restenergy ^c2 from 5 s 1 1 and measure energy with the Ryd~ berg unit. Let us approach this question through an examination of the empirical data. this is sometimes called external screening. relativity same value and the same slope at r=6 as has the effective Tor such a field the energy levels are given by 5 5 1 1 including the and spin effects. it is natural to suppose. fits The development Sommerfeid. Their values are given for most of the elements in Table 5 13 as summarized in Siegbahn s book. * SOMMXEFEID.
hence in spite of the Z 1 occurring in the denominator this is perhaps a slowly increasing function of Z. If we had n electrons on a sphere of radius the potential /&. As it appears here with reversed sign it will contribute a slowly decreas level. As Z increases we have more shells so this term becomes 2 Swe 2/p for the shells present. effect of the internal . amount of charge of the other electrons in the atoms that energy of an electron inside the sphere would be ne jp and this term measures such a potential. We see that it decreases rapidly except at the large values of Z. 9 13 Expanding the second term in powers of a and taking the square root we find (6) TABLE 5 13 . The third term is quite definite as soon as we ing function of Z to the know the screening constant Z Zf Using Z . The Element K levels of the atoms in Sydberg units. The value of Z Z* obtained screening is is between one and two. It is harder to say how the term e 2 Z (b)j2RZ hc f will depend on Z. On the whole it seems reasonable that this increases more rapidly with Z than the first power. The dotted curve therefore shows the combined effect of the external and internal screening. where higher terms in the expansion become appreciable so that the curve becomes meaningless. K Fig. 9 1S is values of Vv^ obtained by subtracting off the third term from the experimental Z. the dotted curve in . It it is some kind of average of the : is closer to the nucleus than the 1$ electron. Element v(K) The quantity (ZZ$ is might be expected to be equal to one or two often called the internal screening constant.320 CONFIGURATIONS CONTAINING ALMOST CLOSED SHELLS .gt. so we see that the as surmised above.Zf = 2.
we find to the first order . If we calculate the doublet interval between LU and ijjj by means of the for the two hydrogenic formula. assuming the same values ofZ (b) and Zf (b) that the interval should vary as Z* Hence we levels. 9 . levels of the elements. . This same model has also been used to discuss the doublet intervals in Xray spectra. Such comparisons have been made by . The quantity calculated in this way is sometimes called the screening constant for doublet separation. L^ corresponds to removal of a 2s electron while L u and LITI correspond to the inverted 2 P given by the 5 2p configuration. Therefore the 2s electron is more L tightly bound than the 2p so the L^ level will be higher than Lu or IU The difference will be partly due to the difference in screening and partly to the spinrelativity effects. For the same n the hydrogenic s states penetrate more closely to the nucleus than the p states. are commonly called irregular doublets. The formula evidently is in accord with the main facts and that is all that can be expected. 13 Fig. Plot of Vv(K) Z against Z to show departure from the Moseley law for the K.9 13 XRAY SPECTRA 321 In view of the eradeness of the model we do not believe there is much to be f gained by attempting to choose Zf and Zi (b) in such a way as to represent the data best. the LT and Z*n levels^ and in general the pairs of levels of the same n and J * 3 but different L. can conveniently test the formula by calculating empirical values of Z Zf from the doublet intervals and seeing if they have reasonable magnitudes. For a reason that has since become meaningless. Let us consider the L levels.
As emphasized in the preceding section. the relative strengths of Ka 2 (1 2 P^) and 2 2 will be as 1 2 according to the results of 6 5 This is in K&i (1 5&. Nat. DUASE and PATTEKSQN.322 COSJIGUBA HONS CG3TTAIKOG AIMOST CLOSED SHELLS 9 13 Sommerfeld and others. In the L series we have the possibility of studying the relative intensities in a 2 P^ 2D multiple! For the hole transition 2p 3d! the lines and measured effect of screening tions of these relative strengths &. PATMHG and GOUDSMIT. Rev. SIEGBAHN and ^A&SL. 563 (1925) Phys. fur Kristallographie. Chapter s. Proe. TJk Structure of Line Spectra. * . ibid. 187 Likewise in the doublet. 10. Ann. Zeits. 81. They also measured the relative j83 K$i and K intensities of the doublets arising in the hole transitions ls*3p (JT j81? Kf}%) (Kfts ).2 Pj) S^2 . 85 (1922). : 5 accord with the experimental data: (1) (2) (3) DTASE and STEKSTBOM. the Xray energylevel scheme of the atoms has the structure of a oneelectron spectrum. Atombau und SpekiTaMinim.* and have shown that the simple screened hydrogenie model gives a good account of the main facts. . 8. Allison K series the lines and Armstrongf found Mo and Cu and l*&.4p respectively for this form the same kind of intensity ratios of 21 and 20 in doublet. Xat. 26. 71. For example. Mme strengths in Xray spectra. f AXUSOH and AEMSTEOKG. From 8 13 we see that the theory of the relative line strengths in a doublet spectrum is applic 2 able here. 5th edition. Sci 6 S 477 (1920). relative intensities are SOMMEBFELD. Acad. No calcula have been published. Sci 11. PAUUHG and SmESMAy. 297.gt.gt. 714 (1925). p. 701. The ratio of the intensity of the first of these doublets to that of the second increases with decreasing atomic number: Element Intensity ratio 23 77 Strength ratio 26 83 W Mo Cu (74) (42) (29) 410 420 dividing the intensity ratio by the fourth power of the frequency ratio.gt. I (1932). The great ratio obtained in the lighter elements is due to the greater difference in the relative The third column gives the ratio of the strengths as obtained by on the 3p and 4p radial function for small Z. Froc. Acad. (1923). der Phys.
176 (1929). 14. 7. Jonsson* has estimated the correction for excitation and has found values which check strength ratio. Zeits. Such satellites were first studied by Siegbahn when observ then they have been the object ing the La. SIEGBAHH. natural excitation. their relative intensities should be the ratio of the relative strengths multiplied by the fourth power of the frequency ratio. 383 (1928). The relative strengths from 2 9 are as 9: 1 or 1: 0*111. 9 (1920). 1 Mat. M levels is so small here that the frequency correction negligible so the relative intensities are the same as relative strengths and are seen to be in good agreement with the theoretical ratio Assuming natural . No. Experimental measurements bearing on this question have been made by Allison. lines of Sn 5 Ag. der Pkys. Then he supposed the satellites to be emitted when one of the * JOSTSSON. Ann. 73. Phys. Naturwiss. Several possibilities are open. Fys. All the experimental values are is probably due to the lack of . 437 (1921). 621 (1928). 34. excitation the relative strengths of the first and third line are obtained from the relative intensities by dividing by the fourth power of the frequency ratio. The 2D interval in the is . WentzelH suggested double ionization (two holes) of the Is shell as an initial state of the satellites is of considerable study. lines In addition to the which are accounted for by transitions in the doublet energylevel diagram of the preceding sections there are observed a number of other lines known as satellites or nondiagram lines. 647 (1924). fl . 46. 66. 14. Since so simple that it is evidently necessary to con sider the energy diagram corresponding to more than one nonclosed shell to get any more detail. J it. the higher level 2 P being considerably less excited than the lower 2 Ps level. J AMJSON.USTE STRENGTHS IN XRAY SPECTRA L a* Element Mo Pd Ag (42) (46) 1 1 1 323 Eli (46) (47) 1 0130 0133 0119 0122 033 024 020 017 (028) (020) (016) (014) As the first two lines have the same initial state. less The than half of the theoretical value f this results are given in parentheses. Ark. The doublet structure of the K lines. much better with the theoretical 9:1:5 Wentzelf has given a theoretical calculation of the relative strengths of the different multiplets originating in the L levels based on use of approxi mate eigenfunctions. fur Fkys. Xray satellites. Astrom. Rev. f WBHTZEI*. and Mo. WiarrzEL. These are close to the more prominent lines which are accounted for by the discus sion just given.
*s) &. The relations proposed by Wentzel are best considered jumped to an outer shell. K more by that is than by another 2p. In the second The energy of we have this diagram extended for the case of two holes. . where x n written briefly for the The values. ( ~ **) line. . not as much as the K of the element whose but to first. a schematic level diagram. 42.lt. * WBTTEBBLAD. 611 (1927). Xow L will be greater than Is 22p Is 2 IsZp* Is2p 0*3 Is 2p* 2p Normal 1S Fig. Similar remarks hold with regard is screened because 2p compared with L. 10 sheE. that for the removal K\ of the second Is electron will be greater than K. WentzeFs interpretation of the by the satellites. fur Phys.324 holes C02STFIGUBATI05S COOTAIXIXG ALMOST CLOSED SHELLS II 13 For initial states of some of the lines lie L with two holes in the K shell and one in the suggested triple ionization 13 from Fig. Hence one readily concludes (. 10 . 1 L". The levels are labelled configuration of the missing electrons. since Is is so much closer to the nucleus than 2p absence of a Is electron is almost like a full unit increase in the nuclear charge in its effect on the others. which is column The first column shows the ordinary level diagram. in Rydberg units. and so on. (*5 .%) is &.lt. . screening owing to L as atomic number is one greater. wave number of the corresponding found by Wetterblad* are given below: Mg(12) 064 067 076 Na(ll) 052 057 065 Al(13) 071 Si (14) 076 0*83 083 091 094 y Moreover. Zeite. This is the case here. so (a e a4 ) of one element should be nearly the (a3 oc^ of the next element.
27. fur Fhys. J On account of the existence of such structure the K satellites can be provided for without using the triple ionization process or shell.s s fs2$ IP Jp Is2p Is ip lip 2s2p 4V 2s 0% ~2p (Wolft) Normal 1S Fig. 1 1 13 This scheme is consistent with the small K . 730 (1925). 37. 445 (1925). Langer s level scheme and assignment the double ionization of the of the satellites is shown in Pig. Si. The mean life is so short that producing excitation by two successive singly ionizing impacts cannot be effective. Rev. ? .XEAY SATELLITES The main 325 objection to WentzePs interpretation concerns the question of these multiplyionized states. $ LASTGEB (abstract only). satellites. . 30 (1924). fur Piiys. The LangerWolfe interpretation of the (Configoration labels are for the missing electrons. therefore the electron impacts must produce double excitation. r.) K In WentzePs work no account was taken of the complex structure arising from electrostatic interaction of the holes. Hiys. . I1 . although he mentioned it as a possibility in later papers. 34. f WEOTSEL. Zeits. more than twice the usual K K K for their appearance than the related main lines. TMs requires oc critical potential to produce the line 4 Backlin* studied this point in Al and found that a4 appeared at definitely lower voltages than expected on this hypothesis. Zeits.) on the tube . It does appear however that the satellites require higher voltages (by about 25 per cent. 457 (1931).f The importance of this structure was empha sized by Langer.
but there still remains much to be done before the satellites structural energies are of the right order of interpretations are satisfactory. 574 (1929). Phys. Rev. 325 COSTEE and DBUYVJSHTKXK. 43. Pihys. 707 (1927). 34. the outer electrons with the open inner Structure of this kind. if appreciable. 0. Phys. Such interactions are pre somewhat smaller than one Bydberg unit and in case of ordinary sumably resolution give rise to broadened lines more than to observable structure. Groningen. . (1934). Bev. J. franklin Zeits. 40. 64 (1028). 43. WOLFE. as was noted by Coster and Bruyvesteyn. tirid. MehtmyerJ has developed a somewhat different view of the origin of the satellites in which twoelectron jumps as well as doublehole levels are employed. 46. Bey. For elements in wMch an outer shell is being incomplete^ so there should be a is but one hole in the the outer shell is filled complex structure due to the interaction of shell. His assignments of the lines differs from Langer s and is shown in the lower row of the figure. Another possible source of more detailed structure is the open shells in the outer structure of the atom. 208. PhiL Mag. COSTEE. the Xray levels depends on a model in which there shells. Zeits. These ideas have had practically no detailed development thus * far. The elements relation of the filling of electron shells to the periodic system of the 13 the doublet structure of I 14 As mentioned in 9 is discussed in . f RICHTMYBE. 221 (1933). 797 (1927). fur Phys. see also KEKXABD sad BAMBEEG. 1928. we should expect to be sensitive to the state of chemical combination of the element in the source. fir Pliys. As.^ Some calculations of the terms arising from these configurations have been made by Wolfef using a Hartree field for potassium. (1929). 1040 Insfc.326 COKMGUBATIO^S COKTAIKma ALMOST CLOSED SHELLS excess in the critical potentials of the satellites over those of the main lines. f BErnneSTEYN. Similar views have been put forward by Druyvesteyn. 45. 765 (1927). generally speaking. twoelectron jumps are weaker than singleelectron transitions it seems that such processes should not be con s sidered unless it is found that the oneelectron jump picture is inadequate. It seems quite likely that the Xray satellites are to be accounted for by double excitation levels. BIss. The calculations show that the account for the magnitude to but the detailed assignments are quite uncertain.
plotted up from the lowest level of the atom. and configurations of the ion which may have importance as parents are shown in broken lines. In this section we shall. More than that. the even configurations on the left and the odd on the right. a rare gas. Moreover we see that Is 2s is definitely lower in energy than Is 2p. The lowest level of the ion of each element is indicated by crosshatching. The fact that in beryllium the 2p energy is considerably less than the 3& leads us to expect boron to have 2p for its lowest configuration. in addition to all the lowlying configurations. In Fig. In lithium we see that 2p is considerably higher than 2s. the fact of 2s being lower than 2p in helium leds us to expect that 2s will be the normal state of lithium. i 14 are shown the energies of the highest and lowest observed levels of the principal configurations of the first eighteen elements. state is connected with the extreme difference in energy necessary to excite one of the elections in this closed shell. related to the energy states of the atoms. This we shall connect with the fact that the 2s comes nearer to the nucleus than the 2p. consider the empirical data on the gross structure of the atomic spectra analysis. As these properties are all. We see that in normal helium the second electron has gone into a la state and that the next excited state is very high much higher than the whole ionization energy of hydrogen. although both have closed 4 shells for their ground states.CHAPTER XIV CENTRAL FIELDS 1. This takes us past the initial hydrogen and helium pair through the second Mendelejefi period of eight. the theory of atomic shall its picture of the arrangement of electrons in closed shells a clear understanding of how it is that element with similar provides properties recur periodically in the list of elements. We have included. this points to 2$ 2 as the normal state of beryllium.* Now the 2s shell is closed. in the last expect the periodic system to play an important part in coordinating the different atomic spectra. we structure through in its relation to the chemist s periodic table. Chemists long ago discovered the great powerof llendelejeff s periodic system of elements as a coordinator of their empirical knowledge of the chemical properties of atoms. at least the lowest con figuration of each observed series.f In the next six elements the normal configuration is in each ease obtained by * That He is. f For brevity we omit mention of the closed shells already present course the complete designation is I*8 2* 2p. At any rate. and speak of 2p when of . and Be is not. We have now to consider some of the relations between the spectra of 5 different atoms. Tlae periodic system. then. as Bohr showed.
lt..? 01 tso J i I TO * ^ I Ki sr&.1 "... ~+&.lt.lt.A W  ^5 OQ I Ui I I h fo t 1111 I 1 U** f t I I I I i } I I   S j ..t* u 1 "..D .&. * l U L. 1 r  f * &.gt.lt.J & J 03 ! ! J *! i o &.+** 3? Q? c/5 O \g * J .
J^ ri iJJ ^i ^LJ ^^ ^ 8 of 4= ^^ s i i : .1 t I L I  L J i S I .ssrtfij?^ i s^^W dpi g^^^PS J L.
There is a close competition going on between configurations of the n 2 n ^ l s and d n for the distinction of contributing the normal type d $ 3 d ^ As aE of these are even configurations their proximity undoubtedly gives rise to strong interactions so that the assignment of a definite term to a definite configuration has much less meaning than in the state of the atom. 2 2 cases heretofore considered. Our knowledge of these owing to their great complexity. At neon the process is brought to a stop by the operation of the is the maximum number of electrons in any p shell. This is in fact what happens. the configurations ds d $ and P 2 2 3 are rather widely separated. Even in nitrogen the known terms of p* 4s are below p* M. the term intervals are such that ds s tz !3 is considerably higher than d9 s 3 3 D which lies 1 only 205cm. is by no means . especially in regard to phosphorus and sulphur. chlorine. 2 14 Here we have a situation which is quite different from that in the first two periods. . Therefore we expect the next element. This us expect a repetition of the previous development in the next eight by successive addition of two 3$ electrons followed by six 3p electrons. is little ground for ambiguity here as to prediction of the order of the low configurations in the element (Z+l) from a knowledge of the spectrum of element Z. to have 4a for its lowest configuration.above the normal spectra. but in titanium the configurations d s and d s . although the lowest level is d 8 * 28 ^. Looking back we see that the inversion occurred at 5 as far back as neon where p 5 4s is definitely below j) 3d. the departure of the effective field from the Coulomb form being sufficiently great to upset the order of n values as it occurs in hydrogen. What next ? We notice in argon that 4s is lower than 3d!. Thus we see that the first period of eight is connected with the sequence of normal configurations obtained by successive addition of two 2s electrons followed by six 2p electrons. This inversion has not occurred in boron. The from is close parallelism of the period from Li to Xe and Xa to A is very striking. Looking at the spectrum of neon we see that 5 2p %s lies below 5 2j? 3p. although our know of the second period far from complete. is overlap considerably. similarly for succeeding elements. As we go from boron to neon we observe that the interval between the normal Pauli principle. while extensive level. potassium.330 CENTRAL MELDS I 14 successive addition of a 2p electron to the normal configuration of the pre ceding atom. The eighteen elements from potassium to krypton are shown in Fig. In scandium. but not so much but that the complete configurations probably overlap. The competition especially close in nickel where. and argon it is quite definite. with the other configurations definitely higher. but by the time we reach sulphur. as sis There configuration and the lowest excited configuration progressively increases.
lias certainly little in common with the halogens. this leads us to But &. system. Then they omit an entry from Group and put the remain ing elements into the second or odd* series of the long period. In the table the rare gases are counted in at the beginning of new periods. wMch has . potassium first ment of the and calcium are clearly alkali and alkaline earth.I 14 THE PERIODIC SYSTEM 331 + complete. whereas the corresponding jp 5 2 and p^sp are not observed in alkali spectra.lt. There are long period differs from that of the short periods and the relation of this to the facts of spectroscopy. fluorine and chlorine. is as much dependent on the internal interactions in a configuration as on the central field. TMs is the case. as far as it has significance. but not for copper and zinc at the beginning of this group. krypton. That is correlated here with the fact that a d shell rather than a p shell is being filled. the eighteenth element after the last preceding inert gas. Copper is somewhat akin to the alkalis in that its level system is mainly a shell. they have to introduce a Group VIII and lump three elements into it. In these eighteen elements the 4s. manganese. In Groups I and II. With these an a and a p shell are being filled. striking property of these atoms is their almost constant ionization energy as con A trasted with the upward trend in the ionization energy during the filling of The lowest levels of the doubly ionized atom are indicated in p parentheses for some of these elements. but from Group III to Group VII the elements do not have such a close relationship to the ele ments of the first two periods: the metal.s expect that the 4p shell will be filled in the next six elements. so we expect them to show more chemical similarity with elements of the first and second short periods than did the 4 first part of the long period. As the d shell is longer than a p shell. 9 2 configurations like d # and cPsp are still in evidence relatively low. In copper and zinc we note that 4p is definitely below 5s. 3d and 4p shells have been built in. but generally it may be said that the configurations d n s 2 and dn l $ so that the question of which configuration gives the overlap completely normal state. TMs is known as the first long period in the periodic table. due to various states occupied by one electron outside the closed $d shell. We thus arrive at another inert gas. many variants of the periodic system employed by chemists: a 14 Let us note how their treat fairly common form is reproduced in Table I . although our knowledge of some of these spectra is quite fragmentary. whereas we prefer to count them in at the end: this is just one example of the kind of arbitrariness present in the empirical led some to suggest that the elements should be distri a spiral curve drawn on a cylinder to emphasize the arbitrariness buted on in the choice of beginning and end of a period. TMs is certainly the case for the elements bromine and krypton at the end. argon.
hort 3 ".s o S I S* i S S i period 3 O * 1 ". ^ i p S S S S ! lr i a i i S c.2 ! &.gt.8 . i a a i  c JD co o .
^ r". j~i * ^ O 2 id! Ill s S si ! !& * .s Illj I I s m Is U 2 S 2 c^ . s fl 5 ill 1.&.gt. s =) c? S S s .1a^ E.1 * * 123 s * 115 * S S ~ 035 Ii ^* e3 A O ".i1j 131 ?. 5 ".
r .lt.r r*T LJ&.J u lUfrf. Lll U*  I i i 1 i 1 f I L I t * i j .
23. f FBBIO. caesium. . In the process the 6s electrons have been displaced so that they must come in again at gold (79) and mercury (80) to give elements chemically resembling copper and zinc. The is statistical The first consider method of FermiThomas. Phil. there is a pronounced tendency tojj coupling. closing the 6s shell. fur Pfcys. In this method the phase space associated with the positional coordinates around a nucleus by the methods of 3 and momenta of each electron is divided into elements of volume A and the exclusion principle is brought in by the restriction of the number of electrons in each cell to two (corresponding to the two possible spin orientations). 2. 7.gt.I 14 THE PEBIODIO SYSTEM 335 It is not necessary to discuss the remainder of the system in such detail. Bend. Proc. and the alkaline earth. interrupted by the rare earths. barium. Soc. From Hf 72 to Pt 78 the filling of tie &d shell. the volume of phase space and corresponding to electrons having less than this resultant momentum 3 is fTrp dv. IS pis the resultant momentum of an electron. The second long period builds in the 5# 5 4d. Finally in the elements thallium to radon the 6p shell is built in. In these spectra. 47. Rev. 48. and provides a convenient summary of the main facts which have been discussed in this section. This is illustrated in Fig. There are fourteen places. from cerium (Z = 5B) to lutecium (2=71). f method of getting an approximate central field which we shall that of Fermi and Thomas. 370 (1935). 49. 542 (1927). having respectively one and two s electrons built on just completed d shells.* These are the rare earths the chemists do not have such an easy time with them either. Camb. continues. Phys. 3 M where the similarities with the are evident. that is. ending with xenon. After this the 65 and 5d electrons start a longperiod competition as before. Let us suppose the number located in volume dv of physical space * See the recent iper by IIJBEBTSON. but now the 4f states enter the competition. 726 (1928). by the FermiDirac statistics. For many purposes it is convenient to have a periodic table of the elements : which shows the electron configuration of the normal state of the atomTable 2 14 is arranged in this way. due to large spinorbit interactions. 73. and shells. 414 ). where the 4f shell is being filled. 5j&. 602 (1027). 550 (192S). who treated the cluster of electrons statistical mechanics as modified to include the Paul exclusion principle. first long period With the third long period greater complications set in (Fig. Lincei 6. The com has plexity that presents itself is so great that thus far very little progress electrons been made in disentangling the spectra of the elements which have/ in their normal configuration. 342. THOMAS. Zelts. The radioactive metals follow almost nothing is known about their energylevel schemes. It starts off like the others with the alkali.
^ 47r/&. 37. 120. Rev. J We confine our attention to its application to the atomic problem.e9 the kinetic energy of the electron is insufficient to permit the escape of that electron to infinity. A .gt. Soc. *j/fr~ (4) where 1 == 7 ?~9o* This equation has been used for an extension of the statistical method to molecules! and to metals. If 9 is the electrostatic potential at the point in question.0. Roy. 727 (1928). fur Phya.lt. 77.gt. J LENS ABBJONES and WOODS.88534a * The introduction of o is due to Grra and f PEDEELS.gt.gt.gt.. 12 (1932). equation of the statistical method: i_JftCTj]*. This means that j? the maximum value of p at each point. Using (1) and (2) we see that the electron negative density at a point is related to the potential o by the equation n [2^16(9 90)3 op (3) Treating the charge distribution as approximately continuous we may to obtain the basic use the Poisson equation of electrostatics. f HCSD. If jpg. Proc. &. 2/*&. o~&. ro&. . Phys. We 47TD 3 is connected with n through the relation 2^ ==.336 of electrons in unit Tolume CENTRAL FIELDS is n._^ ^ ". For the atom we need a solution of (4) which is such that Ze r as r and as r&. the potential energy of the elec tron is 9.oc and which has spherical symmetry. As this must be the case in 9 the atom 9 we write j 2/t where O Q is a positive constant. Zeita. ^ Since for a neutral atom 9 tends to zero at = for regions of space where (2) leads to a infinity we also assume that n maximum kinetic energy. counted from zero at infinity. 217 (1931). so that of the electrons occurring at gives the maximum value of the kinetic energy a place where the density is n. 5 atom we may put coordinate form of the Laplacian and writing It turns out that for the neutral op = 0. 2 14 assume that tke kinetic energy of electrons at each point is as small as possible consistent with the density at each point. Using the polar .
Phys. 1898 (1931). With this approximate potential function Fermi was able to make a } striMng calculation of the number of s p d electrons in the atom as a func tion of atomic number. 38. Such a 14 computed numerically* and is given in Table 3 . . The values given here are taken from the table calculated witn the differential analyser by BUSH and GJLLDWELL. trons in unit volume for which the component of p perpendicular to the radius vector has a value between p^ and p^ f dpA is if we introduce the orbital angular momentum L=pj r. * A short table was given by Fermi. %(x). we obtain for the number of electrons for which L lies between L and L f dL LdL.STATISTICAL METHOD OF EEBMITHO&AS 337 we find that x( x ) satisfies a differential equation free from universal con stants: We need a solution of this such. that x = 1 at r = solution has been TABLE 3 14 The function and ^ = at r = oo. Hence the whole number for which L lies between L and L+dL at all places in the shell between r and r 4. At a point where the maximum value of p is p Q the actual momentum vectors are equally likely to be anywhere inside the Hence the number of elec centred momentumspace sphere of radius p s . Rev.dr is Replacing p* by its value 2/*ecp and integrating over those values of r for which the radical has real values.
The total energy is half of this since by the virial theorem the kinetic energy is average minus half of the average potential energy in a system of particles interacting by the Coulomb law. 5 . Soc. for an electron of zero : T j(iJ) is energy and orbital angular momentum (l + %)fi moving in a central field of 2 (21 +1) is the number of electrons in potential energy. Rev. 36. Rev. that is the energy necessary to remove all of the electrons from a neutral atom. Written in this form where the expression has a simple interpretation h~ l times the integral is the value of the radial quantum number. PHI. 1228 (1929). 794 (1927). Phya. t Toroe. o 14 where the smooth curves give the values of the theoretical N^Z) and the M Fig. An examination of the experimental data has been made by * Youngf for the MEUSE. 9 9 irregular curves give the empirical values as discussed in the preceding section. as given by the statisticalfield method.338 CENTRAL FIELDS ft 914 We shall suppose in this semiclassical L= (1+ 1) and dL^ftm order to find argument that we hare to put dr.lt. 23. ). e&. Numbers of s p d9 and/ electrons in the normal state as a function of Z. The agreement is extremely good. The result is that the total energy of the noimal state of the neutral atom of atomic number Z is W = 2083 Z^ electron volte. The factor a closed shell and the other factor is the number of closed shells occurring. . BAKZB. This was calculated by Milne and Baker. Camb.* The method is to calculate the electrostatic energy of the charge distribution. Fermi has done this: the results are compared with the empirical data in Fig. calculated classically. Another question which has been studied by the statistical method is that of the total iordzation energy. 630 (1930). Proe. 34. (7) A the number of electrons whose orbital angular momentum quantum number is I in the atom of atomic number Z. Ptye.?(r  The integral in this expression has to be evaluated numerically.
de Physique. 7. 77. Manchester Lit. A good discussion of this topic iias been given by HIRTREE. It is of interest because it exhibits the connection with the older quantization rules of Bohr and Sommerfeld. Jour.THE STATISTICAL METHOD OF FEBMITHOMAS 339 elements lip to neon. Proc. BEHXOUET. 518 (1926). this accidentally gave a much better agreement. In this approximation $a^a ~2/i(J? Z7)~*. We enter the wave equation f + ^(EUW = Q with the assumption so that 9 has to satisfy If fL were zero this classical (I) = ef?/s o 2 . we find 8 *+2p(UE) = 0. The WentzelBrHlouinKramers approximation. Zeits. 38. 91 (1933). (2) . For convenience we suppose this has but one mini mum and increases monotonically to the right and left of it. These lead to Hence in this approximation the wave function is given by where a= is i The approximation infinite * evidently not valid where E 17 = as $a becomes inside the and Phil. 3. 828 (1926). Let us first consider motion along a single coordinate under the potential energy U(x). for the first apJS ^S* two approximations. there. This suggests writing Equating successive powers of H to zero in the equation for 9. f 2/z. ffip t WXNTZKL. Milne gave the theoretical coefficient the value 17 because of numerical inaccuracies. Zeite. Soc. He finds good agreement with the exponent of Z but 2 14 that the data are better represented by the formula IF = 156 J^ electron volts. KSAMEES. 353 (1926).* An important method of finding approximately the eigenvalues and eigenfdnctions of onedimensional Schrodinger equations was developed by Wentzel. Brillouin. Phys. 39. . ( U E) = ij&p* (3) would be the same as the HamiltonJacobi equation of mechanics for the action function S(x). and Kramersf independently. ffip Phys.
aj *!))! cos/J Of / *a:s COS  (".^. the latter being taken proportional to the fraction of the whole period spent in going through this interval. (7) f TTJ rJ comes from infinity along the ray t=re".(f)~f*oos(frr). Gr&.gt.".340 classical range of motion.The function may be expressed in terms of Bessel functions of order onethird.lt. In the neighbourhood of these two points Xext let &.0) Applying the asymptotic formulas given in Watson (Chapter vn).2 are both positive. 188.Jx* \a\dx\. I \ WATSON.~J adx + r x \ v$ \cr\* f JJjexpl.gt. is finite (6) is The solution of this which Kramers took in the form everywhere f an Airy integral* which exp(# + #)*. CESTBAL FIELDS 3 14 where E&. us investigate the behaviour near the classical turning points of the motion. &.gt. this is equal to the classical proof being between x and x + dx. . p.gt. that is near the roots x ^ and x 2 (x^ x 2 ) of the equation E . 0) Comparing this with the approximation valid away from the turning points we see that (a.i7r^ and goes to 3 infinitv along the ray 1= re".0) (8) V3 that for large (f&.. the wave equation near either of the turning points assumes the canonical form ff^=0. Writing g = x\(xXi) or a(a? 2 a?).lt. tional properties given in Watson are applicable : .U. where x and x. so that the numerical tables and func where the path C .U(x) = 0. we find a./". (f &. Tkwry of Bessd Functions.
314 THE WBHTZELBRILLOIIOrKBAaiEES APFEOXIMATION &.lt. The equation is Near the nucleus U(r) is Ze*]r + G. (x~x ) (10) &. where the coordinate range is conditions . This completes the discussion for a single rectilinear coordinate where the 400.lt.lt. boundary conditions require that $ be finite in the range For atomic theory we are more interested in the equation for the radial to f oo and the boundary eigenfonctions. With the energy level so determined the approximate eigenftmetion (not normalized) is given by ^ exp r das I.5(0) = J2(oo) = 0.x% 341 These forms will join up smoothly in the region x I (4) only if the arguments of the two cosine functions multiple of IT. in terms of the classical f J with the solution differ by an integral x momentum at the point x } that (9) This is exactly of the form of the BohrSommerfeld quantization rule except for the occurrence of (% + J) in place of n.x&.^&. so the equation has the form If we neglect the constant term in the coefficient of R. It thus appears that the use of quantum numbers increased by J in the old rule gives an approximation to the energy levels as determined by quantum mechanics. this equation solved in terms of Bessel functions to give may be B(r)~A (12) .lt. This implies that 2 or. This was treated by Kramers as follows: oo&.! x: \J i  adx\ .lt.
No. 11. Phil. J PROKOFJZW. To terms of order r*1 this 2 . 13. 364.TlAffjL L T * _ o&.342 CENTRAL FIELDS the asymptotic expression for which Is Let us suppose that we have to take f j /2Za a 2* 2 V as the argument of the complex exponential in becomes VSZrja + _ 2Jfc (2). 13 (1926). Soc. Selskab. STCICBA. Zeits. KgL Danske Vid. (13) where That (f is. J1 V8Zr/a Comparing this with the asymptotic expression for the Bessel function we see that they will agree if At the outer bound of the classical motion in r one may join the approxi mation smoothly by means of the function as before.f They worked by a graphical process. I SUGIUSA and UBEY. Zeits. so their empirical energies gave several points on the curve directly. 2 1) one uses halfintegral values of the radial phase integral and uses instead of 1(1+ 1) in the term representing the effect of the orbital angular momentum on the radial motion. HAETEEE.gt. Prokofjew J made calculations for sodium by a numerical method. 1. 625 (1923).irk. 7. 21. 265 (1924). Math. Thus Kramers is led to the conclusion that one should use the classical quantum condition in } the form . This made the work easier because for the circular orbits the radial integral was zero. fur Phys. Mag. The first calculations with the halfquantum numbers demanded by the new theory were made by Sugiura and Urey. This result is the basis of a method for finding an effective central field U(r) which was developed before quantum mechanics by Fues and Hartree. 21. 48. VBZr/a 2F . Proc. 255 (1929).+i)A=(Zi)A. fys. . * Fmss.* This early work is characterized by the use of integral quantum numbers. ^r = (n. PHI. fur Phys. 495 (1927). 4. 12. so with this accuracy the approximation in the region of classical motion becomes / r \i C os JZ~(1 \2jZa/ r V8Z^+ 7= . Camb. 211 (1922).
to a good approximation Q(p)p for p&.gt.3U THE WENTZELBEILLOtnirKBAMEBS APPROXIMATION 343 If we write 2?=^.000264 s p + 446 pf 05275 1508 p 2 . PRQKQFJEW Q 05 10 15 20 25 30 35 40 r/a 14 field in sodium. can be evaluated exactly.4236 p 44876 01196P 2 4. For smaller values Prokofjew assumes Q(p) in the form 2 ap f ftp f y choosing two coefficients in such a way as to join smoothly to &.02072p4l3I9 2 00005p f 09933p+ 00222 p .6125. condition is U(p)= ~Q(p)lp*. 6 . p=r/a. For large p we have Q(p) ^=p and for all values Q(p) of sodium are essentially hydrogenic.p. Prokofjew gives the following the Q(p) integral table as the result for Q(p) determined this way: Range of p 001 015 100 155 330 6*74 Q(p} 2 to 001 015 100 155 3*30 674 oo Up 244 . Fig. Effective nuclear charge for potential the analytic expression used for larger p values and the third so as to fit the With this form for empirical energy values to the radial quantum condition.284 + p f 1153 p. the quantum where the limits of integration bound the range in which the integrand is Since the /terms real.gt.
344 In Fig. A sketch of the method follows. y(x then ^ ^ g( wtere g ( x )=f(x)y and/(x) is a known function (D=*djdx). We shall not attempt a thorough discussion of this matter as it involves varied questions of technique. Numerical integration of the radial equation. In terms of the back ward difference operator V the finite difference tables for interval h in x. for an electron in sodium. 6 14 is CEKTBAL FIELDS plotted the effectire nuclear charge for potential 3 14 as a function of p for this field as determined by Prokofjew and FermiThomas potential 4. From this we get ^ . now try to calculate the next value of in terms of quantities either known or almost known. fknctions Given an approximate potential function. The computed value of V g% serves to verify 2 the estimate already made. the differential equation to be solved is A trial eigenvalue is chosen. the eigenvalues and eigenmay be found by a numerical integration of the radial equation. of the form jy. ^ and so permits the extension of the table of 2 differences ofg by one more row. We see also for the that the latter does not approach the asymptotic value sufficiently rapidly in this case. By assuming a power series for y(x) near the origin one may find the numerical values of the coefficients and compute a table of values ofy(x) for small values ofx. If they do not agree the computed V #4 is used to get a new value of V^/ and the n process repeated. With experience the first estimate will be right more than half the time and it ought never to be gives us Vy4 and y4 which ^ . we see that V and the unknown ? 2g4 and V 4^5 These must be estimated from the trend in the table and a trial value of V 2 calculated. have D*y = g(x) V^y so may be set up We We Since 1 V = e~m we may express the operator D~ 2V 2 in powers of V by the series Of order from which follows 2 involves the known g% Referring to the above scheme.
mid angew. That would be a lucky accident.. 1 (1907). or Jour. 469 (1928). Norske VId. fur Phys. 48.f&..j In this one tries to represent the unknown function ^ as belonging to a class of functions. Then one chooses the para is normalized. Normal state of helium. the exact energy and eigenfunction will be found &.lt. say ^(a. } in this way.. &.) depending on several parameters a b. No general rules for this The process discernible. This is a minimum when meters in such a way that ized i/t 3 9 $H&. . Math. Zelts. have been given.. is carried out until the behaviour at large values of a: is In general the trial value of the parameter will not be an eigen value so the process must be repeated with a different trial.f&.j&.. From the standpoint of the calculus of variations the Schrodinger equa tion is simply the Euler equation which expresses the fact that the normal H minimizes $H$.lt.f&. Gesammdte Werle. 192.lt. 135. implies a set of equations o.gt.lt.(a. A&ads. furreiae Skrifter. Evidently if the b.) happens to contain the exact eigenfunction for some set family of values of the parameters. From the general principles of Chapter n we know that $Htfr will be greater than the least allowed value of for all except the eigeni/r belonging to this least allowed value. We wish now to consider another type of approximate method of obtain 3 ing atomic energy Ievels namely the variation method.c } . Moreover it is easy to see that ijtH^ is stationary for ^ in the neighbourhood of each of H ift the eigen^ s of and that the stationary value is equal to the corresponding allowed value. In a general way it is a consequence of this stationary pro perty that one can often calculate a fairly accurate value of the allowed energy from an evaluation of fH$ from a relatively inaccurate 0. KL 1932. By comparing the behaviour of the two trial functions one attempts to interpolate or extrapolate to a considerably improved trial value. Generally the method furnishes that tion ^.4M SOBlEBICAIi INTEGRATION OF RADIAL EQUATION 345 In necessary to make more than one correction to the estimate of this way the table is successively extended. 6.6 Cj . . we may use the Ritz method. V 2^.. (i) which determine the minimizing values of the parameters. HYLLERAAS. 5.c .gt.gt. p. * member of the family which gives the closest fit to the true eigenfunc found this way will surely be greater than Moreover the value of $H&. Instead of seeking ^ through its Schrodinger equa tion. and to illustrate its use with reference to the very exact calculations of the normal state of helium made by Hylleraas. Paris. Mat. 1911.. 54... No. 347 (1929). f RITZ.gt.* The key idea consists in recognizing that the Schrodinger equation is the differential equation corresponding to a mini mum problem in the calculus of variations.
and the eigenfonction (not normalized) This gives 1*605 Rydberg units instead of the observed value 1810 for the ionization potential of helium. For the normal state. b. It is evident that the success of the method depends principally on a fortunate choice of the family of functions $(a. as the lowest energy level. especially in the theory of elasticity. namely the one which merely changes the scale of lengths in the trial function. For the eneigy of a function $(ks. Using atomic units for length.. . 3 the plane determined by the two electrons and the nucleus as coordinates.^f atomic units. fur Phys. Thfe method of dealing approximately with variation problems was developed for classical problems. in Then one parameter may be handled at any trial function. the problem has been later treated with much greater precision by Hyleraas.346 CENTRAL MELDS 514 or equal to the least allowed value of H. and has proved to be a valuable tool in that field. $ does not depend on these angles. This onesided approach of the successive approximations to the true value is a useful feature of this method. 44. In the work on helium it has been found convenient to use the dis tances rj r2 and rls and the three Euler angles specifying the orientation of . Zeits. It was first used in quantum mechanics by Keilner* to calculate the normal state of helium. since if we ever find a value lower than the observed lowest energy level the theory must be wrong. c. The simplest possible choice of eigenftinction is obtained by normalizing the product of two hydrogenic Is eigenfonctions (r is in atomic units). let Z2 while the electron interaction us write once. . Here tie integrations are simply performed and give. 91 (1927).) on which the approximation is based.. It gives us a semitest of the theory in comparison with experiment. Jen) we find M 3 * KELLXEB. For the ionization potential as a function of Z we find (in Rydberg units) H{1) Calculated He (2) Li+(3) 54A5 5560 21 Be++(4) 11195 11307 10 0055 Observed % error 5 1695 1810 64 This shows that the simple screened hydrogenic eigenfunction gives quite good values as Z increases corresponding to the fact that the interaction of each electron with the nucleus increases as energy increases as Z. (Z.
quantum led definitely to the wrong value. In the third approximation Hylleraas =.00277 E=.gt. For $ Hylleraas assumes 7i.lt.(s.1 It potential as compared with an experimental will be noticed that the theoretical value exceeds the experimental value by 24 em1 . while in the sixth approximation (f&. When these of the finite mass of the 1 are included the theoretical value becomes 198307 cm.5 14 FORMAL STATE OF HELIUM if 347 where.m= Odd powers of cannot occur since must be symmetric in the two electrons.. we let 9= &. The results of such calculations are extremely interesting and show that quantum mechanics is undoubtedly able to give the correct ionization &. ty u) = e~&(l + 00972^ + 00097*2 . An eighth approximation led to 180749 RJic = 198322 cm1 for the ionization  value of 198298 6 cm..180488 RAc. . fur Pfays.gt. u).which is in agree ment with the experimental value.(s. 65.f&. /co rs ru N=\ Jo ds\ du\ dtu(s*l Jo Jo leads to k = Z//2J/ 5 so The condition 8 Eftk = This fixes the value of k in terms of the other parameters and gives us the minimum value of E with regard to variation of the scale of lengths in &. This is an important accomplishment of mechanics since it is known that the older quantizedorbit theories .gt. Zeits.lt. which appears to contradict our statement that the Ritz method is due to the neglect always gives too high an energy value.gt.j&. t.180648 RA. 209 (1930).f&. In order to calculate the ionization potentials of the ions isoelectronic modified the details of the use of the Ritz method so as with He 3 Hylleraas* * HYIXEKAAS.lt. the neglected spinrelativity potential to within quantities of the order of and nuclear kinetic energy terms. The discrepancy helium nucleus and to relativity effects.
759 (1930). finds that the electron affinity of the hydrogen atom  6 . in Rydberg iinitSj neglecting the finite mass of the nucleus and the relativity correction is given by the formula J?= Z2  1252? + 031488 . This e/r e state.00175221 4. In approximate work these auxiliary conditions make iff minimum value f$H$ under the auxiliary condition that to the normal state. from which seen that there is agreement within the experimental error known lonization potentials. which  is is roughly 06 electron volt (5000 cm". Excited levels in helium.348 CENTRAL FIELDS . since in the absence of exact knowledge of the ^r s for the lower states al one can do is require orthogonality to the approximately known is auxiliary exemplified by the calculations of Hylleraas and TJndheimf on the la2s*S level of helium. f HYLLERAAS and UXBHMM.2 . lomization potentials of twoelectron atoms* 6. 514 to obtain the ionization potential as a series in Z~~l The result. Using hydro v.1 }. This condition alone serves to make it exactly orthogonal to the normal lower states. This inaccurately applied auxiliary condition in general intro duces a large error in the calculations by permitting the trial to contain a component along the true $ of the normal state. The next higher level is characterized as the The be orthogonal fHift a minimpm under the two auxiliary conditions that ^ be orthogonal to each of the two states of lower energy. with a resultant sagging of the minimum value $H$ below the correct value. and the third level is that which makes trouble. variation method is peculiarly adapted to calculation of the lowest energy level of a system. for this is the level which corresponds to an absolute minimion of $H\[t. Nevertheless the existence of quantum numbers that are exact permits the exact fulfilment of the conditions in some cases. 65. TABLE 4M. Zeits. a symmetrical function of the position coordinates. In so far as He has exact RussellSaunders coupling this ^ must be an antisymmetric fonetion of the position of the two electrons. The data of the for comparison of theory it is and experiment are given in Table 4 14 .CK)0548.*** W17 (1930). fur Phys.
(1) where s and t are the elliptic coordinates of the preceding section. is 02469 Rhc which is considerably higher than the experimental 035048 R he. may generalize $~ek (1) to *[(Gi + C& + C&. relative to the normal state of the He ion. Preserving the requirement of antisymmetry. f ECKABT. on the term experimental value being value or 29 per cent. = 2 for the 3 eigenfunction (not normalized) for and 2 $ becomes Is state Zl $~e& [(& . They tried a more general form 4 iff and applied the orthogonality condition by a special device. Rev. . A more the accuracy is to note that it gives the significant way of estimating 025 Rhc to within 54 per cent. agreeing with the experimental value to about 001 per cent. + CsU8)smhct + t(Csr 0coshc] (2) and choose the parameters to minimize $H*ft. 07 per cent. 36. He made calculations with hydxo 383 (1930).02616 Rhc. to the normal state and the 2 S Orthogonality of the 2 P terms relative obtained by the proper use of the dependence on levels may be accurately 3 level the angular coordinates of these eigenfuactions.It coshf q. lies considerably below the observed 029196 because of the impurity of the normal state which is contained in the trial wave function. Eckartf 1 term.2 349 for the 2s state. 569 (1930). that is.gt.6 14 EXCITED LEVELS IN HELKTM . Phys. an error of 18 per cent. Bev. higher than the observed value. 36. the and Z%p as the parameters. The value obtained was . Calculation of the 2 the hydrogenie functions for Is was made in this way by Breit. . In this way Hylieraas and Undheim found 035044 Rhc for the energy of this level. Phys. they calculated $Hi(s for the symmetric function analogous for the 2 1 S level. Instead of taMng the least root. The value offH^ for this.* by using and 2p in the proper combination. The minimizing conditions expressed by 5 14 1 are satisfied by several values of the energy. the genie elgenfnnctions with. * BRETT. This gave a value 0*28980 Rhc. obtaining 0245 made the corresponding calculation for the 2 P P instead of the observed value . The value.02475. one value. with the effective nuclear charges Z& . 35.2}sinhft. measured in atomic units. on the departure from the hydrogenic value. 878 (1930). they chose the parameters in such a way as to minimize the next to the least value of the energy. of departure from the hydrogenic value the actual departure from this value.02664 Rhc. To illustrate the error involved in failing to apply the auxiliary condition to (I) properly.03422 Rhc.
This implies a correction to the energy of (l*ff(r) Is) j (Zl) for the nl + (ril\v(r) .lt. He assumed that the Is eigenfunction was almost entirely confined to smaller values of the radius than the nl eigenfunction. fur Pfcys. one may use as a good approximation the hydrogenie eigenfunction with full Z for the Is electron and the corresponding function with nuclear charge electron.e2 /r\nl) do not correspond to U(r) but to purely Coulomb fields instead. Zeits. Heisenberg s calculations were confined to the Is nl configura tions with !=0. This provides the additional terms 2 is (l%Jfe /r12 l*7iZ) (I$nl\e*jrl2 \nl Is) (ls\v(r)[ Is) (nl\v(r)\nl) with the result that the whole energy becomes independent of the choice of j   TQJ to the first approximation. The results were. and at the same time smaller than the values of r for which R(nl) becomes appreciable. well as He I. It is The third and fourth terms are nearly equal and opposite: on account of the spherical symmetry of the Is eigenfunction its field is like that of a charge * HEISEJCBEBG. .r ) An electron inside r moves in the full field while one outside r moves in screened field of effective nuclear charge. so he could take for the potential energy function of each electron r (r&. In calculating the first order perturbation one needs the direct and exchange integrals of the Coulomb interaction as well as the to allow for tbe fact that they perturbation energy corresponding to the fact that the true central field the field. in Rydberg units: P and 2 3P levels in Li II as He I Li II series of configurations because of the orthogonality of in the angle variables.350 CENTRAL FIELDS 6 14 3 21 genie functions and variable Z for the 2 $. 39.* It was in this paper that he laid the foundations of the theory of atomic spectra by showing the importance of the symmetry of the eigenfunctions. 499 (1927). Evidently the method could be applied to find the lowest levels in any the trial functions Historically the first helium calculations are contained in a paper by Heisenberg. Ze^/r . If rQ is taken rather larger than a/2 a Zl.
The values given by Heisenberg are 7.* The separation of the singlet and triplet states is given by calculating the exchange integral (lsnl\e (Rvdberg units): z ]T 12 \nlls). so that the trial function contains four variable parameters. out directly The minimizing with regard to the scale factor  can be carried 5 14 Because of the complicated way to in which a. The most careful calculations of the polarization effect are those given by Bethe. For the Li isoelectronic sequence the most complete work is that of Wilson. * BETHE. f WILSON. Normal states of firstrow atoms. 1. . These two terms fail to compensate exactly because some of the B(nl) charge distribution penetrates to smaller radii than some of the Is charge. 339 (1933). J.6 14 EXCITED LEYELS IN HEUUM 351 concentrated at the centre. For the radial and oc.00020 00098 . 210 (1933). since here plays the same role as k in . 17.0OW70 00032 x 1CT5 Li+(3) These values do not give a good approximation to the location.. 2d ed. Chem. Handbnch der Physik 24/1. When the outer electron is present its field acts on the inner electron to distort its wave function and give an induced dipole moment which gives rise to an altered interaction between the two electrons. in principle. of the mean of the singlet and triplet terms because we have neglected polarization. f functions he uses the forms He works with an antisymmetric 6 combination of oneelectron functions as introduced in 3 6. The numerical value of the units) as calculated third and fourth terms together (in Rydberg by Heisenberg 2p is 3j? M 67 He (2) . In this section we shall review the work that has been done on the use of the variation method for finding the energies of the normal states of the atoms in the first row of the periodic table. $. This polarization effect can. be calculated with the aid of the second order per turbation theory. r) and appear in the expression for fH$ it was not possible values of the parameters so a grapMcalsolve analytically for the best numerical method was used. Pkys.
R(2s). ibid. f ZIHEB. 61. TABLE 514 En&gies . SLATES. GuTLLTwra. 38. so Zener and Slaterf have pointed out that good approximations can be obtained by simply omitting the second term in . Pnys. fur Pkys. 878 (1930). r j this would make the numerical work extremely difficult. work are hydrogenic in character The R(%s) functions as used in the varia tion problem are not directly comparable as they stand. Zeits. The results show that the first term in JR(2$) is much larger than the second. so lie has just two parameters to vary. 86* 51 (1930).and ZESTER. The results of all such Table 514 summarized by Wilson are given in where the energies are expressed in atomic units (twice the Rydcalculations as berg unit).352 CENTBAi FIELDS 7 14 To compare with earlier work by Eckart and by Guiflemin and Zener* it should be noted that Eckart s M(2s) is obtained from Wilson s by the special = 7 = a. Rev. of the Li isoelectronic sequence* The S(ls) functions used in all this except for the variable scale factor. since they are not * ECILLRT. 36. . 199 (1930). 57 (1930). leaving them with three parameters to vary. Comparing with Hylleraas precise calculations on helium we note the absence of any dependence of the trial functions on the mutual electronic distances. and Zener s is equivalent to writing = ij in Wilson s. Rer. Phys. while Guillemin ization. The calculated values of the ionization potential are the difference between the calculated normal state of the threeelectron problem and that of the corresponding twoelectron problem.
NORMAL STATES OF FIRSTBOW ATOMS 353 orthogonal to the R(ls) functions and therefore cannot be regarded as belonging to the same effective central field. D. 7 3 where been made orthogonal to the E(ls). hydrogen like. . 7 *. since this change in R(2a) corresponds to adding to one row of the determinant a constant multiple of another row. This does not alter the value of the /? T in determinant form. choosing sidering JJ(2s) so that B(2s) is orthogonal to J?(ls). Wilson. by the fonr processes are 14 2 (2s) is plotted after the E(2s) has compared by Wilson in Fig. One can correct this by con = E(2s) + ft M(ls) as the proper 2s radial function.) has applied the variation method to the normal states of s the other atoms in the first row from Be to F. different R(2s) functions obtained. 036 Comparison of different approximations to R*(2s) for Li I. B GuiHeminZener. cit. Zener (loc. A. Slater. The four E introduced a node into Slater form for B(2s) although it was nodeless in the original form. It will be noticed that this process has 1 Fig. The figure shows a striking similarity of the R(2s) for the three forms which gave best agreement with experiment. C.
61.354 8.gt. fur Phys. 6 N E i&. At the other extreme we have the case in which ordinary the variation of $ is wholly unrestricted. 35. 210 (1930). The dependence of E on any more explicitly by writing shown fr particular factor of #. Let us suppose each of the w s normalized. although as yet they are not specified to be solutions I 6 and 2 6 If we use of a particular centralfield problem as they were in 6 the approximate Hamiltonian 1 1 ? neglecting spinorbit interaction. Rev. Zeits. that of seeking the be classified according make $H\f* stationary for normalized $. the value of JrHJt is * . Proc. I ) This dependence on u^al) exactly of the form of the dependence for a oneelectron problem in which the electron having the quantum numbers a 1 moves in an effective field for which the potential energy function OK) /%2  is S */f. Hence if HAETBEE. let all us neglect that requirement for simplicity and write for the the simple form (2 6 4) to the complete set # belonging A instead of the properly antisymmetrized function (3 6). Camb. The most . In between these extremes we may admit trial functions of special forms and determine their detailed character by the variation principle. Soc. In the Eitz method a trial to the type of trial function The s which may function depending on several parameters is used. FOCK. 126 (1930). say ^(a*).f Although we know from Chapter vi that $ must be antisymmetric in the electrons. . then the Euler variation equation is just the Schrodinger equation of the problem. is JJ K ^ S e2 u ( + terms is independent of %(#*). 8 14 different applications of the variation method. 24. This makes the value of and the stationary values are sought by $Htfi depend on these parameters calculus methods. Phys. 89 f SLATER. CENTRAL FIELDS Hartree s selfconsistent fields. Phil. since they occur symmetrically in (1028). ^f admitted for 0. useful of these is a method devised by Hartree* on physical considerations recognition of its connection with the variation principle is due to Slater and to Fock.j**i 6 6 and 7 6 the calculation of the matrix components being exactly as in only simpler because there are no permutations and hence no exchange integrals. This is true for each of the * u s.
For example. This field. or set of fields. Hartree s procedure is to solve this system of equations by equations for the But they numerical integration using a successive approximation process. 232 . being nonlinear and the appearance of u(a^) u(a?) under the integral integrodifferential through sign in (2). spherical symmetry in the atomic problem would be very difficult and would not correspond to an improvement in the final result. Physically the set of equations appears to be very reasonable.). Jour.(mf) priate to the set of quantum the normalized spherical harmonic appro numbers a1 This means in the variation pro *. * BRILLOUEST. Each electron actually does move in a field that is due to the fixed nucleus and to the action of the other electrons. 3. Hartree calls sdfconsistent in the sense that their own eigenfunctions are consistent with the potential field from which they are determined. In this way the variation principle leads us to a set of simultaneous w s. are very difficult. Brillouin* has developed it for use in the theory of metals.lt. For probably that reason Hartree does not use the actual nonsphericallysymmetric potential field defined by (2) but the result of averaging this field over all moving in an effective central field.8 14 HABTBEE S SELFCOKSISTENT FIELBS 1 355 E stationary by varying each. To keep this symmetrizing process within the form of a variation problem we may assume for each ufa*) that it is of the form of the wave function of a directions. This results in each electron s centralfield problem. each must a oneelectron Schrodinger equation in which the effective field is satisfy that of the nucleus plus the classical potential energy field due to the other we make electrons calculated according to their quantummechanical probability distributions. u^a ) independently. i ^(aO = J2(^S(Z mf). de Physique. In {! ) the of the electrons with quantum numbers integral representing the interaction and o? is now of the form J(a\ of) = f ftij(a*) u^) JJ % Ufa?) %(aO dvfa . It was set by such an argument that Hartree up his equations rather than by way of the variation principle. 373 (1932).I&. The method is evidently applicable in principle to the calcula tion of other problems where several electrons are involved.)^(a S(a ". T is (3) where S(Z%ftf) = (Z%f)&.gt. blem that only the of radial function B/r is subject to variation. Generally the potential in (2) due to the other electrons will not be spherically symmetric owing to a departure from spherical symmetry of J ? To consider such departures from the charge distribution ".
.356 CENTRAL MELDS 8 6 There . (5) .. Therefore if we use for each value of m\ not the field given by (4) but the value on averaging over the values of m\^ we have the same result as if we had taken the noncentral field (2) and averaged it over all directions 3 of r t . k J j ?".gt. For any fixed value of Vw$ 9 the a s of Table 2 6 have chapters* As that F the property that the average over m] vanishes for k ^ and is equal to unity for & = 0. It is evident that we shall have JS^S *(*). f fi 2 \XWV)dr. that is. as in Chapter vn and later A k structure involves integrals of the type anyway. feV 1 (4) This is a central field. From this expression it is clear that the effective 1 central field for the electron with quantum numbers a becomes F(a&.fi)Ti 2 +S 1 (&. The characteristic value e(af) of the equation for the iih electron is not the work necessary to remove it to infinity with no kinetic energy.&. but its value depends on the m t of the electron in question. Nevertheless it turns out empirically.* c=M) S S a*(Fml Vm\) ^ 3*(n?V) dr. This is an undesirable feature since we have to use the various complete sets belonging to a configuration to calculate the details of the level structure of that configuration.gt. r)  fa* f 7". the system of equa tions becomes a system of ordinary integrodifferential equations for the is This the field this operation of introducing central N radial functions. ^ F(a*.). consistent it must be that the correction for the self The value of E from (I) is given now by using our results wave functions. N N ".gt. so terms are quite small. it is not likely that we gain much in accuracy by dealing with different central fields for each ml value. each in three independent variables for the functions.S (a*afe*/ra f a&. as we shall see.gt. to be sure.. for in the actual process of removal its contribution to the effective field in which the others move is removed which in turn alters the characteristic values of all the other electrons.). with which the Hartree method actually works. where the a s are the coefficients in Table 2 6 and the FB are the radial 6 integrals defined in S loa. JT &. 8 14 whose evaluation we have considered in k we have 9 seen that J(a\ of) = S a*(V ml V m/) F*(nfl* nW). By symmetry. S(af) 9 instead of a system of partial integrodifferential 4 equations .lt. that these characteristic values for the deeplying electrons do provide good approximations to the Xray term values. ^(a Let us next see what value this method gives for the energy of the atom.
the removal from the equa tion for each other electron of the positive potential due to the i th electron will make each (af) (a *) so the first sum is negative. 25.jB) =  (oJ) + If V) . As a consequence the $ s obtained for the different configurations are not orthogonal and so cannot be made the basis for a calculation in which configuration interaction is taken into account by the perturbation theory. In so far as we can r ? &. CAUOT. 24. 89. Camb. . 225. In this same approximation the third sum vanishes. This shows us roughly why the quantity (a{ ) is equal to the energy of removal of _the fr th electron^ Before proceeding to discussion of the numerical results of the Hartree method we observe that each electron^ field depends on the particular configuration being considered.a* of) which exhibits the terms responsible for the difference between (af) and the ionization energy of the i ih electron. 310 (1929). Roughly. 111. so the interaction energy has to be subtracted from Se(a*) to allow for this. The increase in energy for (W .. Proc.* Suppose we compare this 1 electron problem in which the electron a* is for the with the energy E N removed: = where. Therefore we can use a more strict centralfield * approximation as set up in Chapter vi. 426 (1928). 5 calculate r (d) *(a?) by taking the average over the state u(aj ) of the change in potential energy without allowing for the change in u(a?) itself. PhiL Soc. On summing over in the first terra therefore the interaction of the electrons is counted twice whereas in (1) it should be counted but once. however.lt.8 M HABTHEE S SELECONSISTE^T FIELDS i th 357 is since the interaction of each other electron with. the term f 7 = (aWe2/r^ j^W) so that the first two sums cancel each other (a *) (a?) approximately.(0] + [ V o?eVr&. the electron counted i once in the equations by which each e(a*) is determined.lt. for its whole value arises from the changes in the functions u(a?) and u(a k ). the values of the terms occurring are calculated from the altered selfconsistent field (indicated removal of this electron is by ). On the other hand the various complete sets belonging to the same configuration do have orthogonal eigenfunctions since their orthogonality depends simply on the spherical harmonics and the radial functions found by the selfconsistent field method to calculate the term structure of any one con on the basis of figuration by the methods developed in previous chapters the spin functions.
358
9.
CEOTRAI, FIELDS
Survey
of consistentfield results.
9 14
In this section we shall give an account of the numerical results which have been obtained by the application of Hartree s method to particular atoms. The computing labour involved for accurate results is considerable but the results so far obtained indicate that the method is an excellent one for obtaining good radial functions for a first approximation to the atomic structure problem and as the starting point for more exact calculations. Therefore a number of workers are now engaged in a programme of these
calculations, the chief activity being that of Hartree and his students at Manchester. He is constructing a differential analyser of the Bush* type
which will be largely employed on this work and will soon add considerably to our knowledge of this type of atomic wave function. Owing to the rapidity with which these calculations are being made this section of our
book will probably be out of date soon after publication, so the reader who wants to keep abreast of the field will need to follow the current literature.
According to a summary prepared by Hartree for the summer spectroscopic conference at the Massachusetts Institute of Technology in 1933, the work may be divided into two classes according to the standard of accuracy
with which the selfconsistency condition is fulfilled. In class A the maximum
or three units in the fourth decimal place. Class includes calculations of a decidedly lower standard of accuracy. Of class the
error
is
two
B
A
following were complete at that time:
Oxygen Xeon I
I,
H,
III,
IV
Sodium. II
Copper II and chlorine negative ion Potassium II and caesium II
Silicon
V
HABTBEE and BLACK, Proc. Boy. Soc. A139, 311 McDouGAii, unpublished. McDouGALL, unpublished. HABTBEE, Proc. Roy. Soc. A141, 282 (1933). HABTBEE, ibid. A143, 506 (1934). McDouGALL, ibid. A138, 550 (1932).
(1933).
In addition to these he reported that various persons associated with were at work on Be, A1IV, A, and Ebll and that he would shortly under
take the negative fluorine ion and Calll. In class B the following were complete:
Helium I (and twoelectron
Lithium I
ions)
Mm
CALDWELL (Mass. Tech.) and unpublished work by Hartree.
HABGBEAVES, Proc, Camb. HABTBEE, unpublished.
PML
Be
II
and Be
I, also
B III
Soc. 25, 75 (1928).
Nel, 3? I, and Boron I
fluorine negative ion
BBOWIST, Phys. Bey. 44, 214 (1933).
BBOTO, BABTLETT, and Dusra,
ibid. 44,
296
(1933).
and
in progress were carbon
by Torrance
(Princeton)!, silicon
by Lindsay
(Brown), and titanium V, silver II, and mercury III by Hartree.J It would take too much space to make a full presentation of all details. Therefore we shall tell only of the programme of Hartree, in collaboration
*
f
J. Franklin Inst. 212, 447 (1931). completed: TOBBASTCE, Phys. Eev. 46, 388 (1934). J For mercury see HABTBEE, Phys. Rev. 46, 738 (1934).
BFSH,
Xow
9 14
SURVEY OP CONSISTENTFIELD RESULTS
359
with Comrie and Sadler, and the work of Hartree and Black on oxygen, as work.* After representing some of the most interesting possibilities of the and standardizing the computing method, Hartree arranged with Comrie
Sadler to carry out the detailed computations. The procedure, as Hartreef
explains,
"From
was
as follows:
the earlier work, I make revised estimates of the contributions to the field from the various electron groups, and the computing work carried out professionally is concerned with the calculation of wave functions in the
field so constructed,
wave
functions.
For
from these regarded as given, and of charge distributions reference I will call these calculations the standard
calculations.
Unless estimates of the contributions to the field have been calculations are not yet unusually fortunate, the results of these standard near enough to the selfconsistent field to be quite satisfactory, but they should be near enough for the effect of any variation of the estimates to be treated as a first order variation from the results of the standard calculations.
further revision of the estimate is made if necessary and the variations in the wave functions, etc. due to the variations in the estimates from those used in the standard calculations are calculated, and the variations of wave
"A
functions, etc.
added to the
results of the standard calculations; the varia
shorter and tions are so small that this variation calculation is very much of the easier than the main calculation. If necessary, further revisions variations from the results of the estimates are made and corresponding standard calculations are worked out, until a thoroughly satisfactory
approximation to the selfconsistent We now turn to the results for
electron in this state lying within r
field is obtained."
01"
and On*. If
given
radial function of the selfconsistent field,
is
R(nl) is the normalized then the total charge due to an
by
this being
a special case of a more general set of radial functions
Zk (n^n^;r)^rk P*
which
strength
i*S(nl*)R(nW)dri,
nuclear charge for field arise in other parts of the work. The effective 13 is then, at radius r, (which we called Zf in 9 )
the
the configuration under consideration. being over the nl values of  ZQ (nl, nl r)] is the contribution to Z at radius r from unit The quantity [1
sum
;
Si IV starting
terns an extended discussion of the calculation of the 8oa A138, 5oO from the Hartree field for Si V, see MoDoraAi*, Proc. Koy. HABTBEE, Proc. Eoy. Soc. A141, 282 (1933). f
* For
ftmction J Haxtree s notation for this
is
fc
of the
^^..^S^
(1932).
(V, nl
\r).
300
CENTRAL FIELDS
"
It is in charge on the nucleus as screened by an electron in an nl state. contributions to Z that work on the selfconsistent field is terms of these usually done, and the extent of the agreement between estimated and
calculated contributions usually expressed." In the standard calculations the contributions to
Z
were evaluated to
by one or two units. The standard of selfconsistency was such that the difference between the estimated and calculated contributions to Z for each whole group of electrons of the same
three decimals with the last uncertain
value did not exceed 002 at any radius. Hartree says: stable in the sense that "The contributions to Z may be called
*
5
if
the
estimated contributions from any group is increased over a range of r, the effect of this is to decrease the calculated contribution from this group (and
from others
in the field
also); for
an increase of Z means that the attractive
is
electron towards the nucleus
increased, the
field on an wave functions of electrons
become more compact, and the proportion of the electron tribution lying inside any given radius is increased
dis
14 Fig. 8 . Illustrating overstability in calculation of Hartree field for Cu II. Full line shows change of estimated contribution to Z; broken curve shows the consequent change in the calculated contribution to Z.
4
but the groups of the outermost shell, it is usually if not always the case that the change in the calculated contributions is smaller than the change in the estimated contributions. If this were so for all groups, an
"For
all
iterative proems, taking the calculated contributions from one approxima tion as the estimates for the next, would give a series of calculations with results converging to those for the selfconsistent field; though this process
would be unnecessarily lengthy as with experience It is usually possible to make revised estimates better than those obtained by simply taking the
,
calculated contributions of the previous approximation. But for the groups of the outer shel! and particularly the most loosely bound group, there
3
sometimes occurs a phenomenon which may be termed overstability, in which a change of estimated contribution to Z causes a change in the calculated contribution larger than the change in the estimate. When a group is overstable in this sense, an iterative process would not converge, but, for small variations, would oscillate and diverge, and it is then quite
necessary to choose, as revised estimates of contributions to Z, values
SURVEY OF CONSISTENTFIELD RESULTS
better than the calculated contribu
tions of the previous approximation; it is also unusually difficult to make
361
satisfactory estimates and adjustments to them, so the process of approxima
tion to the selfconsistent field
is
most
troublesome in such
cases."
An example
(Fig.$
is
M
)
of this kind of
overstability given in the calcula tions for the 3d 10 group in Cull. The
tables of the radial functions obtained
are given in full in Hartree s paper. To exemplify the point discussed in the preceding section that the individual
electronic eigenvalues, (a i ) agree fairly well with the Xray terms, Hartree
,
20
gives this table:
From
the radial functions the total
40
charge distribution in electrons per atomic unit of the radius can be calcu
lated.
Using the
results for
KII and
Rbll
RbU,
following
the alkali ions preceding and Cull in the periodic system,
an interesting comparison is made in 14 from Hartree s paper. This Fig. 9 shows clearly that the charge distribu tion for Cull is much more compact than for either of the alkali ions, a fact which is reflected in the interatomic
distances in the crystal lattices of the three metals:
Half interatomic distance
KH
Cull
RbH
2309 1275 243
Charge distributions in KII, Cull, and Bbll as obtained by the Hartree method.
14 Fig. 9 .
362
CEXTBAL MELDS
$ 14
distribution curves shows that Comparison of these rallies with the charge is just a little greater than the in each case half the interatomic distance
curve. abscissa of the last inflection point in the total charge distribution
10. Seliconsistent fields for oxygen.
While most of the calculations on selfconsistent fields are for atoms or the case in ions in which all the electrons are in closed shells, this is not Hartree and has been made by oxygen for which an interesting study This affords a more severe test of the method than closed shell Black.* structures in which there is no approximation involved in averaging the
over
all
directions in space.
The
results obtained for the total charge
_...
O O o
O
I
II
ra
IV
1S Fig. 10 .
Charge distributions in O I, O IE, O HI, and by the Hartree method.
IV, as obtained
14 which indicates clearly the density distribution are shown in Fig. 10 increasing compactness of the atom as the degree of ionization is increased. This closingin is mostly due to the change in the 2p radial function as is
M brought out nicely in Fig. 11 which shows the radial charge distribution of the 2p electron for several stages of ionization. The curves are not accurately repiesentable as a single function plotted to different scales of
abscissas,
however which
s
is
the approximation implied
when
the wave
functions are treated as hydrogenic with appropriate screening constants. In using these radial functions to calculate the energy levels of the normal
configurations of the oxygen ions, the quantity YIPF is evaluated, where is the properly antisymmetrized combination of the oneelectron functions,
Y
as in 3 S 6. This integral can be evaluated for each state of the zeroorder
* HJLETSKB aad BI^CK, Pfroe. Roy. Soc. A139, 311 (1933).
[014
SELFCONSISTENT FIELDS FOB OXYGEN
363
Approximation in terms of the F and G integrals as in Chapter vi and then these may be used as in Chapter vn to find the energies of the RussellSaunders terms. The present calculation goes beyond that of Chapter vn, for now we have the radial functions and so can get approximate theoretical
values of these integrals instead of treating them as adjustable parameters. There are two points to be noted in extension of the developments of
Chapter vi: 6 s and 7 6 depend essentially First, the results of Chapter vr, especially of on the fact that the oneelectron eigenfunctions, w(& ), are orthogonal. If the
,
functions are not orthogonal, analogous results can be developed but they are much more complicated. The selfconsistent functions are orthogonal
01
Oil
o o
in rv
r
14 Fig. 1 I .
Change in
E2 (2p) with increasing ionization in O I, O II, O HI, and O IV.
and l because the spherical harmonic and spin with respect to 1 9 s, factors have been retained, but they are not orthogonal with regard to n since different central fields are used for R(nl) and R(n l). This is most simply
remedied by using for R(nL) and R(n l) not the fonctions given directly by the Hartree method but linear combinations of them that are orthogonal.
This does not affect the value of T because it amounts to performing the same linear transformation on all the functions in the same rows or columns
of a determinant. (Compare
7 14 .)
f
m
m
We pause to note that the fact that this
of ways without affecting the result shows that the exact distribution of the charge density among different values of n,
may be done in a large variety
same I,
is
without significance. Thus for the Is and 2# electrons any two orthogonal functions for which J22 ( Is) I H?(2s) is the same function of r as is given by the Hartree field will do equally well. In the actual numerical
for the
364
work
it is
CENTRAL FIELDS
10 14
found convenient to take the foEowing combinations as the
),
orthogonal functions (denoted by
where
(
I
 $ 2 )i[I?(24  SR(ls)],
R(ls) R(2a) dr.
*
S=
I
Jo
Second, in the Hartree method the radial functions are not, as in Chapter vi, eigenfonctions of the same centralfield problem. As a consequence the
calculation of the quantities
becomes an actual calculation, whereas before we could replace
at once
field
the u(a?) were characteristic functions of this centralproblem. This makes necessary a fair amount of additional computing. The results of the calculations are very good, with regard to both the
by
&lt;((/)
absolute values of the terms and the interterm separations. Measuring each term down from the normal level of the ion with one less electron, the values
in atomic units are:
o in 2/
sp
0fl
2
01
2p*
/&gt;
is as good as can be expected. On the standard first the interval ratio ( lD^S)j^P^D) should be 15 while the approximation observed ratio is only I 14 in 1 and III 5 7 ), so evidently large per (cf. turbations of the second order are here.
The agreement here
important
CHAPTER XV CONFIGURATION INTERACTION
Hitherto
we have
neglected matrix components of the electrostatic and
spinorbit interactions which connect different configurations when applying
the perturbation theory.
Now we have to consider what properties of atomic are distinctively associated with these matrix components. So long spectra as the interconfiguration components are neglected, the resulting eigenfunctions are precisely associated with definite configurations; this has been
the standpoint of the preceding chapters. If they are no longer neglected, their effect may be treated as a perturbation which causes interacting energy
levels to
be pushed apart and results in an intermingling of character through
linear combination of the *F s of the interacting levels.
in atomic spectra. a level cannot be accurately approximated by a single of Generally the 6 definite function of the type 3 6 or of combinations of them belonging to one in the last configuration such as we have considered exclusively except In Chapter xiv we have seen that more general forms were needed chapter.
Such interactions are of quite general importance
Y
an accurate calculation of the normal state method is used, all attempts to recognize the of helium. When the variation trial functions as the wave functions of a centralfield approximation are wave given up. The reader may readily satisfy himself, however, that any function depending explicitly on the distance r12 of the two electrons in helium corresponds to no definite configuration assignment in any centralfield problem. In such calculations of energy levels the centralfield ter elsewhere minology is more in the background, however, so we must look
by Hylleraas
in order to obtain
for really distinctive manifestations of the interaction of configurations. These are of several kinds. So far very little theoretical work has been
done in the way of definite and detailed calculations of these effects, so this sketch. chapter must be in the nature of an outline have alarge electro First,it may happen that two particular configurations static interaction which is sufficient to make the order of the terms be other than that given by the ordinary firstorder theory of Chapter vn. The best 2 in Mgl, which we example is the interaction of sd and p configurations
consider in
1.
entire series of Second, one term of a configuration may interact with an terms with a consequent departure of the series from the simple Rydberg or Ritz formulas which usually hold for series. This we shaE discuss in 2. of an atom are in Third, terms lying higher than the ionization potential states in the continuous spectrum correa position to interact strongly with
366
result
COXHGUEATION mTEEACTION
I 15
relative to the ion. As a spending to unclosed electron orbits of one electron suet levels lose their sharpness and acquire something of the cha racteristics of the continuous spectrum. They give rise to broad fuzzy lines,
their lifetime is altered
their intensity relationships become quite sensitive to the partial pressure of free electrons in the source. This pheno menon, which is analogous to predissociation in molecules, has not been
and
treated very exactly theoretically in any special case.
We shall report the
c
known facts in
3.
9 Fourth, as already mentioned in I , the possibility of socalled twoelectron jumps/ that is line emission in which the apparent configuration change involves two of the id values, is connected with breakdown hi con
3
figuration assignments. This is discussed in 4. in the alkali spectra Finally, in 5 we discuss the intensity anomalies
which are associated with spinorbit interaction between configurations.
1
,
Interaction of sd
and p2
in
magnesium.
The general theory of the RussellSaunders term energies (Chapter vn) 3D 3D for the 1 simple s d configuration and for the interval *D gives D
the
ij) 82)
= f fl(na,
&lt;Z),
do not need where the 6 is defined by 86 15b. From their definition the to be positive like the JF s, and so at first sight it appears that the singlet might on occasion He below the triplet on the energy scale. This is actually the case in the 3^ 3d configuration of Mgl. However, Bacher* noticed that no reasonable approximation to the radial functions jft(3s) and R(3d) would make the G integral negative. Using radial functions determined by a devised by Slater he calculated iJ9 3D~ 44000 cm1 whereas
&lt;?*s
,
the actual experimental value is ~ 1600 cm" 1 1 below its Thus the *D is actually about 5600 position calculated by the ordinary method. This Bacher ascribes to interaction with the 3p 2 con
.
cm""
figuration,
which gives *D,
3
P and I S terms.
Since
JL
2
and
S2 commute with
Xe
2
will Xj* the electrostatic interaction
have no matrix components con
necting terms differing in regard to L and S. Likewise since the electrostatic of II 6 there will only be interaction commutes with the parity operator
&
interaction between configurations of like parity. The parity condition is 2 1 ofp 2 with satisfied, so we expect an interaction of p and sd, but only of the
D
the 1
D of ad. The former is above the latter and as all such interactions make
move apart the situation is right for an explanation of the effect.
for the
1
the levels
What is surprising is that the interaction is large enough,
above the ionization
1
D ofp* is
level of
Mgl, about 15,000
cm"
1
above the mean of
D and 3D of the ad configuration.
By setting up the electrostatic interaction in terms of the zeroorder wave
*
BACKER, Ptys. Rev. 43, 264
(1933).
UITOSB. Rev. Such producing strong departures from the usual BydbergRitz series have been known for a long time and various explanations irregular for them have been advanced. He nd 7idn. Bacher finds that the nondiagonal matrix component 1 2 1D amounts to ! Their interaction energy is cm". 44.! following a evidence that they are suggestion of Langer.s compares the results with observed data in f . R the Rydberg constant and ft and a are constants. Ftys. altered intensities. 3 2 and nd^n^s. is that of Perhaps the most interesting effect of configuration interaction formulas.* who calculated the interaction between the configurations nd ris. effects due to configuration interaction here. latter. the energy of binding of an s electron We n value is about the same as that of a d electron. Its true wave D function will be a linear combination of those for sd W and 2 3 j? D in which a large component of the e.gt. so that there is a large amount of overlapping of the terms arising from such configura x . IN aiAGNESIUM 367 and transforming to LS eigenfunctions.2 s*. . Ti II and Zr II.200 aecting sd D and p Junctions . J have given very convincing due to configuration interaction. Calculating the effect 1 1 in detail he finds that the interaction pushes the sd !) down to 4000 cm". Perturbed series. thus comparable with their unperturbed separation. 415 (1932). 13. The Ritz formula is of the form 2. * R where a n is ^ the absolute energy value of the n th term measured from the series limit. As to the inaccuracy of the final result.[is INTERACTION (MB sd 1 AND 2 3&. and finds definite evidence that the configuration interaction have seen in I 14 that in all the has altered the intervals between terms. 35.g. the exact assignment of the to the configuration sd is quite meaningless. but Shenstone and Russell. perhaps no better agreement can be expected because of the approximate character of the radial functions used. 649 (1930). Phys. whereas it is only observed 1600 cm1 below. Bev. of course. The conclu sion is that the configuration interaction is certainly adequate to account for the inversion. elements where a dshell is being filled. Phys. by methods explained in conChapter vm. Naturally this alteration in the character of the wave function will bring with it other special features of the spectrum. 732 (1933). a being small. Hence tions as dx d x *s and d quite generally we may expect large of one higher . * . t SHENSTONE and RUSSELL. below the triplet. With such a below sd there is 3 D 1 large interaction. although as yet the only detailed calculations we have are those due to Ufford. Eev. Another detailed study of configuration interaction has been made by 2 Ufford. 39.
On (2) ^O the added term in the formula for the effective quantum number representing the effect of perturbation of the series members by a foreign level at the term value GPO Such. . 286 (19SS). 404 {193% . while the Bitz formula is a straight line with intercept /i on the axis of ordinates and slope a. Shenstone and Russell find that they can represent many series which is quantum number n* defined It Is convenient to study the behaviour of series $ji f depart from (1) by the formula n* = n^jJirX(J n 8 i . Soc. As the perturbing term has larger intervals than the series would have if unperturbed. In this series the maximum up to the perturbing term and then rapidly sink to zero as one goes up the series. by plotting (n* n) against a n In that case the Rydberg formula (a = 0) is represented by a straight Hne n*~m = parallel to the axis of a. bola with a vertical asymptote at 0". Boy.* Pincherle has given a theoretical calculation of the per 21 turbation of the 3s nd a series in Al II term and finds orderofby the D %&. 404 (1933). 3 2 and 3 1? each of which are separately perturbed D D D extraneous term. . Free. ibid. by the corresponding level of the Numerous examples of other perturbed series are given by Shenstone and The subject has recently attracted the attention of a number of spectroscopists. To indicate haw accurately the hyperbolic law is obeyed. 83. CONFIGURATION IXTEBACTION effective 2 15 by the relation given in (1). As a result the value of n* n would rather rapidly by a whole unit in going past the value of the perturb ing term ". TMs is due to the fact that there are three series. S Related to the perturbation of the intervals increase to a D levels of the series is the perturba tion in the intervals between the levels of each term. 37 (1933). Beutler has extended the * work of Shenstone and PKCHEBLE.because by counting it in the series all Mgher terms would be erroneously assigned an n one unit too high. Curve (1) shows the n* n values as usually given and curve la shows how this becomes a hyperbola with asymptotes at a = CTO when the Hglier series members are given the altered n assignments. Nnovo dmento ID. counted in as a member of the series. THs is illustrated in Fig.363 The . a formula plotted with n* n against & n represents a hyper . the extraneous term was often . this tends to increase the other intervals by the differential effect of the perturbation. In curve (3) the values of (*)j3 (a cr ) are plotted to an exaggerated s 9 tt scale wMch shows in another way how accurately the formula is satisfied. fur Phys. shows the series of the 3D^ levels of Ca I.gt. 83. I 15 wMefa. Russell.=cj Before the perturbation of series levels by an extraneons term was recognized. 3 3 . curve (2) shows a plot of (n* n)(cr n G ) which should not contain the singularity in the curve of (ri*n) against a. BETCTLEB* Zeita. D magnittide agreement. A142.
44. Phys. ibid. 3. Rev. PHILLIPS. In the oneelectron problem the continuous range of positive energies has * EJLBBISON and JOHSSOX.* The most thorough calculation by quantummechanical methods of series ^regularities are those given by Whitelaw and Van Vleck for Alll. 757 (1931). Some general theoretical work on the which configuration interaction affects line strengths has been done y Harrison and Johnson. Phys. 44. An Autoionization. 551 (1933). 38. 44. Phys. angstroth has made quite a detailed study of perturbations in Bal. Rasmussen. Rev.f ay in Mr \6M 6060 ff n 1S Fig. 1 .000 in cm". 40. At all energies higher than the minimum necessary to remove one electron of an atom to Infinity. 316 (1932). } WHITE. f WHITELAW. J This inversion is shown to be capable of production by interaction with configurations of extremely high 6 energy in which one of the electrons of the p shell in the core is excited. . explanation involving configuration interaction for the occurrence of inverted doublets in the alkali spectra ( 8 5) has been proposed by White and considered in detail by Phillips. Rev.PERTURBED SERIES Lussell on the perturbed P and ew experimental data on the 1 3 369 P series in Hg I. has obtained F series in Ball showing perturbations. the spectrum of allowed energy levels is continuous. 644 (1033). 8000 imOO * 12. 1 The perturbed *DI series in Gal. 544 (1933)? VJLBT VLECK and WHITELAW. icluding the effect on intensities. ibid.
gives rise to energy levels lying above the least ionization energy of the atom. acquires to feature of the states of the continuum is that they are unstable in the sense that one of the electrons moves in an orbit which extends Hence as a result of interaction with them the discrete level some extent the property of spontaneous ionization through one of the electrons moving oS to infinity.370 CONFIGUBATION INTERACTION 3 35 associated with. but that owing to coupling with the continuous spectrum there is a probability per unit time that the atom will make a radiationless change of state over into a state of the continuum of equal energy. This property is called autoionization. Owing to this possibility of leaving tion field the discrete state rather quickly. There are two mathematically equivalent ways in which we may regard the broadening of the lines. To label these states the integral total quantum number n of by the continuous variable E which gives the limiting value of the kinetic energy of the electron when at large distances from the nucleus. in the midst of the continuous spectrum. if there is interaction the of the quasidiscrete level becomes coupled with the s and the configurations involved in the do not exhibit any special properties on T Y of the neighbouring levels in the continuum. In the spectroscope wave trains give rise to a broadened line because the Fourier integral representation of the short wave train involves a band of frequencies in the neighbourhood of the mean frequency. The direct spectroscopic effect associated with autoionization is a broad ening of lines whose initial levels are subject to the effect and an alteration in the intensity of these lines with variation of the concentration of free electrons in the source. As a consequence the state assumes something of the character of the states of the continuous spectrum. it a continuum of states for each value of the orbital angular momentum. At each energy E the T of the corre equal to the these short sponding state in the continuum will contain a certain component of the eigenfunction of the assimilated discrete level. B 9 while the ordinary continuum combines weakly or .e. It may happen that a configuration in which two electrons the discrete states is replaced are excited. We may say that the discrete level. Assuming that the assimi lated discrete level. However. but in which both are in discrete levels of the basic oneelectron problem. remains sharp. the interaction of the atom with the radia is limited to the production of short wave trains of mean duration mean life of the atom in the discrete level. If there is no interaction between these states 5 continuous speetrum these levels account of their location in the continuous spectrum. is capable of strong radiative combination with a E lower discrete level. as a level. A. This will be larger the nearer is to the original position of the discrete level. The most important to infinity.. Another way of regarding the matter is to treat the discrete level as com pletely assimilated into the continuum. i.
(1925). very little has been done so far in the way of attempted The theoretical quantitative calculations of the amount of autoionization. 29. . See also LOOKER. 484 (1932). Comptes Rendus.K . correspond to electrons of K K considerably less energy.3 15 AUTOIOOTZATIO2* all 371 not at with B. 6. de Physique f AUGEB. ^&. i Fig. ). Phys. One trail is long and is c\j interpreted as due to the primary photoelectron shell by the light quantum. Of equal energy (Fie. when present. If these are not to vanish. fur Phys. ejected from the K Another of the trails was found to be of the correct length to correspond to a kinetic energy of about and L are written for the corre 2L. it is clear that the intensity of radiation from the con tinuum in combination with the discrete level B will be dependent mainly on the amount of W(A ) contained in the eigenfunction of the continuum at each level JL. is related to that underlying the theory of predissociation. r. whereby a molecule may spon analogous phenomenon in which taneously dissociate if put into a quasidiscrete state exceeds the energy necessary for dissociation. 183 (1926). 321 (1928). where excitation energies of the atom. Autoionization or Auger effect in a 15 A ieveL * WBKTZBL. This has been discussed by WentzeL* Apart from the general formulation and some qualitative discussion based on the application of the selection rules. de Physique 6. energy. As this is a maximum at the original location of the discrete we obtain also by this argument a broadened line at this place. 1215 (1926). 40. 182. Phys. the problem in molecules. 773. Autoionization is thus a consequence of the presence of matrix components of the Hamiltonian connecting a discrete level above the ionization energy with the states of the continuum at the same energy. Other sponding trails. 524 (1927). 180. Asm. Zeits. ". shall s have to be i i ? * spectroscopic in character. 205 242 . 2 15 . 43. Augerf showed that when a gas in a Wilson cloud chamber absorbs j Xrays there are frequently several electron tracks diverging from the same point. 65 (1925). Zeifcs. Jour.lt. these states must be of the same parity and the same J value. L and S The perturbation theory for this case requires some modification to take into account the fact that the interaction is with a continuous spectrum of states. its energy In view of the lack of an accurate detailed theory we content with a review of the main experimental /$ facts The first evidence for auto ionization was noil. 2 . The interpretation of the 2L is clear from the diagram trail of energy G%t K ** The atom is left in the Jf level by removal TT 11 of an electron from the A shell. more over in case of RussellSaunders coupling they must have the same values. Rev.
The short process.. According to him. nrnnber. but such roughnesses axe acceptable in view of the lack of precision with which the electron energies are measured. 2 L. The probability of antoionization of the K K level may get out either processes are by no means rare. p of atoms emitting level is given by i p. from the K level by autoThe abscissas are the atomic numbers Z* The heavy curve is the theoretical value as estimated by Wentzel. though rather rough. K electron trails are supposed to be due to further autoionization processes 2 occurring in the ion in tie I* 2$ configuration. Such spontaneous ionization 3 cm". 6 r~ i r COMPTON HARMS I ^ ^ Theoretical (WENTZEL) 2 15 Fig. in detail in that argument we have supposed the energy of removal of the second 2s electron also equal to L.372 with the the CONFISCATION INTEBACTION 3 15 K atom Hence level is the configuration Es. 3 9 radiation as a function of the atomic Fraction. ionization. For light elements the autoradiation of a by K K ionization processes occur much more frequently than the radiation. while the reverse is true for heavy elements. TMs is shown in Fig. the probability of autoionization is 5 p. The which implies expulsion of an electron with energy is correct in principle. An atom in the line or by autoionization. 3 15 3 where the ordinate tion. gives the fraction of all atoms in the so that 1 p gives the fraction which pass K level which emit K radia nearly independent of Z 9 so the whole variation of p . ". where the autoionization may pass over into this configuration by W2sQ E=K2L.
* SHENSTONE.* Shenstone discussed optical region the effect in general and especially in connection with the spectrum of Hg I. and this raises the problem more affected than the other levels of the same term. Cd three cases the 3 and Hg respectively. Phys. Phys. . 947 (1926). p configuration. 873 (1931). However. Y( 2 coupling escapes mixed with *SQ and hence unstable. f LAWBE*CE. D becomes subject to autoionization through interaction with 45 Ed. These were interpreted by Shenstone levels which are subject to autoionization. The absence of 3 P 2 is interpreted as due to strong autoionization pro as to why this level should be so much bability. fur Phys. Through partial 3 2 P ) acquires a component of Y^Dg) and tilus the 4j&. Here the striking thing is that in all P and 3 PX levels are known but the 3P2 cannot be found. but later work by Beutler J on the farultraviolet absorption spectrum shows that this particular identification cannot be the correct one. Nnovo Cimento 8. 2 3 terms due to 4p 2 . that is. 28.gt. This view seems adequate to no detailed correla explain the observed facts. . P should become and so of LS Z . Rev. 2 *S and 1 terms sub These give rise directly to interactions making the breakdown of the LS coupling in ject to autoionization.. 38.. J BEFTLEB. 710 (1933). probability of ionization of Hg atoms by impact of electrons having energies close to the ionization potential shows discontinuities of slope as if new ionization are becoming effective with increase in the modes of producing as due to excitation to the voltage. MAJORANA. The 4s Ep continuum (correspondingly the 5$ ooZ in Cd and the is due to an odd configuration and hence cannot give rise to autoionization arises the 4s oci limit in Zn of the even 4p 2 configuration. approxi 4 mately as Z? in the Recognition of the importance of autoionization in atomic spectra is due to Shenstone and to Majorana.* See also SMITH. with 4s Ea and 4s Ed. 37.f Lawrence found that the . Rev. the fact is that the interaction here 3 seems to be much weaker than for P 2 but Majorana s theoretical discussion does not show clearly why this should be so. which can only be unstable through inter action with even parts of the continuum. Zeits. 86. 5jp 2 and 6p in the s paper deals with the Majorana P spectra of Zn. although at present there is tion between the values of the ultraionization potentials and known spectrelevels. Among other things he showed how it provides an explanation of the ultraionization potentials discovered by Lawrence.3 15 AUTOIONIZATIO3T 373 with Z Is due to the increase of the radiative transition probability. The autoionization by interaction with the continua associated with 6s col in Hg). Phys. 808 (1931). Shenstone thought the levels responsible for the ultrascopic g ionization potentials were probably connected with the d s*p configuration in Hg. Rev. 107 (1931). As P 1 is the only level in the configuration with J = 1 it is not subject to breakdown 3 autoionization.
Pfcys. in air at various pressures Allen also studied the variation of relative intensity of the lines arising in a term with change in the arc current. 42. originating This is in fact the case. approaching zero relative intensity at currents below one ampere and approaching constant values for currents above twelve amperes. Rev. raregas spectra.. fur Phys. This could nullify the effect of autoionization and build up the strength of the lines from the unstable levels. comes into play. S6. . (3d 4:s6s) D of dlQ Ed if there up to 80 atmospheres. lines arising from the Dj and D levels should be sharp from the other two levels of the quartet should be broadened. 87. Rev. This view has not been subjected to a quantitative discussion. But lines from 4D and 4D were found to approach finite width at zero pressure whereas those from the other two levels approached vanishing width at zero pressure. 176 (1933). But according to the J selection rule 4 4 only the levels D and D^ can show autoionization. It seems likely that this effect is due to the fact that the atoms in the unstable states normally fall apart by autoionization before they can radiate. 39. 710 (1933). This D arises from an even con and so can show autoionization through interaction is enough breakdown of LS coupling to permit violation of the selection rule on S. 2016 (1931). in which free electrons are caught up by an ion. It was found that the lines from the unstable levels of the quartet term were very sensitive to arc current. with the same rate of increase for unit pressure increment. Particularly interesting is the behaviour of lines in multi4 term which lies in the range from 95 to 2164 cm. But if there is a high concentration of free electrons around the ions the inverse process. The breadth of all lines originating from the quartet levels was found to increase linearly with the pressure. Therefore in a multi 4 4 while those ple!. These intensities are relative to other lines of the spectrum.1 plets arising from a D above the d with 2 10 ocl 9 4 ionization limit of Cu. Allen measured the line breadths in a Cu arc running figuration. f WHITE. some of which give rise to broad lines. 38.374 The CO^MGITBATION INTERACTION 3 15 arc spectrum of copper is known to have a large number of levels above the ionization limit. The arc in these experiments ran 4 D at atmospheric pressure. 19. Ebys. J BETOOK. Results of the experiments of Allen* find satisfactory explanation in terms of the autoionization process as was pointed out by Shenstone in a note appended to Allen s papers. Zelts. as BeutlerJ has found a long absorption series in * Hg vapour corresponding ALLES. Autoionization effects observed in spectra of the alkaline earths and in shown by White. auxiliary experiments having shown that lines not subject to autoionization retain constant relative intensity with varia tion of arc current. 55 (1932). f provide further examples of the operation of the selection rules.
apparent two. of this point. transitions are called in the elements of the iron group. etc. This is clearly due to the breakdown of precise configuration assignments. magneticdipole. the existence of radiative from the nonvanishing of the matrix components (xljajJS) con where a stands for any type of electric necting the states of A with those of B. that the only nonvanishing matrix components con quantities of type nect states differing in regard to one individual set of quantum numbers. or inferentially * CONDON. appears there have not been as yet any apparent twoelectron jumps. 38. ibid. arises or magnetic moment of the atom. As we observed in I 9 it is a consequence of the fact that the various moments electricdipole. that broadening by the autoionization process and the experiments show the amount of the broadening decreases as one goes up the series.or manyelectron jumps may of the to be fully adequate for the interpretation This view A may combine with configurations excluded by this rule in virtue quantitative investigations calculation the amount of configuration interaction either from a precise from the observed from the fundamental wave equation. If the configuration interaction expansion will appear and the experimental spectroscopist tion. Such only between configurations differing in regard oneelectron jumps. be permitted. 4. for In this way of the other configurations involved in its eigenfunction. 1121 (1930). jumps.3 15 AUTOIOOTZATICm 375 These are aU subject to to the transitions &P Q 6s* S :L tf +5cP6s*np L P l . are . electricquadrupole. one configuration in each with a considerably larger coefficient than the others. 36. not too great. Phys. F Therefore in the approximation in which an energy level is assigned definitely to one configuration of a centralfield problem.* to (J5) corresponding If we know accurately the eigenfonctions Y(4) and transitions between them two levels A and B. These are known as twoelectron jumps. showing that terms near the ionization limit are more unstable than those of similar character at higher energies. 225 (1931). Rev. What is needed are estimates of GOUBSMIT and GROPPEB. However. However. Manyelectron. is The oneelectron jump will assign the level to that configura rule will not then apply to this approximate label. lines are observed corresponding especially to transitions in which two of the nl values change. T(4) and T(B) involve several different configurations for general this expansion will (4) and for Y(jB). radiative transitions occur to one of the nl values. In terms of the eigenfunctions of the states built approximation. If we try to describe the will atom in terms of appear as expansions in a centralfield on that central field. . in many spectra.
it is only the where (L m S) f first the radial factor of the eigenftoaction which is altered. The result is generally in agreement with experimental results. . 59. If we write R(np J) for the factor in 2 Pj in the first approximation. For 2P the value of L*S is S while for ponents connecting different P it is I The nondiagonal matrix com members of the 2 P series are then r r) o R(np) R(n p)dr. J and M.6 : s components of the spinorbit interaction connecting different terms of the 2 P series. 7 2 S is between 35 and 45 although the ratio seems to have the normal value for the first member. Because of this perturbation. The spinorbit interaction. The different experi as mentioned in mental results are not in complete accord. 680 (1929).gt. Zeite. As the perturbation is diagonal in I. This was explained by Fermi* as an effect of the matrix P&. This result involves the assumption that the radial factor of the wave function the 2 is the same for the two levels of P term. 6 2P^6 2 $. order eigenfunctions are altered and by different amounts for the two levels of 2 P. fur Phys.gt. we have R f 30 Jo fW n n 2 2 2 calculate the strengths of the two lines 2 Pf~ 5 and Pj&.876 CO^HGUEATIOX INTERACTION 4 15 perturbations of the energy levels. is the appropriate value of L*S. 9 5 3 but in the case of the higher members of the principal of Cs the ratio is found to be larger than two. 2 5 from 2 45 S is 2 . and (np) for the radial factor before the spinorbit interaction is considered. * The ratio of the line strengths FEEMI. With this one could calculate the relative transition probabilities for the different configuration transitions to compare with measurements of these transition probabilities. $ the calculations go through as before that we must use these altered except When we radial functions in calculating the integral irR(np) R(n $)dr whose square enters as a factor in the strength of the line. given by (r)L*S. Spinorbit perturbation of doublet intensities* We have seen in 2 9 that one of the simplest conclusions from the sum P&.gt. but agree in indicating that the 2 ratio for the second member of the principal series. 5. 2 rules for line strengths is that the two components of the doublet 2 $ should have strengths in the ratio 2: 1.
This is what makes possible the departure of the Hne strength ratio from the [J 9 value given by the simpler considerations of 2 The numerical values of the integrals involved have been estimated . by Fermi. multiplied 2 2 3 by the square of the r ratio of the two radial integrals. 377 $ and Pj.5 15 for 2 SPINORBIT PEETTTBBATION OF DOUBLET INTENSITIES 2 Pf&.gt. Introduction of a small component of the radial func 2 tion of the lowest P term into their radial functions produces a relatively the fact that the first series large effect because of member combines so much more strongly with the normal 2 S level. 5 5 series members. .$ is thus 2 rom the angle and spin factors. For the first member of the principal series the smal change does not produce an observable effect because its strength is so great relative * 9 to the higher members of the series (cf Tables 7 and 8 ) that the introduction into it of small components of the radial functions of the higher members . who finds that in the case of Cs the values are probably large enough to account for the observed intensity ratio. For the Mgher situation is reversed. the produces no appreciable effect. The quantities which measure the change in the radial function are small compared with the energy differences En En so the actual change in the radial functions is quite small. however. : R(np ) R(n*a) dr] [j r E(np ) B(n s) dr].
In such a scheme Likewise the magnetic perturbation energy is given by (1) without Therefore the magnetic energy is simply o times a constant of the motion. so the effect on an level characterized energy by the quantum number L would be to split it into 2L + 1 equallyspaced levels by addition of the quantity olML to the unperturbed value. in which case the radiation is circularly when viewed along the zaxis. M which Alf^O. The whole theory of the effect of a magnetic an atom is therefore given by a study of this 5 field per turbation term. The ordinary dipole radiation involves transitions between states for the MLfi* momenta. aH the energy levels are split by the magnetic field in the same way. effect for the general case. the observed splitting of all lines is the same on this view of the matter. leads to 10 5 o is valid for each of the elec trons in the atom. Since. The transitions for which +l propagation. the term The argument of 105 which N (1) with o = eJfY2/Ltc as in 10 on the energy levels of 6.L ^ L ^ L. Sz term. which is devoted to the In 10 5 Zeeman 1. in electric vector in the which case the radiation is linearly polarized with the plane determined by the z~axis and the direction of AJ/X =1. according to the foregoing. 9 The normal Zeeman effect. This serves as a simple pattern for the present chapter. The transitions for which AJ/ = will all have the same frequency and will coincide with the unperturbed line. and polarized ML^M L * Tim is actually the case for singlet levels (5=0) in KraseHSaunders coupling. Prior to the intro history duction of the electronspin hypothesis in 1925 had atom was given by the sum of the L vectors for the individual electrons. where . physicists attempted to give a formal description of atomic spectra in terms of a purely orbital scheme of electronic states.CHAPTER XVI THE ZEE1IAN EFFECT we have treated the Zeeman effect for oneelectron spectra. is Ls the sum of the ^components of the orbital angular a constant of the motion which is quantized to integer values . so that a magnetic field of strength jg? in the direction of the saxis contributes to the Hamiltonian. so that the entire momentum of the angular Before developing the theory from this standpoint it will be instructive to consider a little of the of the Zeeman effect. .
that bigher frequency by the :&.gt. The conventional way of exhibiting this result. For longitudinal observation. components which are circularly polarized in the directions indicated if one in a imagines the magnetic field to be up from the paper.gt. for the low frequency component polarized. I 16 With longitudinal observation one sees simply the two . for senJcrecJit) to the field. the Zeeman effect Thus. By comparison of the observed behaviour of some of the zinc and cadmium lines with the Lorentz theory. .n see". Almost a year effect on other lines showed that the elapsed before further studies of the new . Soon after. Observation direction transverse to the field shows all three components.[is THE FORMAL ZEEMAN EFFECT emission will all 379 have the same frequency which will be in fact shifted 1 toward lower frequency from the unperturbed line by an amount O/ZTT 1 The transitions for which L*M L 1 will be shifted toward O/STTC same amount. spectral lines was discovered by Zeeman in 1896. the radiatioD is ciris polarized in the 3ularly polarized: for the high frequency component it is. and This agreement between theory and experiment for the lines of zinc cadmium gave a great impetus to the infant electron theory. is shown in Fig. the others showing linear polarization perpendicular (a. the undisplaced one showing linear polarization parallel (77) to the field. means necessary.r cm". The same result follows from a consideration of the action of a magnetic field on a vibrating electron moving according to classical mechanics. in the very beginning of modern of light is connected with provided very strong evidence that the emission the motions of electrons in the atoms. The normal Zeeman field triplet. a simple electron theory of the effect predicting was given by Lorentz. it was found that the displace ment corresponded to negatively charged particles having the same value beams. rfr*t Q I Q 1 . of e}p. left Longitudinal Transverse A 777* +1 fir \ gr Fig. as had been found for electrons by deflection of cathode ray atomic theory. which we shall adopt. direction of the positive current which in a solenoid would produce the it is oppositely applied magnetic field. I 16 . &. Although we have described the the normal The influence of a magnetic triplet on this is by no theory of the normal triplet in terms of quantum mechanics. M observation in the direction of the magnetic field.
find the weakfield perturbation of a RussellSaunders level charac M (1 16 1) terized by SLJ. This characterization remains in use even applicable. that the ratio of magnetic moment to angular momentum is Nevertheless the twice as great for spin angular momentum as for orbital angular momentum. so it will be convenient to begin the study with this case. is simply a special case in which the 9 effects of anomalous effect remained a great puzzle until the electronspin hypothesis was introduced and that was a quarter of a centuiT later. If this were not the case introduction of electron spin would make no alter be written for 2. we must calculate that part of the matrix of To H can be written as JZ ^SZ and since Ss commutes with JS9 this part of the matrix will be diagonal with to if. Since . so that it was something of a happy accident that the first lines studied were those to which the simple Lorentz theory was With characteristic love of the simple. Before leaving this brief review of the historical setting it may be remarked that the essential feature of the spin theory is the occurrence of (LZ + ZS^ in (1) rather than (Lz f Ss ). so it is also convenient at first to consider the case of weak fields. As we have already seen in 105 special effects arise . magnetic strong enough to produce energy changes comparable with the separation of the levels of a term. meaning by this fields whose effects are field is If the small compared with the unperturbed intervals the fields commonly used are weak in this sense. which LS +2SS given in 103 .anomalous. The weakfield case: RusseHSaonders terms. for Jz would simply Lz everywhere with no change in the observable results. In terms of the complete theory the socalled normal effect electron spin are absent. physicists fell into the habit of referring to the triplet pattern as normal*. That is. The diagonal element of Jz for the state SLJM is MH. Most of the work on the Zeeman effect applies to spectra in which RusseliSaunders coupling holds quite accurately. The name PaschenBack effect is given to the special features of the Zeeman effect which arise when the field is not weak. the respect diagonal element of Ss for this state is obtained as a special case of the results refers to this level. all other forms of the effect were caEed ".380 THE ZEE3IA3T EFFECT I 16 normal Lorentz triplet Is by no means the general behaviour of a spectral line under the influence of the field. Generally speaking the patterns are much more complicated. ation in the theory of the normal triplet as just sketched. Perhaps the continued use of the adjective anomalous is appropriate in view of the long time during which the general Zeeman effect resisted the attempts of physicists to understand it. If we identify Jx with S and J2 with L 9 the diagonal matrix . today although we are now In possession of a complete theory which gives a rational account of all the observed effects.
gt. and of the initial and final levels. (1) would give the splitting which corresponds to normal Lorentz triplet. and since the gr s are rational actions.5E. Zelts. More generally.lt. the Zeeman pattern depends only on the S. Runge s rulef says that the displacements om by the formulas (1) and (2) was worked out by Lande. In other words. For J = the formula for g gives g. Boy. This formula expresses implicitly ys that all the lines in a spectral series have exactly the same Zeeman tttern. iglet levels. These results which we have so easily obtained are in good accord with the apirical data. and g is usually Qown as the Lande factor. but the scale of the splitting differs from the simple theory the factor g. 232 (1907). Soc. as before. The table shibits some interesting properties. furnishes a good account of the subject as it stood just efore the electron spin and quantum mechanics gave the theoretical basis the experimental material. so the Lditional term vanishes. which. Bays. : the diagonal element of the perturbation energy the value (y 8LJM\H*\ySLJM) = oKgM . but &.r * PBESTOX* Trans. Lande s formulation was based on the modem srperimental measurements by Back. Dublin 7 S 7 (1899). The winning of the result (2) as a generalization from the apirical data was not so easy and represents a great amount of study by Preston s role* which &.gt. In Table I 16 are given the g values for the terms of interest. L. These states are 2Jf I in imber. . f Era&.ectroscopists. (I) e g were equal to unity. The empirical fact that the Zeeman effect of RussellSaunders terms is atom in question. Since the displacement in a line is actually the difference of the dis[acements of the initial and final states. the theory of the normal Lorentz [plet applies to the Zeeman effect of lines which are combinations of e matrix . This is due to the fact that the perturbation energy (1) is indepen*nt of y which stands for all quantum numbers other than those explicitly ritten. provided RussellSaunders coupling obtains 3 r the of the Zeeman components the unperturbed line are rational multiples of the Lorentz splitting 27rc. it follows that this rule is contained in our results. This work is admirably summarized the book by Back and Lande. see that the energies of the perturbed states are distributed sym3trically around that of the unperturbed level. 8. The factor g differs from unity by a term which arises from r We component of Sz For singlet levels S = and L = J.THE WEAKFEBIiD CASE: EUSSELLSATJ^BBRS TERMS 381 3 3 i merit of Sg is given by a combination of 10 2a and 9 I Altogether we find . Zeemaneffekt und Mutiiplettstruktur der [ven i pektrallinien.
ia which L and 5 have to be parallel vectors. For L = 8 the g factor singlets give equals f for all values of J. EFFECT 2 16 / = implies 31 = 0.J=L + S. 7 {? 1 and 8 G show negative g values.382 THE ZEEMA2S". . which means that the . and 5 are L+2S L+S . As akeady remarked. The simplest cases sax&. the normal separation.L. positive charge 5 if the electron were a I 15. In the vectorcoupling theory one regarded 5 and L simply as two classical angular momenta whose sum is J. For J = L + S we find S. as it would be and the behaviour normal. and J.gt. sense of the effect is turned around. A somewhat surprising feature is the fact that certain terms the splitting is of course zero since such as 4D 5 J\ and 6 (? have g = Q and so are not split by the magnetic field others such as B Fi .in which L antiparallel. Land gfaclorsfor Ru&dlSaund&rt terms.
2 .I tu. . 2 22 GW579U (0)t:2)3S by reducing the values of the factor in brackets to a common de characterized nominator.components at {f and f. Using a prime to refer to the initial final Ievel 3 and a double prime to refer to the we have tO)l_ 2 12 where AJf = M* rule M . The value for J = L I ". but r is . ^ /5 5 ? 16 Fig. Normal effect. S* P t S 1 L2S+1 * ~_ l W4 ~ J+i~ 3^8+ 1 Let us now consider the pattern to be /*2 I r i ! expected in the transition between two levels. The relative The different Zeeman components are by no means of equal intensity. Thus one may readily calculate that the values of the bracket factor for 2 P to 2D are (1)35 3 (t)IFf3 IS (4)8(12)1624 15 m3) 15 17/321 15 which means that there are TT components at ~^and ff of o/2?rc from the undisplaced line and o. By the selection / AJf for the components show 213 = I ing parallel polarization. while Alf for those showing perpendicular polar The pattern is readily seen to be symmetrical about a& and is conveniently ization. common Zeeman patterns for several multiplets. Following Back and Lande the numerical values of the numerator {2)4 3 which correspond to parallel polarization are put in parenthesis.i ioes not correspond to the expectation based on this simple view.$ s however. the is independent of which is the pattern initial and which the final level.THE WEAKFIELD CASE: RUSSELLSAUNDERS TERMS which Is 383 just the ratio to be expected from the fact that the spin angular momentum counts double in magnetic . In this notation. as we strengths of the components of each multiplet are indicated by the lengths of the bars (divided by the indicated factor in the case of the weaker satellites).
An energy level of a free atom is always rigorously characterized bv a number J quantum of resultant angular * momentum. Zeits. Weak fields.d6 4s 4Df in Mn as studied by Back. 1 o . In the preceding section we have considered the Mghly important case of the Zeeman effect for RiisselSaunders terms.* Table 2 16 has a row for each state of the 4P level and a column for each state that the pattern is symmetrical around the position The upper figure in each cell is the theoretical value of the displacement. for some common transitions. j 3. Experimentally both the 916 Zeeman pattern and the dis tribution of intensity provide important aids to the recognition of the of the energy levels involved in a spectral line. Fig. 2 indicates clearly the diversity of the patterns contains such diagrams. getteral case. For the Zeeman pattern it similar to those by of tie 4D^ of the is convenient to make a doubleentry table used for multiplets. Let us now consider the nature of the effect for an energy level of any type in the weakfield case. It is in zero field. 15. 140 ! 65  15 j 435 4348 1 1512 . 206 (1923). . ^ the Lorentz splitting. 1* j 31 ] 21. The states resulting from the BACK. for Phys. the unit being of level. the lower is that observed by Back.gt. The relative in tensities are readily indicated graphically by drawing ordinates at the 16 positions of the lines whose lengths are proportional to the intensity. The method will be illustrated akeady of the pattern for d & 4p 4 P&. TABUS 2 W .384 stall see in EFFECT 4 1S .
The special result of the preceding section is obtained if s*ords all (2) a = y SL. and L in this scheme. S. The vector of the type considered in 93 and hence S Therefore the magnetic alteration of the energy level is. ySL 2 \(y SL J a J)J 2 which multiplies g(SL J) on the right Eg(a/)E a since the coefficient a hand side of the summed equation is equal to unity because the transforma tion is unitary. we obtain (4) g(SLJ). ) in terms of the LScoupling scheme. 0=l + (aJ:S:acJ). but now Ms factor is given by the general equation (2).16 WEAK weak is FIELDS: GENERAL CASE S 385 pplication of a S resultant spin field will be characterized by J and M. JM we lave ySL Eence the matrix component that we need T(a JJf)= SY(ySL JM)(ySL Jla J). Actually of course in an atom there are an infinite number of levels associated with each value of J that occurs at all. The result contained in (4) is known as the gsum rule. The amount of the splitting is governed by a Lande g factor as in BussellSatuxders levels.) In other energy levels are split into 2 J f 1 equally spaced levels sym metrically distributed around the unperturbed level. so (4) merely becomes an uninteresting oc = co cs if applied to all the levels of the atom. Its importance 25 . (1) (aLJM\H*\KJM) = clSgM LS in 2 16 1 5 where we have. however. The ^(Jg+Si) *? combination occurring after the summation sign is. The whole theory of the weak leld effect for any term is If we express the state *F(oc thus reduced to an evaluation of (a J:$:aJ). whereas the quantity on the left is ^(a J) 31 ft . is T(a JM) (Jz + S2 ) T(a JM) ySL Since JZ +SS = LZ +2SS ( ) is diagonal with regard to y. If we regard a as a variable label running over all the levels which have a particular J value. hence we have the result (ae/) = S g(SLJ)\(ySLJ\xJ)\^ (3) which expresses the g factor Lande for an arbitrary level in terms of the ordinary factors of the RussellSaunders scheme and the transformation coefficients (y SL J\cnJ). simply g(SL J) MK. and sum (3) over oc. in general. in place of 2 16 2.
which in the LS levels of are *S l9 3 Saunders g values are 3 f the J= 1 Pj and *D^. For P 2 ). B2 which have a g sum of ^. 9 and 1*137. In this case (4) tells us. relative strengths of the lines are therefore given by application of formulas 9s ! 1 as noted in 7 4 ? where the necessity arose of summing over all these separate transitions to find the total strengths of the lines of an The unperturbed atom. the sum of the g values for all the levels of a given J in the configuration is the same as in RusseilSaunders coupling. with sum equal to 1 . This revealed quite generally . ". y Si are restricted to those values associated with the electron configuration as x. 1229. The corresponding Bussellsum of 5. observation was made of the longi tudinal effect (radiation along &f) and of the transverse effect (radiation emitted In any direction perpendicular to 3ff). The corresponding states in the LS scheme are 3 P2 JD2 with experiment. if we let a run only over levels of a given configuration. P 1J 3 1. f with a sumrule check although the individual values are 5022 providing a far the Lande values For J = there are three states with experimental . The a field will arising from a given spectral line when the source is in be said to form a Zeeman pattern. as we have J list seen. The coupling is as we have one with J J= 5 far two with from the 3 RusseilSaunders f5 13 ) in which the levels would be labelled P0s Is The level of J = 2 Is 3 P2 regardless of coupling so we do not need the ysum S to tell us that the g value for the state of J = 2 should be 7( the I and Paschen found 1503 which is good agreement. that although the individual ^r are by a breakdown of RusseilSaunders coupling. 4.2 g 1301. The J= i 5 configuration 2p 3* gives rise to one level with = 2. Thus in where the states Y(x J) may be assigned electron configurations. This Is exemplified by the measurements of Paschen on the Zeeman effect in neon.g\ 3 Pi = } s a good agreement. In the early work on the Zeeman effect.in good agreement Intensities in the Zeeman pattern: weak fields..388 lies in THE the fact EFFECT 3 16 state in the summation over y which expresses an actual atomic of states of the RusseHSaunders scheme Is finite to a good approximation. whereas g\ P 1) . This two states with I /=! Paschen found ^ = 1034 and i =1464 so Sg =2498. and 0699. Here J = 1 is represented by four levels. 3 3667. are connected with the different changes in M . The experimental values for are 1084. 1340. be applied to Paschen s values for the levels Similarly the g in the 2j/5 3j? configuration. The different com ponents. 0999.
gt. 31. They are id J&. Van Geel used the ieoretical values of the intensities of the perpendicular components. Zeits. 826 (1925). HONL. 90 (1925). 3 16 . It should be explicitly emphasized that these formulas are valid in any is. For the Zeeman pattern of any line in which there is no change in /. 885 (1925).gt. Zeits. fur Phys. that . it is evident that the pattern of rengths given by these formulas is symmetrical about the position of the =^ M&. 31. are independent of the nature of the quantum umbers symbolized by a and a The positions of the components of the eeman pattern depend.5 INTENSITIES IN THE ZEEMAN PATTERN : WEAK FIELDS 387 phenomenon of the circular polarization in longitudinal observation of e lines which appear polarized perpendicular to in transverse observaand also the absence in longitudinal observation of the lines which are m. fur Pfcys. Zeits.~/f 1 transitions rengths J 1 transitions in transverse observation. and Honl. Since transverse observa gives the complete pattern and is more convenient experimentally. taken by Back. eeman patterns * CtosTEiN and BUBGER. 340 (1925). e $ darized parallel to &.s 8 Pf (A4852) and a 8 S^z 8 P^ (A4752) in MnL he theoretical pattern for A4852 is given in Fig. Zeita. f KEOOTG and GOUDSMTT. that the arrangement which is always used in modern work.M 1. M+ aperturbed line.n ^ in transverse observation.gt. write two more sets of formulas giving the relative Similarly of the components of the Zeeman pattern for J". fur Pfays. t VAX GEEL. Xaturwiss. 241 (1924). 252 .f As an example of the experimental test of these formulas we give some Leasurements by van GeelJ on a plate. 13. 29. )upling scheme. 33.gt. which gave good for a 8 $&. on the other quantum numbers. as we have seen. the relative strengths do not. first obtained empirically by Ornstein and Burger* id later derived in terms of the correspondence principle by Kroiiig and lit These formulas were oudsmit. we may aJ^ (*)}  ( hese also give patterns that are symmetrical around the undisturbed line.gt. fiir Phys. the 4 rengths of the components in transverse observation (9 = ?r/2 in 7 4) are oportional to \(*JM\P\aSJM)\*=\(*J\Pi* J)\*M* (rr}\ ) ( a J(a/JtfPaVJlfTl)j 1 has equal and opposite displacement nee the component om the original line to that of M&.
independently. the same calibration was applicable to this. have seen in vn We Chapter that the inclusion of the electrostatic interaction of the electrons necessitates . 5. (1) Suppose we set of N start. The relative intensities of IT.and orcomponents. with a set of states based on a complete individual sets of quantum numbers. As the line A4752 was on the same plate. all of which agree well with theory. whereas the theoretical values are 40:36:28:16. 3 s a a z$ 38 2 Fig. . The theory has already been presented for one electron spectra in Id 5 . . The paper of van Geel includes more examples of this sort. as a means of finding the blackening curve of the plate. were: 7rcomponents orcomponents Observed Theorv 57:46:27 54:45:25 70:56:37:22:12:? 73:52:35:21:10:3 several These are evidently excellent agreements. 15&.388 THE ZEEMAN EFFECT 4 16 together with the observed blackening of the plate for these lines. the departure from the above theory of weakfield Zeeman effect which occurs with a magnetic field strong enough to produce splitting comparable with the interval between levels of a term is called the PaschenBack effect.gt. 8 &. The PaschenBack As already mentioned. Ps Zeeman pattern. the is 1 16 1 value of the diagonal matrix element being oB(Jffz +21f ff ). Now we may consider the effect in general. The magnetic perturbation scheme of states in which H* of ML and M evidently diagonal in any B appear as quantum numbers. 3 . Using this blackening curve he found as the experimental values of the relative intensities of the parallel components 41 36: 27 5 . as in Chapter vi.gt. Theoretical relative intensities in the 8 5r effect.
L is a quantum number in both schemes. For values of Jf such that HM is large compared to the energy of spinorbit interaction. In view of M commutes with 2 and S2 and that we can have a scheme the fact that H of states in which SLNS L are quantum numbers. we see that the groups of states having different values of If may be treated independently. This is the weakfield case of the preceding sections. M tendency of the magnetic field to orbital or spin angular momenta break down the coupling of the individual and SL* of the electrons into a resultant L In the RussellSaunders case therefore the PaschenBack effect results from a competition between the spinorbit interaction which works for the scheme and the magnetic field which works for the L scheme. than However. On the other ^ H components the eigenstates of energy will be nearly those in which J and 31 are quantum numbers. . Predominance of the magneticfield energy therefore draws the eigen states toward those in which J/s and L are quantum numbers. this is of purely theoretical interest because the fields necessary are much greater any attainable ones. For values of matrix components are small compared to the spinorbit interaction matrix hand HM is not diagonal in a scheme in which J and 31 are quantum numbers. They do not commute with the orbital angular momentum. transformation from this scheme to an obtain states in \ M M M such that the theory of the RussellSaunders case.gt. JM MM M M M N MM MN nearly diagonal * This is true in so far as we treat the magnetic perturbation as of the form of (1). Since S = s 4. For a M M variation of &t? from zero to such strong values there will be a continuous in the character of the eigenstates from one of these limiting types change to the other. Kigorousiy however there are other terms proportional to the square of the vector potential as mentioned in lO5 ^.16 &. For the the energy values either in the S L scheme or in the JM former we need to have the nondiagonal matrix components of the spinorbit interaction and for the latter we need the nondiagonal matrix com L scheme is more S ponents of the magnetic energy. In group we may set up the secular equation for dealing with a particular scheme. THE PASCHE3TBACK EFFECT 389 $coupEng scheme in order to which this part of the Hamiltonian is in diagonal form. Hence we see the place of the PaschenBack effect in the diagonal form. we see that there is no M . In I 7 we saw that s and L can be retained as quantum numbers in an LS~ 3oupling scheme it is only when the spinorbit interaction is included that it is necessary to pass to a scheme in which J and 31 are quantum numbers in order to obtain a scheme of states in which the complete Hamiltonian is in a. The matrix in the the matrix in the J 31 scheme at the outset for strong fields. the magnetic term will dominate and the energy eigenstates will be nearly those in which s and L are quantum numbers. and so at fields strong enough to make them important L and the individual Ts of the electrons are no longer quantum numbers.
* Soxnmerfeldt showed the relation of an old classical coupling theory of Ybigt to the effect* The quantummechanical treatment was first given by and Jordan and detailed cases were discussed by Darwin. SOMMEBEEID. The best experimental illustrations of the PaschenBack effect are in connection with hvperfine structure (5 18 ) where attainable fields can a complete transition from one scheme of states to the other.gt.gt. 89 257 (1922). fur Phyg. 273 (1922).390 for EFFECT weak fields. lengthy calculations vhich have very little applicability to spectroscopy since the fields needed to produce large PaschenBack effect are seldom obtainable. SCM:. ibid. TTne first reference includes a number of other cases. The second reference provides accurate Intensity measurements on the forbidden lines for various field strengths.i :s 9 6. G. 765 (1925). Roy. Except for the These matrices may of oneelectron spectra. A115. 1 (1927). which has been already fully treated in 10 5 this procedure will not be carried out in detail. it is evident that they hold with appropriate minor modifications ia the case of any other coupling for the unperturbed atom. VAST GEEL. K. Zeits. Zeits. a simple consequence of tie fact that the states in a strong magnetic field are not by precise J values. At 18. PJiyriea 1 261 (1921). Zeits. ShoTsame Jf Trr:Ls the sum of the magnetic changes in energy of all states of the equal to c$ J/2*J where Sf is the sum of the Lande g factors for the corresponding states witn in a neaJt field. of course.4s4p P multiple! in Zn 1 which has been studied by Paschen and Back and later by van Geel. 263 (1926). TMs is. TMs is known as Pauli* s f/permanmce ruh. The PascheaBack illustrative effect: Ulustrative examples. 5 16 be obtained from tie calculations already given in other chapters so that the secular equations can be written down for any special case and solved by the usual methods. . fur Phys. The PaschenBack effect was important in the prequantum mechanical theories of atomic spectra for the information it gave about the coupling relations. characterized * f J HZKOBSTBEBG. 51. PAUII S ibid. for Phys. C. for definiteness. 155 (1923). 8. 264 (i928).gt. fiir Phyi. HnsENKRBG and JOBDAS. 37. 3 3 example we take the 4*4cZ jD&. for it can lead into very . was studied in this connection by Heisenberg and by Pauli. P completed to all nine lines instead of tie usual six. tie emphasis being on As an the fact that strong magnetic fields bring out lines which violate the ordinary S rale on J so that in the magnetic field the 3 multiplet is D~&. 31. *fcat for all : &. PASCHEK and BACK. DABWBT. 51 (1028). J Although the preceding remarks have. been made for the RussellSaunders case. 16. Zeits. PROBLEM. Proe. BAEWIN.
Using the matrix .6 16 PASCHEXBACK EFFECT: ILLUSTRATIVE EXAMPLES 391 The matrix components of HM in the SLJ3I scheme are obtained from and IG 3 2. The 3D intervals. 3 Applying the perturbation theory to D we find for If = 3 a linear 3 variation with the field of the energy of Df 3 For Jf = 2 there is an inter action between the corresponding states of 3D 3 and 3D 2 and for Jf = 1 there is an interaction between these states of all three levels of 3D.1 below the SD indicating a strong perturbation of it . As drawn the departure for 3D 2 B PQ appears to be linear and too large. components (oK/hc) 9 (!) and the unperturbed level separations and writing TJ for we readily find for the quadratic perturbations: Coefficient of ff in quadratic perturbation of Jf=2 1 The numerical value of TJ is 4674 x 10~ 5J^ where Jf is In gauss. 5 which we with the addition of a smaH mark on the wavelength lines are &.gt. TMs agrees within the accuracy of the data. The broken lines show the splittings as given by the weakfield theory. 5 by 4p 21 D as discussed in I 15 . are only 323 and 494 cm so the quadratic term in the perturbation theory is important here. the heavy lines are drawn through the experi mental points. scale at 3281927. so the quadratic displacements of the a P D 1 components which involve the If = 1 states should be 022 cm whereas i and + 1 components respectively. they find 015 and 040 for the Jf = The TT component involves Jf = for which the shift should be 0*35 and they report 032. 4 16 given in his Fig. reproduce as Fig. Since tion of 3 2 . The interval ratio shows that we are fairly close to RussellSaunders coupling. Van GeeFs measurements on these which is the position of unperturbed 3D2 3 P given from the energy values of the levels. . The 4s 4d 1D is 300 cm. . For the fields used the secondorder perturbation is adequate. . For this field TJ 1*84. They are 9 3 1I = * ( J L is /^w VJ ~~ ^ * where g(SL J) the Lande factor of 2 16 . however. Paschen and Back publish data on the line 3D 2 ^ S P for Jf". = 39340 3 does not split this gives us directly the magnetic perturba gauss. The Zn 1 4s 4p 3 P intervals are 190 and 389 cm 1 so the weakfield theory 1 is adequate for them. That is because the broken lines have been drawn to converge at &.gt.
are the same as we have already used. PaschenBack effect in S D \ S &.000 to be . For example. and for the component involving Jf = compared with a theoretical 0360.* It is easy to see how the intensity changes occur. is When the change is made it is seen that the too great for a satisfactory comparison with theory.gt. &.gt. some of the . 51. Zeits. 3 D 3 1 &. That Is probably because this is a line which is forbidden in weak fields and is weak even at the fields used and so is difficult to measure.. 62 (1928). The theory for this was given by Zwaan. 3282*18 P multiple* in Znl.0185 and cm1 for the theoretical value finds a shift 0297 as 1. The data on line. 328195 Fig. whereas the components involving 31= he 0*268. 9 2 5) where the matrix components. The more interesting part of van Creel s work. given by (1).392 uncertainty of the points THE ZEEMAN EFFECT 6 16 328195 instead of 3231*927.gt. however. for Phys. concerns measure ment of the intensities of the forbidden lines as a function of field strength. The state that grows out of 3 D therefore acquires ^. 4". the state which in zero field becomes ZD\ is represented by a T which is given by the perturbation theory to the first 4 ordering as (cf. P are probably For this 0334 line he is finds the quadratic effect at more accurate since this is a stronger Jf = 30.
tan tan L8 2.gt. in powers of a simply the leading term of development 3 M* he found as well the coefficients of tf for the lines.0 IOQO 5GOO iOOOO 290m 3Q8GQ H Fig. for instance. was worked out in this way by Zwaan. strictly. Dependence of 3 forblddenilne P HI Zn I.gt.16 PASCHEISBACE: EFFECT: rLLUSTRATIVE EXAMPLES 393 iharacteristics of J= 1 and J=3 in addition to the J=2 which it has.he ! 9 . If therefore we calculate the matrix component of electric moment for transition to 3 P.Q ~1 ". The field *DI**PQ as a function of the 16 Geel s Fig.000 ganss. The components of the 3 P for which A J = 3 were found to vary as 3f4 while the two lines and 3D 3 S P 1 for which AJ = 2 varied as Jf 2 for weaker fields.) This JF 2 variation . &. 1) where the log of the agreement is shown in Fig. The magnetic 2 3 to tf? so the quantity j( Pg . . Component: 10 0~&. we find )I\H^DD other two terms vanishing by the selection rule on J. for 3 in gauss D2 5. &. 3 P and 3 3 1V The results for the relative strengths of the lines D 2 = 3*0 x 10~5^f ): as found by Zwaan are (p is &. 5 (van Van # D2 ^ 3 P .Pj^i)l which perturbation term is proportional 2 measures the radiation intensity will vary as Jf of all the ordinarily forbidden components as a function of The .^ *D*^PO t V 3 I relative to Geel measured the sum of the intensities of between 10.000 and 30. (I is effect strength on field in PaphenBa^k line the strength measured with yfo of the strength of the ^V^PO as toait.gt. vhen unperturbed. intensity Seld strength Line 3 D 3 &.gt.gt.
28 y 1079 (1909).) \(*Dt \A)\* 3 \( B) +g&.lt. 212 (1908). whereas the 2 respectively. 11. where gD gp are the g factors for the D 2 and In this 3 P levels respectively. normal we can get. 658 (1925). Zeits. 1 P 1 given by theory. value of the normal spitting. Calling the quasisinglet level A quasitriplet B we have 1GOf. .0 3 given by the p terms and found good agreement with theory. 1 &. From that = 101 for this *P.394 Intensity ratio Is THE plotted log Jf . The data are due to Gmelin. have made good use of this method of treating f ttnresoled Zeeman patterns. 1193 (1910).^ He worked with low resolving reported all the Zeem. a fair agreement for such data. Phys.gt.gt. of the 1 It we may If we a specific )hefoiindtobe472x iOSerar gauss.117 of the Lande values is = 2*17. BCT. of 104 and 110 for ID2 and D way Gmelin^s data leads to observed g values The sum is 214. Phys. in some old data on the Zeeman effect which provide an illustration of a PasehenBaek interaction between Hgl a a triplet term made possible because of the breakdown of KusseilSaujiders coupling. of an unresolved ( it is the relative intensities of the pattern components are easy to calculate that the centre of gravity of intensity t f# x would come at an apparent specific splitting the normal. 9. EFFECT 8 16 The broken line Is that given by the theory. 88. and LOBISG. fur MJB. have since made much better measure a more detailed comparison with the intermediateoonpling theozy than 9 that given tere. by the method of 3 18 a estimate of the departure from RnsselSaunders coupling. and for (65 BdW^P^) he found 495. PML Mag. but van Geel s are of forbidden the only quantitative intensity in this field.. ?&. J BOIJMA. He also studied the departure 10 components from the p 2 law as of the intensity of the i&.gt. The by Pasehen and Back contains a number of other examples of the in the magnetic field. TMs Is a very satisfactory agreement. 8. This rough result is out by intensity measurements by Bouma f who found A5769 and A5790 of equal intensity.ATB.an patterns as triplets.der Phys.lt. 888 (1934). which would indicate 5 ments on Ann. For A5769 (85 6d 3D 2 *Pi) he found of 538. 46. 765 (1929).. The We now to a brief discussion of spmtingofA4916(te^ 5 ^ft?6p which is witMn 1 per cent. and BT. From the departure of the g values 5 g(A)=g?DJ K^U)!* r g(B) = ff ?D 2 ) (U&.*D t ) D \B)\ 2 Z the observed values of g(A) and g(B) together with the Lande values ofg( t) 3(D%) lead to l wMch D which is a rather departure from LS coupling.
Soc. 217 (1909). . Soc. A108. being a property of the levels and not of the transitions. . 451 (1928). A120. 51. SOMMER. More accurate measure nents on this line are desirable for a more definite check. a components and a quadratic effect of components. 327 (1928). associated 4 have already been worked out in 6 9 shanges in The first experimental work on this point is that of McLennan and M . Zeits. If we had pure LS couptug there could be no such effect because the magnetic perturbation has no components connecting different singlet states. 7. The first transition in the normal 2p configuration Zeeman effect observations were taken in the longitudinal direction. Proc. lownward equal to 32 Vorking out the details we find that the centres of gravity of the a and TT 10 a^f 2 1*33 x somponents should show respectively displacements of jad . Boy. This corresponds to a =040. From 2 and Alf = bhe results of 6 4 we see that in this direction the All= &. 501 (1925). This interpretation Gmelin s data disagrees with that given by Back. 395 Zeeman* found a quadratic displaceaent of A5790 which was later studied by Gmelin. The theory of the Zeeman effect for quadrupole lines has been developed ncidentaUy to other work in preceding sections. Roy.f matter to hyperfine structure.16 PASCHESrBAGE: EFFECT: ILLUSTRATIVE EXAMPLES for the firstorder effect. Quadmpole lines.gt. somponents have vanishing intensity. McLEKNAN. As discussed in 5 this is the jS 4 of neutral oxygen. Zeits. D . A106. 10. der Experimentalpliysik 22.gt. Handbuch. J MCLEHKAH and SHBUM. Phys. i&l (1929). D . 138 (1924). it is 3 Me to show a PaschenBack interaction with 9D^ 3 It happens that 1 3 a quadratic effect 1 is only 3*2 cm".f who tries to relate the &. t BACK. in rood agreement with the value 032 derived from the departure of the g*s rom the normal Lande values. so brief comment relating t to the experimental work is all we need here. so the pattern is like that of a dipole * ZEEMAS. 1 1 n D3 ShrumJ on the green auroral line.348 x lO^aJ^ 2 where a is written for ( 3 2 j^)j 2 What Gmeiin 10". for PfcjH. The splitting of the energy evels. In view of the fact hat the qnasisinglet A has a large component of 3 2 in its eigenstate. The details of the picture with different soncerning angular intensity and polarization. below X hence its states will show aatrix So much D D . is given by ihe discussion of other sections of the chapter. Proc. .". It thus appears that the existing data on A5790 is in accord with the theory observed was no 141 x 10~ 10 ^ shift for the TT 2 for the ind exemplifies a PaschenBack displacement of a quasisinglet line arising rom departure from BussellSaunders coupling.
MniA&. 724 (1931). Phys. fur 38. 74. as well as the TT components at normal separation for the theory. For sodium the D fields giving a measurable splitting showed a complete PaschenBaek effect in this term.396 line. 825 (1932). A31 of equal intensity. This was done in the oblique direction at 45 degrees. in agreement with of the 2D* 2 S doublets in Segre and Bakkert studied the Zeeman effect sodium and potassium.gt. Phys. Rev. 72.. In analogy with the discussion of the preceding section the perturbed matrix components can be expressed in terms of the unperturbed matrices by means of the trans formation matrix from the unperturbed to the perturbed eigenfunctions. This work provides a detailed verification of the 2 interval is so small that all theory in several respects. we have to calculate the matrix components of the quadrupole moment with respect to the perturbed eigenfunctions.} that the two lines can be studied separately. Such calculations hare been made explicitly by Milianczuk J and the results found to * well with the experimental results of Segre FBEEICHS acd CAMPBELL. For potassium the doublet interval is great enough (232 cm.czrK. and Bakker. .components separation. corresponding to AJ/= r 1. The transverse effect for this line was studied at twice the normal by Frerichs and Campbell* who found the o. 151. all 2. Zeits. fiir Pfcys. as well as transversely. J Zeits. and the theoretical expecta 1 verified. 1460 (1930. polarization of the components For higher fields the PaschenBack effect begins to alter the intensities The theory is exactly like that for to new and tions as to relative intensity and permits dipole Hues components appear. THE ZEE3IA3* EFFECT 7 16 The measured displacements gave gr= 1 from which the singlet cha racter of the line was inferred. f SEGPJE and BAKKER.
f EPSTEIN. Epstein effect in terms of quantized orbits and the observed line patterns exactly. 50. levels by the field. Generally the splitting of a spectral line is much smaller than in hydrogen although there are special cases in other spectra where the effectis comparable in magnitude with that of hydrogen. independently. 69. 3. ra. New . It soon turned out that hydrogen occupies a somewhat exceptional position. so that it was an important additional success of that theory when. Berliner Akad. the destruction of quantized limit of the Balmer series toward the red by allowing the effect of shifting the * VOIGT.. J KBAMEKS. 297 (1899). Sitzber..SCHWABZSCHULD. We shall see that this is connected with the accidental degeneracy in hydrogen whereby terms of the same n but different I have the same energy. der Phys. 197 (1901). At very high fields another aspect of the effect becomes im results of the older theory. Danske Vidensk.gt. We shall also see that the cases of large Stark effect in other may combine according to the spectra are those in which two terms which optical selection rules lie close together. 1916. 548. fur Phys. Later KxamersJ carried the predicted theory further by using the correspondence principle to provide estimates and Schwarzschild f calculated the of the relative intensities of the lines in a pattern. Selsk. It turns out that the positions first order effect (that pro concerned is the same as on the quantized orbit But the effects of second and third order differ in quantum mechanics from the experimental work which carries the study up to high fields has shown that the effect is in agreement with the new theory. 3. 169 (1920). He also made attempts to discover an effect on the Dlines of sodium but without success. 4. is was the first application of the mechanics. 287.* Stark s discovery was made on the Balmer series of hydrogen. except for the small relativity fine structure.CHAPTER XVII THE STAEK EFFECT The influence of an external electric field on atomic spectra was discovered by Stark in 1913 and is known as the Stark effect. Ann. p. Ann. 480 (1916&. namely. . The theory of the Stark effect in hydrogen perturbation theory in quantum of the components in hydrogen as far as the portional to field strength) theory. This has portant. Skrifter (8). It came in the same year as the Bohr theory of the hydrogen atom. It was natural to expect such an effect as soon as the Zeeman effect had been discovered and inter preted theoretically in terms of the electron theory. Voigt gave attention to the electric perturbation of atoms as early as 1899 and came to the conclusion that the effects would be very small. der Phys. and Zeits.
those with 17 = con stant to z = f x.lt. slioini. al energy levels are allowed. Hydrogen. . Owing to the degeneracy of the unperturbed states of hydrogen it is the particular choice of unperturbed eigenfunotions with necessary to to which ecfz is a diagonal matrix with regard to the sets of initially degenerate states. 80. 1. The paraboloids of both families have their foci at the origin. But the spectrum. We consider first the application of the ordinary perturbation theory to hydrogen to find the effect of weak fields on the energy levels. in the negative zdiiection so the Suppose the electric field of strength electron is on by SL force in the positive zdirection. as Schrodinger and Epstein* have by solving the hydrogenatom problem parabolic coordinates. Eev. 28. those with f= constant extend to z= oc. r values of (1) x / Because of the fact that the potential energy tends to x for large positive z. 695 (1926). For these coordinates we have The and and the Sclnodinger equation for the perturbed atom becomes TMs permits a separation of variables $=F()G( to the equations for F and 0: (4) * SCHBODKGER.f in the field of the nucleus is then U=ez. der Phys. We write by separation of variables in surfaces so defined are paraboloids of revolution for and q planes for 9. TMs is accomplished. Piys. Its potential energy &. EESTEE?. Ann. 457 (1926).398 THE STAKE: EFFECT l 17 the continuous spectrum to encroach on the part of the frequency scale which is to the line spectrum in the absence of a field. has a quasi discrete structure which be investigated by treating ~~e$z as a per turbation in the usual way.
9 p l9 and /22 each as a power series in f and then solving in succession the equations obtained by equating s coefficient of each power of f to zero.gt. may be calculated from known properties of Laguerre polynomials and to be diagonal in k und and m. &. j The formulas (11) and (12) for the coefficients of ^. The solutions of these ey nations are tiere ugj n = ki ( td and &2 being positive integers or zero. r that states for which 1^ the electron to be at z 2 &. Roy. 1 (1929).* mpared We shaE not give the details of the calculation of the second. The diagonal elements have the value k2 ) a.7 HYDROGEN 399 discussion of these equations for the case = In the usual way shows that can be solved in terms of Laguerre polynomials. due to an we need the matrix of 2 with regard to the states of the same n. Soc. ae final result for 7 the normalized wave function of a state characterized the quantum numbers n km where k is written for k is For a ais 3ctric field firstorder calculation of the perturbation of the atom. The energy levels are. but by writing 1?\ G. and SCTT. A119.and &* in the Starkeffect displacements in the usual seconde z which are nondiagonal in re not obtained by using the elements of d thirdorder perturbation theory (this would involve a very inconvenient summation over in the levels of the discrete and continuous spectrum). Erom are those which give a greater probability this result it follows at once that the storder alteration of the energy of the state n km is f&fojyekfa.and thirdder effectsf but shall pass now to a comparison of the theory with experiThe calculation including the fine structure was carried out independently by RQJANSKY.+ and * ys. The values of in terms of k or fc 2 are given by (6) A^".gt. 33. 0. As the Stark displacement becomes comparable with the fine Ticture a nonlinear effect sets in. Rev. (9) the states in which the electron is more likely to be in the z region e lowered in energy. which for larger fields goes asymptotically into that given in 3 text.at is. W i .4 and \L f !).gt.(k I (8) &.AFP.gt. (nkm\z\nkm)=^^n&.. the me as are obtained by solving in spherical coordinates or /? 2 2 5 ). 313 (1928). i linear effect for very the hydrogen fine structure ( 45 ). . It turns out that there weak fields owing to the degeneracy of the levels 2Zjr. This calculation neglects the relativityspin fine nicture so is applicable only for fields producing perturbations large with this fine structure. Proc. of course.
I give radiation Also for transverse observation the transitions \m = like the Zeeman effect.lt. Ann. (9) becomes v^n I i t2 ) = 00642 n . Consideration of the range of quantum numbers shows that the pattern will be symmetric around the position of the unperturbed line. The original absolute measurements of Stark gave an experi mental value of 0068 but recent precision measurements by Sjogren and by Kassner^ agree within 1 per cent. filr Phys. In Fig. the unit of abscissa being the basic splitting 1 00642&.and the ordinates being proportional to the relative intensities in the pattern for any one line. The crossmarks indicate measured relative SJOGBEN. From 54 we know that the AOT = show parallel polariza tion in transverse observation and will be absent in longitudinal observation. Here Hie patterns are entirely due to the splitting of the initial levels since the final Is level is unaffectec! by an electric field. Theoretically each of these gives circularly polarized but in the source there is an incoherent superposition of the two contributions giving no polarization in longitudinal observation. Ana. GORDOX and MESKOWSKI.or thirdorder effects are appreciable. this latter effect is most difficult to control and is probably the principal source of discrepancies between theory and observation on relative intensities. THE STABK EFFECT in kilovolt/em I 17 and write v^n k^ 1*2 ) for the (l\ first order 1 . 19. Xaturwiss. polarized perpendicular to the field. 17. * (foe. the theoretical patterns for the first four lines of the Balmer series are shown. ( 10) where the numerical value of the coefficient is calculated from the theoretical expression. with the theoretical value. (b) differ in intensity because (a) individual transition some components are the sum of several transitions. This is also true for fields where second.400 ment. cit. 991 (1914). So far. Here the line due to a transition (m )&. Zeits. 43. KASRTCB.f cm. der Pbys. As always. These predictions concerning polarization have been checked experimentally J so transverse observation is used to get complete patterns. 368 (1929).).k2 } . this is just There is a difference in the longitudinal observation. 77. Xearly all of the experimental data refer to the Baimer lines.(* 1) is at the same frequency as light m}*( ?i). der Phys. I 17 made by Schrodinger These agree when a correction in Epstein s work . has succeeded in obtaining the Stark effect of the Lyman series. f For fields up to 100 kilo volt cm the quadratic effect is negligible in comparison with the linear transitions will effect. 346 (1933).  STAKK and WENBT. Theoretical calculations of relative intensities were and by Epstein is made. The com { ponents in a pattern probabilities differ. I (1934). ibid. If we measure alteration in cm". f FBEKICHS. the lines due to transitions where m changes show circular polarization. 290 (1932). 81. excitation conditions may put unequal numbers of atoms into various (c) states of the initial level.gt. In the Zeeman effect.
Ann. The theoretical relative strengths of the components of each line are shown by the lengths of the bare. 1914. cs 26 . PhiL Mag. 1170 t WIEBL. der Phys. itensities. Starkeffect patterns for the first four Bakner lines. (1930). WILSAB. Nackr. 45. Rev. 85. field the others (and are stronger bo the high frequency components of the Stark pattern are weaker than when the atoms move in the direction opposite field). Ann. p. Ann. SLACK. with very weak components indicated by half circles. 563 (1927). I . der Phys. 43. the relative intensity of the ifferent lines is disturbed by what appears to be due to differential destrucon of excited atoms by collision from the different states of the initial level. 82. cLer PJiys. that of the Since the high frequency components arise from states * energy in the initial state. 82. The general agreement is good but attempts to make an accurate the theory encounter many difficulties. Ann. the larger values of ifrf are on the forward. Gott. 576 (1927). st of fc has been shown* that when the atoms are moving in the direction of the Hn T 3 2 Q I /4 tO 8 6 i ! Jl 1 32282420 16 t2 8 4 26ID&222638 17 Fig. When the hydrogen atoms re moving rapidly as in canalray sources. 1005 (1914).f WierlJ has * of the atom) are more subject to quenching by collision than those of shown that the intensity dissymmetry is not STARK and KIBSCHBATJM. der Phys. 35. 517 (1914). The cross marks indicate the measured relative intensities (principally from Foster and Chalk) of certain components of the same polarization. Phys. 3D. f BOHK. 394 (1915). exposed/ 3f higher side lower energy.17 HYDROGEN 401 . the experimental result indicates that these states (for which. LusfELAKD.
Soc. StABK and WKBL. Phys. which can produce a Stark effect. but this can be made smaller than the electrogives & t dynamic Stark irrmc effect. This has been studied up to fields of 10 s volt/em. The experiment is extremely difficult and the pictures obtained are quite unsharp. 58. 4.TO. 55. 38. Jour. when The intensity measurements by Foster and Chalks Mark and Wieri. Roy. V&s YLSCK. 662 (1926). Similarly the theory for the thirdorder effect has been worked out by Doi who finds for it the energy change n]. Zeifcs. and others* do not agree in detail with the theory. Tokyo 9. J&p. Ann. The ratio of the basic is (3. (12) MO AeL cil. 49. 526 (1029). cier Pfeys. 1 (1928). WKNTZEL. The theoretical energy change in the quadratic effect has been to be This differs from the quadratic effect in the classical theory by the ap pearance of the additive f 19 in the brackets and by the fact that the m values are all one unit lower than in the older theory. Zfelts. of the Zeeman effect t* constant. 12. Sci Pap. (1926). ISBGCDA and HITAMA. 193 (1915). Kiun. fir Phys. Piiys. Rev. * FOOTIEB and CHALK. Prw. STAEK. 108 (1929). A12S. f WXEN. 527 (1926). 1009 (1920). 1. fur Pays. Sci. The observed effects agree with theory to within the rather low accuracy attained. Proc. der Phys.T. Giiem. 156 (1929). Ann. 48. 38. WAT.402 THE STABK EFFECT I 17 present when the field is perpendicular to the motion of the atoms. 695 (1926). Such speeds were used by Wien. but provisionally we shall regard this as due to the large number of variations in physical conditions in the experimental work. We turn now to a discussion of the experimental results for the quadratic and cubic Stark effect in hydrogen. Res. ibid. Remit only jHished in ISHTOA Mid HIYAMA (Joe. For iO 8 cm/sec the ratio energy change f&fa to the where a is the fine structure but as the strongest lines in the Hy pattern are displaced 15 to 20 times the basic unit we see that at such the electric effect is about 20 times the Zeeman effect. Of course the magnetic field to a Zeeman effect. lust. 842 {1916). nor the canal rays go into a high vacuum. An interesting experiment has been performed by Wient by sending a so that the atom s hydrogen canal ray beam through a magnetic field v is perpendicular to $* From the standpoint of a coordinate velocity system moving with the atom this gives rise to an electric field of amount v x 3f c. J Enwrap Phys. . 13 (1925).a)(i?c) is 14. Nat. 28.}.
6e? in million volt/cm in order that the coefficients be of com order of magnitude. quantummechanical theory The column headed transition gives the quantum numbers kj^m of effect is positive. 54. f GEBitJEE and * KICTI. 82.f a report of this work. Ishida and Hiyama have given a table. Zeits. Zeits. for the strong components the polarization of the component. which &. fur Phys. 289 (1930). 658 (1929). we reproduce as Table I 17 of the coefficients a.lt.) = off .f 403 It convenient to express the shift of a particular component of a Balmer 3 2 1 line in the form (13) ACcm. Coefficients of Stark displacements in (13). fur Phys. 262 . 307 (19M). TABLE I 17 . 56 * EATJSCH vox T^TTBEKBEEG and GEBi^B. RUJSCH vos TuiraESBEMJ. initial and final states for the transition in which the linear that headed label gives the linear effect in terms of the basic splitting. b c Transition Label Old Old care The quadratic effect was discovered by Takamine and first studied von Traubenberg and Gebauer. H f$ and H y There are two columns for b and c corresponding to the and the old quantizedorbit theory predictions.I 17 HYDBOGEN is c&.? measuring parable of H a.lt. 57. By reversion of the series (13) we see that the field from the observed shift strength can be calculated A by the formula *&.* The cubic and by Rausch fully by Kiuti 18 IT and 1577 of Hy in a later paper effect is studied on the components We shaE content ourselves with by Gebauer and Rausch von Traubenberg. and . b s c.
for com We higher parison. 2. to the various components of the patterns. the potential energy of the oo as z tends to large positive values. in the experimental work. This is the case to an accuracy of about 0*1 per cent. 2".404 STABK EFFECT If the theory is correct this formula gives the same value of the field strength on a particular plate when applied.and thirdorder Stark effect on the 18 IT violet component of Hy . Stark effect at the series As already mentioned in the limit. spectrum of allowed values is really . The procedure was to calculate & from the observed effect on H jS and then to compare the observed effect on Hy flow and flSw with the theoretical values as calculated with the values of g determined from H /?. the quadratic plus cubic effect. electron in the applied field tends to This has as a consequence that the preceding section. and the quadratic plus cubic effect as calculated on the old It is clear that the data axe best theory. effect. are given theoretical curves for the amount of the quadratic effect Fig. We may violet have prepared Fig. The points give the observed data and. the theory of the linear effect as already adequately tested in other experiments and subtract its theoretical amount from the observed shift to obtain the observed amounts of the shift due to the order effects. alone. There appears to be a small systematic departure at by the curve the higher field strengths which is perhaps due to the fourthorder The data are evidently not well represented by the old theory. represented representing quadratic plus cubic effect on the quantummechanical theory. The second.. 2 17 in this way from the data on the 1877 component of Hy.
f J7 (aid) and ^Z7 (a/d) respectively. natural to expect that this energy value and the distance d play an the important role in the Stark effect.f 5 where the due to the nucleus is just balanced by that of the external field. Nevertheless we have seen that the spectrum gives sharp situation patterns in Starkeffect experiments. In that theory only those orbits which are conditionally periodic. electric force =d= Ve/&. y = 0. In a general way this might lead us to suspect that the of space developments have a validity only for small (a/d) and. 973 (1928). Phys. of Lz is JL This value of Lz leads to an upper limit of the discrete spectrum classical which in wave numbers is given by ?7 is whereas the value of the extremum of potential energy given by where g is measured in * I0 6 volt/cm in both formulas. there being admissible wave functions for all values of the line energy. so the upper limit of the discrete energy is the maximum value of the energy for which conditionally spectrum periodic orbits exist. This is in fact the case. ROBERTSON and DEWEY.lt. The potential energy z U of 1 17 1 has an extremum at the point x = 0. Rev. and similarly for the cubic term of 1 17 12. Examining It is formulas 1 17 9 and 1 17 1 1 we see that the coefficients of the quantum numbers 8 can be written . They found that total energy is greater than there exist no quantizable orbits whose and quantizable orbits in the neighbourhood of this limit only exist provided that g / ne* \* * In the mechanics the orbits for which L3 = are ruled out because Hence the least admissible value they lead to collisions with the nucleus. At this point the Z7 = s potential energy has the value (1) 2VeV. .2 17 STARK EFFECT AT THE SERIES LIMIT 405 continuous. These two expressions 31. as the region th state has linear dimensions of occupied effectively by an electron in the n th the order n 2 a we may expect the perturbation theory to fail for the n state } when d~n 2 a* The first theoretical discussion of the special features of the problem in this region was given by Robertson and Dewey* from the standpoint of the classical can be quantized quantized orbits. We wish now to examine the more carefully.
At first sight this may seem a surprising result. 66 (1928). at the energy corresponding to the lowest place in the rim. If the particle has enough energy to get to the configuration where the field we are apt to think that it wiU surely do so. A simple mechanical example is that of a ball rolling under gravity inside of a spherical bowl.406 THE STABK EFFECT . Rev. Fiiys. of the bowl. 3 17 From this we see that the discrete spectrum may extend up to higher energy values than the extremum of the potential energy function. 518 (1930). Zcits. 431 (1930). TMs feature of quantum mechanics was first discussed by Oppenheimer t who applied it to 5 a calculation of the probability of ionization of hydrogen in the normal state by the application of a steady field and showed how this mechanism could account for the emission of electrons by cold metals in strong electric fields. 62. So much for the classicalmechanical theory of the problem. 204 (1931). It has become well known through its application by Gurney and Condon * LAXOSQS. 217 are plotted as functions of S In Fig. 2009 17 Fig. Classicaldynamical energy limits for quantized orbits in the hydrogen atom in an electric field.f complicated by the peculiar dynamical interaction of the motion in the f and 7] coordinates. whose total energy exceeds the energy limit where the nonperiodic motions force balances the nuclear attraction begin. 81. The ball may perform oscillations in a vertical plane which does not pass through the broken wall. fir Phyi.lt. 3 . The quatttmnmechaniea! theory has been treated by Lanczos* and is based on a direct discussion of equations 1 17 4 for the case ^0. S5. But is not the case. . one side of which is partly away (as with the Mad Hatter s teacup). that is. j OFFESHEDCXB. 88. but the essential point is the coupling of discrete and continuous energy eigeastates of the same energy value. The problem is somewhat &.
such as the dotted one in by replacing i7 1 () for large f by some other curve. These Then the W^^k^m). Mature 122. We shall call this relation are presented values of equation does not lead to discrete with the phenomenon of the leaky potential barrier. and 7] coordinates for hydrogen of interested only in the quasidiscrete levels. 4 17 . 33.m) the wave function will oscillate l9 Wi(p ki. GAMOW. The effective potential energy functions in the two equations are forms indicated in Eig.?(TJ).lt.kt. parametrieally on j8 2 number of nodes in first . 204 (1928).m). will the figure.m) = W & + jB2 = I * GUBNEY and CONBOK. where the relation Now let us consider the fact that the true U^g) slopes downward for large For a & instead of having a horizontal asymptote as in the dotted curve. and have I\ value of W=Wi(Pi. 439 (1928). so that the new equation has discrete energy levels. &13 and m. has already been taken into account. fur Pkys. W W = TF (& ^ m 2 = )* Tlie for a fixed &.jW STABK EFFECT AT THE SERIES LIMIT by Gamow* 407 ind to the problem of ocparticle disintegration of radioactive dements. m and the quantum number k2 which gives the &. Rey. Effective potential energy functions in the in an electric field. Zeits. associated with values These can be found with considerable accuracy of below the maximum W U^). 127 (1929). Phys. instead we We are 1ZTFig.ki. . The second of them leads to discrete energy levels which depend sdiich are of the . depend parametrically on &. 417 The wave equations cannot be solved exactly but have been treated by the WentzelBrillouinKramers method. 31. say are the values of IF for which levels of the allowed F= energy problem t (lpi.
I iviil be quite similar. for in calculating the electricmoment matrix component the wave function of the lessperturbed state wiH be essentially zero outside of this region. and thus we avoid dealing tinuous spectrum wave functions. We shall want the wave functions is equal to unity. and 1 which measures the penetrability of the barrier between regions I and III.408 nodes in the region I. \ .) In computing tie transition probability from any energy IF to a lower state which shows a much smaller perturbation it is only the part of the wave function in region I which plays an essential role. for the behaviour of the oscillatory part of each value of is essentially out to with divergent integrals and the special technique for normalizing con f= x wave function from a large the same. THE STAUK EFFECT ". TMs change in character to small inside large outside* takes place as inside small outside * * a continuous function of IF but occurs in an extremely small range of energy values near the value W^^k^m). Such a packet . The value of depends both on v 9 which is the classical ". is proportional to I dojX where X= e~~ of the spectral line (i. The halfwidth 3 X frequency of vibration in the  coordinate for the state in question. but owing to the slight difference in the wavelength in region II so of the de waves it will increase quasiexponentially Broglie that the oscillatory portion in region III Trill have a much larger amplitude of the eigenfunetion from relatively than before. k2 m) T & .e. 5 If at I = we are sure that the atom has an energy about equal to that of the energy level in question and that the electron is in the region I. we represent the state by a wave packet built to give constructive interference of the waves in region I and destructive interference in III. the interval between the two at which the radiation intensity has sunk to half value) is evidently energies equal to 2JT.will 2 17 In the region II it approach zero in a quasian oscillatory exponential way and in the region III it will again assume character but will have a greatly reduced amplitude relative to the amplitude from 1 (^ I in I. so that the integral of their square out to some large value of f (TMs suffices to give the correct relative normalization. Lanczos was able to show that the intensity of radiation from initial states in the energy range da* at JTjJ/Jj . For a value of IF m\ the behaviour in differing slightly F . By applying the WentzelBriUouffiKramers approximation.
nization. or a from the bound state of region I to the 3gion I state of region III. & time goes on the constituent waves in the packet will get out of phase. so le amplitude of the packet will decay in such a way that the probability f the electron being in I contains a factor e~a where 8 = 23/e.gt. Avoiding the leaky barrier. General theory for nonhydrogenic atoms.gt. in the red state the electron is reckless and dolet rom the low &.f is we shall sketch the general results obtained by calculating perturbation of any atom by the perturbation theory. then the Hamiltonian of the atom H=H* + gP. for the high state has a more penetrable might expect carrier to go through. The by the matrix components H is written for the Hamiltonian of the atom in zero is perturbation therefore determined entirely . The explanation is that the initial state of high energy orresponds to the electron being mostly on the opposite side of the nucleus place in the potential where the leaking takes place. this section In ield . rfiere (I) field.. red components of Hy which are in general agreement with the experiThe rather surprising result is that the violet component emains sharp and strong to much higher field strengths than the red sonent which fades out at about 072 million volt cm. Then the total probability of leaving region I in unit is (a f S). The actual calculation of the quantities v and I for high fields is omewhat laborious although the values can be expressed in terms of Uiptic integrals. Suppose a is the probability per unit time of leaving by radiation. The his fraction &. In the component s initial state the electron is cautious and conservative.I This /7r.he electric &. so the rocess corresponds to :ee m idiationless transition of electrons an ionization of the atoms by the steady field. iminution in region I is compensated by an increase in region III.17 STARK EFFECT AT THE SEBIES LIMIT 409 be built by superposition of states in the energy range of the order of X.f mstrelj hurling itself against a less leaky barrier often enough to rob itself the chance to shine ! 3. of the value from this level is therefore would have been in the absence of the field Thus the effect of the field is to give an uasharp line whose width is and whose total intensity is diminished by the fieldionization rocess.lt. If the in the negative z direction and P is the scomponent of electric in the field is noment of the atom. Lanczos has made some calculations for the IS^r violet i/e~ 2J /7r nd aental work. ime so the fraction of excited atoms which leave total intensity of the radiation it by radiation is /(ocfS). As the violet ponent arises from TO com com an initial state of higher energy than the red component the opposite.
we are already quite familiar because it measures the strengths of spectral If for a particular atom we already have a rather complete knowledge of the energy levels and corresponding eigenfunctions. The details of the results so obtained naturally will depend a great deal on the mode of interaction. The combined effect of an entire series of terms on a given term may be appreciable however. make some remarks which hold quite all generally for In the atoms before treating the separate special cases that arise. nevertheless. 1 for a field of 100 kilovolt/cm. Third.between two states . This transforma tion also enables us to calculate the values of the perturbation matrix components connecting these perturbed states with the distent states and .which 3 17 of the zcomponent of the electric moment.410 THE STABK EFFECT ". This can be made by forming a secular equation from the matrix of the perturbed Hamiltonian by including just those rows and columns refer to the small which community of close. interacting states. the order of magnitude of the nonvanishing matrix components involving electrons in states of total quantum number n will be the same as computed with hydrogenic wave functions. This qualitative restriction coupled with the parity and J selection rules suffices to make most cases tractable in this way. place Ps has matrix components only between states of opposite parity. we see that the interaction of two terms several thousand wave numbers apart is negligible. 1 as the limit of accuracy and is carried out at smaller fields.". 2 study 10 ) of the general features of perturbations we know that the effects will be given quite accurately by the secondorder formula provided the ( initial separation of two interacting states is large compared with the energy of interaction between them. coupling of the angularmomentum vectors and the amount of configuration But we can. Because of this the secondorder perturbation whose energy difference is more than 10 (64) 2 w 4 ~ 400 n4 5 1 is almost sure to be less than 01 cm. for a state of given / value it has matrix com ponents with other states whose J values are / 1. TMs we shall see is of the order 64 n 2 cm". As most of the experimental work has 0* 1 cm". J and J f 1. In such cases the displacement of the terms is small compared to the effect in hydrogen and is strictly proportional to the square of the field strength. Solution of determine the mutual perproblem turbation of these states and the transformation to a new set of states with will this finitematrix transformation regard to which this part of the Hamiltonian is diagonal. From our previous ". we may calculate the matrix of Ps and proceed to apply the perturbation theory. Second. So for terms separated by more than about 6*4 ?i 2 it wiP be sufficient to use the secondorder formula.even at 1C volt/cm. 1 cm". For a group of states lying close to each other a more accurate calculation is needed.". a quantity with lines.
we may write for the displacement ice on le M (2) fere r ^(aJlPjjSJl)!* a^S 11 ". The results are summarized in the table: nd M jBlf 2 is produced is by the transitions Jf &. The relative strength of the different and a+ are and J+l components of the line pattern for observation resulting when these states combine with an unransverse erturbed level y J is likewise given by 93 11 just as in the Zeeman effect sf. The TT component whose displacement from the position f the unperturbed M&. 4 16 ). a direct picture of the perturba Let us next consider quite generally the kind of pattern to be observed in quadratic Stark effect of a state described by the quantum numbers J M. Using 9 3 1 1 in the secondorder formula of 9 2 4 to express the dependof the matrix components. the observed line pattern being on of the initial state.gt. There is another qualitative remark of importance.If 2] for If ^ while for Jf = the strength is 3 proportional the relative strengths of the proportional to J/(JfI). Generally the electric Isplacement of excited states is much greater than that of lowlying energy vels so that in most cases the displacements of the final state of a line are 3gHgible. line is A 2 proportional to 23f .gt. TMs procedure is exemplified in the next section.7 GENERAL THEORY FOB NONHYDRO GEKIC ATOMS know how the secondorder action due to them is 411 LUS to distributed over te community. The a component 1 so its whole strength land T ame place is produced by If to [ J ( J + 1) . Writing (2) in the form A(aJJf)=^l5J/ 2 J (3) *t us consider the transitions from the states of the level a J to a level y J f the same J value.1 and a J* J M transition may be worked ut. In the same way ines in the patterns for a J^ J .gt.3f so its whole strength &. assuming line at the qual population of the various initial states.  j  $ &QLJ&PJ1 = J 1. a ^presents the perturbation by the levels for which J f milar expressions for the perturbation by levels of J = J ^spectively.gt.BJ/ 2 i Polarization .11 M &.3f 9 * Relative strength of line component at S A .
By the results of 92 we have. It is evidently proportional to It will often happen that only one term in one of the three sums is appre ciable. of course. where the subscript refers to the unperturbed eigenfunctions. Hence. The strength of the forbidden pattern is then given by the square of .) of the same parity as j8 (with which it therefore does not combine in the absence of a perturbation).Jf). is analogous to the corresponding case in the We Zeeman effect as treated 16 by Zwaan (6 ). The theory. But in the electric field the eigenfunctions / become perturbed so that in the perturbed eigenfonetion arising from (j8 J If) there appears some of the eigenfunction of the states (ot J". if is a final state. M". whose perturbation by the field we may (y neglect. The states $(j$J 1) M) which perturb the state $(zJM) (where J =J or are of opposite parity and therefore will not give dipole radiation in combination with the states which combine with ^(a J". +f}J M. to the first power in g .412 THE STABK EFFECT 3 17 These relative strengths are the analogues of the weakfield strengths of 4 16 In the Zeeman effect since they are calculated with the unperturbed eigenfunctions. the matrix component of electric moment con necting the two states is given by (5) This expression can be somewhat reduced by using 93 11 to express the of the first factor of the numerator in each sumdependence on Jl and ff M mand. Thesquared magnitude of (5) measures the strength of the component produced by the transition y J* the square of the applied field. If). J".J1". can also obtain some general results with regard to the appearance of forbidden* lines in the Stark effect.
Likewise knowledge of the eigenfunctions in con figurations showing intermediate coupling permits us to make corresponding of 10 3 to write down formulas for the predictions concerning the Stark effect. 3). ". Proe. is which one can say without consideration of special cases. for which In this spectrum the triplet intervals are so small that they may be neglected. (6) The pattern to be expected is therefore that which applies for a combination with the perturbing (not the perturbed) level modified by the factor the ratio of the perturbation of the state in question to the un perturbed interval between the interacting levels. He uses matrix components given by use of hydrogenic wave functions. A117. The method is so straightforward that there is no point in writing down explicitly formulas for the various shall turn therefore to the application of the theory to special cases. TMs is the case when the perturbation is principally due two neighbouring terms. 2 /S lies 5857 cm". this more explicit suppose that the important term in (5) in a case is one of those on the first line for a particular value of a. The lines for which the Stark effect is studied are the com binations of the states with n = 4 and 5 with the 2 S and 2 P terms. Erom (5) to the interaction of we see that the relative intensity distribution in the pattern of the forbidden line is not the same as in the case of a nonforbidden line. below 2 *P. so by 3 2 the mutual perturba 2 1 where ff is measured in = states amounts to 0*0285^ cmtion of the f 5 (cf. We typical cases in the experimental data. 6 2. 137 (1927).3 17 that GENERAL THE0BY FOR XONHYDBOGENIO ATOMS 413 term alone. Thus in the BussellSaunders case we can use the results electricfield interaction of adjacent RussellSaunders terms. It is of the knowledge concerning the matrix components of which we have acquired in connection with the intensity problem is available is This about all evident that all P for application here. Helium.* who carried out the calculations and applied them to his own experimental data on helium. * FOOTEB. Boy. Then the given intensities are proportional to To make /} . Soc. . 4. First let us estimate the Stark displacement of the final terms to see that it 17 1 1 is negligible. M . first The application of quantum mechanics to a nonhydrogenic Stark effect was due to Foster.
10 5 volts /cm Starkeffect interaction of the 4 *#. .414 THE STABK EFFECT 417 3 10 5 volt/em. 4 *P. so the mutual interaction here is even smaller in P the ratio in the . the unperturbed D level and the abscissas are ff in 1 P volt/cm They form an excellent illustration of the perturbation theory. 1. 4 !JD. but even so its perturbation is large com states. 1 components of the P level . 4 1 D and 4 s * JF levels in helium. The S term is so far away that It is very slightly perturbed. 5 .1 below 2 P. especially in regard to the = and 1 start out with larger displacements than the components with 2 state but are prevented from reaching as large displacement as the the each other is M M = 2 state because of repulsion by the M = M F 0. 4 F and the hydroIf and J as genie matrix components (1) together with their dependence on s 3 for the cases given by 9 11 and 11 8 Foster set up the secular equations If = 0. These effects are quite negligible alongside of the Interactions n = 4 and n = 5 groups. 5 17 where the ordinates are wave numbers measured from 3 5 100 02 0# 05 OB 10 * in 17 Fig. The If = 1 state of 2 1 Is not perturbed by 2 *S. Similarly 2 $ 3 lies 9231 cm. The tendency of the terms to repel pared with that in the 2 S or 2 terms. 3 l 1 Using the observed intervals between 4 8. The results are shown in Fig. 4 1 P. There nicely brought out. 2 and calculated the roots for fields up to 10 5 volt /cm.
An interesting feature of the intensity theory is that certain com P ponents may fade out at a certain fieldstrength and reappear again at a larger value. Selskab. Tokyo 9. H BECEBB. Ann. so it can only be said that the observed intensities agree qualitatively with the theory. A122. calculations were based made by Dewey. 5.** It gives fairly good values in all cases where it is applicable. lust. reached through the correspondence principle. Ghem. ** LABENBUBG. 369 (1929). Roy. The if = 0. This was checked experimentally. 414 (192ty. Phys. 9. group. fur Phys. 82. Zeits. 355 (1927).TTMA. Consideration of the effect in the alkalis falls naturally into two parts the : very small quadratic f J effect on lines whose initial and final states are very * ISHIDA and KAMT. Passing over the older theoretical work. Zeits. The observations do not include intensity measurements. using the hydrogenic and the empirical values of the separations as in matrix components weak field of the terms A discussion of this formula in comparison with experimental data has been given by Ladenburg. We shall consider next the effect on the oneelectron spectra of the alkalis. Proc. Rev. Res. agrees with the quantummechanical theory. 30. KgL Danske Vid.fys. A study of the relative intensities of the lines in the patterns has also been on an application of the formula to the Stark effect as suggested by KramersHeisenberg dispersion Pauli. 332 (1922). 782 (1930). S I F P P J J 2^4 D 1 5 Foster also calculates the variation of the relative strengths of lines in the patterns with the fieldstrength. The accuracy with which the data is represented by the theory is shown by the experimental points for 10 5 volt/cm as given by Foster. Nature 123.f Her Foster has studied the perturbation of certain helium lines in the presence of both electric and magnetic fields. 599 (1928).J This formulation of the problem. 7. Math. goi. Phys.41 representing data from the 2 1 * *D 1 group and the x s from the j? *P. 35. This is done by the transformation finding to states in the groups which makes the perturbed Hamiltonian diagonal and calculating their matrix components of electric moment with 2 1 S and 2 1 as final terms. Rev. Soc. the o s X . FOSTEB. No. PAUU.f f Foster s helium calculations. Phys. ^f who simply considered the interaction in a jj of the same n but different I. the first quantummechanical cal culations are those of Unsold. This type of calculation has been extended to stronger fields by Rojansky. 28. 117 (1928). Ishida and Kamijima* have obtained plates of the effect in helium up to 5 x 10 5 volt/cm and find their data in good agreement with the theory. . f UNSOLD. ft ROJAHSKY. 1 HELIUM 415 level are really not Identical but components of the coincide within the accuracy of the drawing. Pkys. DEWEY. 3 (1925).417 above. der Pliys. Alkali metals. 1108 (1926). Papers.
This accords P) with the data except that Grotrian and Ramsauer could not detect the theoretically weak A( 2P:) component in a polarization. fir Phys. As an example of the first Mad we consider the data of Grotrian principal series of potassium. as in helium.f For 52 P 2 in potassium the experimental values of the A s are 044^ 2 . hard to say anything definite about the absolute value of the coeffi cients.. According to 3 17 the 2 P terms will be perturbed by the 2 S and D terms. and A d are coefficients measuring the perturbation by the S and D series respectively. 28.lt.416 THE STARK EFFECT 5 17 sightly perturbed. Zeits. the single component appearing of relative strength 2 and 2 and a polarization. The kind of pattern to be expected and the relative intensities are readily worked out from the results of 3 17 The prediction is that the line from 2 P.lt.f * OEOTBIAN and RAMSAUER. Phys. 28. If this be done it will readily be found that the 2 term in a oneelectron spectrum can be written perturbation of a P (I) in which A. . . They are small both because the nearest perturbing terms are about 3000 cm* 1 away and also because the nearest S and D terms below 5 2P are It is almost as close as the nearest 8 and D terms above. . 846 (1927). These formulas are based on the supposition that the 2D interval is negligible and the 2 P interval large compared with the amount of the effect. we may use formulas of 10 3 in the As remarked at the end of that section RussellSaimders case to find the relative values of the perturbations on the components of a term. so there is a tendency toward cancellation of effects. &. while from 2 Pg we have a 2 component displaced by A( P) which has strength 4 in TT and I in a polariza tion and a component displaced by A( 2 of strength 3 purely in a polariza tion.f 2 respectively (unit of = I0 5 volt/cm) which are represented by taking *4 S =(H3 and J^=OG7 probably within the accuracy of the data. 51 (1925).Zeits. and 0*37&. and Ramsauer* on the The data were obtained in absorption for the 2 second. when the interacting terms lie very close together.f . 021&.lt. is displaced by the amount A( in IT 2 P). third and fourth lines. and the transition from quadratic to linear effect. f LADE^BrBG. The quadratic effect on the sodium D lines has been studied by Ladenbur^.
Ishida and PukusMmaf have published observations on the 2 P 4 PDF and 2 P 5 PDFG patterns which show in all respects agreement with the qualitative predictions of the theory. and in which the displacements are quite accurately given by calculating the secular equation with hydrogenic matrix components. The 4D and 4 F terms are close enough that a linear effect sets in at fields of the order 30 000 volt/cm. Inst. 5 * COSDOS. Chem. Tokyo 9. 648 (1933). 141 (1928). Pap.been 417 As an illustration of a more hydrogenlike alkali spectrum we shall mention the effect in litMnm. . This has discussed by Condon* in a manner analogous to Foster s work on helium. Res. Rev. 43. while the 5 D 5 F and 5 G are so close together that their interaction gives a linear effect from the outset. Phys. t ISHEDA and FUCTSHIMA.5 17 ATiKATiT METALS ". Sci. Phys.
". although much remains to i&.gt. Phys. 694 (1930). Ffeya. in connection with the theory for atomic hydrogen. 1 ). 4 5 freedom for few years and done. In this chapter we shall the way in which the nucleus affects the structure of atomic spectra. following Pauli 9 is to be associated with quantum numbers specifying a degree of .f The energy of a system of N electrons^ eaeli of mass p. Effect of finite The theory for a nucleus of finite mass in an ATeIectron problem has been by Hughes and Eckart* and also by Bartlett and Gibbons.". t BIETLETT and GIBBONS. as a consequence of which the nucleus has some energy. * HUGHES and ECKABT. The most obvious feature to be considered is the of the nucleus. The effect of this on the atomic energy levels we consider in 1 But more interesting is the fact that some spectra show a fine struc ture of the lines. conjugate to U. when expressed as a function of the conjugate to %. This is known usually as hyperfine structure and. Bev. and P. 36. The theory of the energy has received a great deal of attention in the well understood. finer than the ordinary multiplet structure (on a scale of 0*1 to 10 cm". levels resulting from this picture of the nucleus. position vectors of the electrons We Introduce the position vector R of the centre of masSj vectors gt which give the location of each electron relative  the to the nucleos s ___ ***". kinetic energy becomes.". The very fact that this topic can be put off so long indicates that the effects are small. . 538 (1933). Then the p i . we have treated the nucleus so far not as a dynamical particle but as a fixed centre of Coulomb force characterized solely by the atomic number Z. Rev. 4*. and a nucleus of 31 is given in terms of the T to a velocities by and nucleus relative r are the origin. Nevertheless they are of great importance and afford a tool for studying atomic nuclei.e 1. is momentum now fairly mass.CHAPTER XVJII NUCLEUS IX ATOMIC SPECTRA Except for brief consideration of the finite mass of the proton in Chapter v.
For any element the result readily follows from the fact that the potentialenergy function is homogeneous of degree 1 in all the positional coordinates. as considered in 7 Suppose we know the energy levels for the case of infinite nuclear mass. spinorbit interaction) is what we found in Chapter v for hydrogen to multiply these levels by jLt //i= [1 h/i/Jf TMs and hydrogenlike ions. these are the same for all the states of the configuration.K)(a&. This part has been called the normal effect.a&. In the case of the p*p configuration all the electrons outside closed shells have the same parity. we may as well confine ourselves to since states for which 0. so the diagonal matrix components of S contain only the contributions due to interaction of the s closed shells with the p electrons.gt. j&. is . Then we see that the finite nuclear mass has altered M P P= the kinetic energy part of the Hamiltonian in two ways.lt. which we treat as a perturbation.lt. In the zeroorder scheme. j". Phys. hence all of the diagonal matrix components in the ( parity operator 1 first term vanish. Since the translational energy of the centre of mass cannot change appreciably in a radiation process and is a constant of the motion. Now p is a vector which anticommutes with the 6 1 1 ). 214 (1933). In the * BBOWS. 272 . we have from 7 6 7 the diagonal element (A 8\A) = i ^E {(a* j&. Moreover the second term will vanish unless a k and a & refer to individual sets of opposite parity.* They calculate the matrix components in the zeroorder scheme and from these the perturba sum tions of the RussellSaunders energy levels are obtained with the diagonalrule (exactly as in the calculation of electrostatic energies in Chapter vn). 44. Similar remarks can be made .gt. about the nondiagonal matrix components given by 7 6 With the main features of the S matrix known the detailed calculation of the energies due to this term may be made in any special case by the same methods as for other types of perturbation. by the substitution of ft for p in the first term and by the appearance of the second term which we shall call $: This 6 evidently a quantity of type (?. the reduction to individual oneelectron matrix components being possible because pipj factorizes.gt.) .(tfi\p\a?Ha!\p\a*)}. Rev. The specific effect is that due to the matrix components of 8. Bartlett and Gibbons have carried out the calculations for the 2p 5 3p lines in 5 ^&.I 18 EFFECT OF FXOTTE MASS 419 where \L is the reduced mass pM\(p f ). Then for finite mass the is effect of the change in the first term (neglecting 1 .2p 3s neon using the Hartree field found by Brown.
* although the theoretical value of the absolute shift &. Pap. too small. j&. various theories of nuclear structure agree in assigning to the size of the nucleus a linear dimension of this order of magnitude. and 00293 cm. Phys.gt.gt. mercury were considerably larger than the experimental values. This is in accord with the observations of Xagaoka and Mishima. Local unclear Unquestionably the nucleus is not truly a point centre offeree. Rev. Tokyo 13.1 more than the triplet lines. differences in spectra associated with different isotopes Data on * XAUAOKA and MISHXXA. 293 (1930).1 for the Xe 22 and Xe 20 P psP 5 Hence in the ps p s array. Calculations of the effect on atomic spectra of such departures from the Coulomb law have been Breit. and Rosenthaif Nothing very definite is known about the nature of the departure from the Coulomb law. 343 (1U32). 1 for the p p levels. Res. lead. instead of the values used in the of heavy paper. that the theoretical values of the isotope shifts of spectra of thallium. In the later paper. THE NUCLEUS IS ATOMIC SPECTRA is I 18 not the ease. t RACAH.gt. Breit shows that much of the discrepancy can be removed if a semiempirical One of the most uncertain elements entering formula for first 2 (Q) due to Goudsmit is used. into the calculations is the value of the atomic eigenfunetions at the nucleus.1 for the p s s l level.420 5 j&. so that the Coulomb potential 2e2 /r. Calculating the specific shifts 5 configuration this for the P isotopes and taking the difference (heavier minus s calculate net shifts of 00136 cm". 723 (1932). is much 2.0. and it tunas out there that the 3 term 1 is displaced by 31% while the P term s displacement is 1% where Jc is a matrix component connecting the 2p and 3$ states. last. .Experi ments on scattering of aparticles by nuclei have shown that there are 12 departures from the Coulomb law in the neighbourhood of r~ 10~ cm. In the first work it turned outs on assuming that the radius of isotopic nuclei varies as the cuberoot of the atomic weight (constant nuclear den sity). 42. they levels. 41. of lighter). Fiys. Xature 129. Racah makes the simple assumption that the nucleus is spherical in shape and that the potential inside the nucleus is constant and made by Racat 3 continuous with the value at the boundary of the nucleus. The calculations of Rosenthal and Breit are carried through using the Birac equations of the relativistic theory (5 5 ).gt. the singlet lines will be displaced 00105 cm*. cm.. ROSESTTHAX and BBEIT. cannot be correct in the limit as . 459 (1932). fields. Fhys. Rev. Sci. Chem. and r~&. BRER. Rosenthal and Breit work with a model having a discontinuity at the nuclear boundary corresponding to the potential barrier model used in current theories of xparticle disintegration.
But such structure is observed in atoms having no isotopes. f FKESCH and STEIC*. 85. 4 (1933). Somewhat surprising is the fact that those nuclei which are supposed to 3 jontam an odd number of electrons also have magnetic moments of this * PABU. notably bismuth. said than that reasonable assumed departures from the in the neighbourhood of the nucleus can account in order of for the observed effects. Phys. noment 25 times larger than (e/Jfc)(Jft). Friseh. rnd Zacharias  which uses atomic instead of molecular hydrogen. Zeits. Bev. denoted by J. developed by Rabi. This hypothesis of nuclear spin has also proven of great importance in the theory of molecular spectra. Nuclear spin in oneelectron spectra. 17 (1933). 12. With nuclear spin postulated. This was first obtained from the classical picture of a nuclear magnetic moment whose energy in the magnetic field produced by fche electronic structure depends on the orientation of the nucleus relative to that field. It is supposed that a nucleus of given Z and 31 always has the same spin. But this appears not to be bhe case according to the recent experiments of Stern. The result was a magnetic . 85. { KABI. ibid. 46. so some addi tional hypothesis is needed for description of this structure. This was sup plied in 1924 by Pauli. This brings up the question of the magnitude of the nuclear magnetic moment. so that it is now an indispensable part of atomic theory. and ZACHABIAS. It is difficult in the present state of knowledge of nuclear structure to say anything about this that is very definite. so it was natural to suppose that for a proton the magnetomechanical ratio EFOuld be efMc or ft/Jf = 1/1838 times as great. . 741 (1924). That the spin of the proton is \H a known from the band spectra of E2 This unexpected result for the proton s made certain by a more direct method. and Ester mann f 3 in molecular which the magnetic moment of the proton was measured by a beam method on molecular hydrogen. 157 (1934). but that different kinds of nuclei have different spins. For an 3lectron the magnetic moment is e/ftc times the angular momentum. we need in addition to know the term in the Hamiltonian corresponding to the interaction of the nuclear spin with the electronic structure. fur Phys.2 18 LOCAL NUCLEAR FIELDS 421 elements is being accumulated rapidly at present and may in the future prove an important source of knowledge about the nucleus. but at present not much more can be Coulomb law magnitude 3. KELLOGO.* who postulated that the nucleus itself may have a spin angular momentum and an associated magnetic moment. NatorwiBB. Kellogg. ESTEBMASW and STEBN. The effects considered in the two preceding sections do not produce a splitting of the levels of a single atomic species and so can only give rise to a hyperfine structure when several isotopes are present.
For positive M. It is easy to see that we here another have of vector coupling. not reproduce the calculations in detail.J Irf and the other with F=I~. The factor i belongs with an I. not to be explicitly mentioned but we do need to introduce J/j the zcomponent of nuclear spin. 141. of the nucleus and M the actual F T magnetic moment ^ 2 {0) is the value of the normalized value of 5eigenfunction at the nucleus.* The moment M of the nucleus gives rise to a field described by the ^ = ^Hxr. including the interaction with the nucleus through the vector potential given by (1). 320 (1930). The first moment magnetic quantitative theory of the interaction of the nuclear magnetic and the outer electrons is due to Fermi and Hargreaves. Roy. 407 (1930). that is Then. this makes it appear that a nuclear electron is quite different from a free electron or one in the extra nuclear structure.422 THE xrcLErs rs* ATOMIC SPECTKA 3 18 size. AIM. as a coordinate and quantum number. is proportional to the nuclear angular momentum I. This is just one of the properties of nuclei wMch lends support to the never view that nuclei are composed wholly of protons and neutrons and do not contain any electrons. . it follows analogous to the Lande ^factor in the theory of the Zeeman are represented by three nonthat the components of M commuting matrices whose rows and columns are labelled by the values of 5 Jlj . M (2) where gs is effect. A127. HAJBGXEAVBS. We start with a scheme in which tie We J of the outer electron and the I of the nucleus is known. Fermi handles the oneelectron problem with Dirac s equations ( 5 ). All this is exactly what we have been through in studying the coupling of S L to form J. 568 (1029). the displacements from the unperturbed positions Fermi being (3) Here /% = e /2/tf is the magnetic moment of the Bohr magneton. 0. the s $. The resultant Fis the vector sum of these two and we have to transfrom a scheme of states in which JP and are diagonal to one in which P F2 is diagonal. See. the level with J = * fur Piys. I vector potential (I) it Since the magnitude of the nuclear spin is constant in all states of the system. terms of the oneelectron ns configurations are spit into two levels. since . Proc.
H BABI and CoBm. and by the recent accurate measurements of the hyperfine structure Intensities by Joffe We thus have three different methods leading to value in the case of this nucleus. j magnetic difficult moment from the observed splittings Is of course a much more and uncertain matter. JACKSON. The I . ibid. in general into four levels whose J values are 1 1 f. 935 (1933). Hrys. M. 707 (1934). 58. Positive M corresponds to the magnetic moment parallel to the angular momentum as If the magnetic moment were produced by rotation of the positive charge distribution of the nucleus. S^ That the nuclear spin of Na I is equal to f is shown by the measurements of Rabi and Cohen by a modification of the StemGerlach experiment. Likewise Fermi finds that the 2 P. 2 Pj level is split . consists of two doubled by interaction with the nucleus and that a splitting of the 2 P levels is negligible. 658 (1928). f ECLEPFOV and GBOSS. The calculation of the nuclear the same Granath and Van Atta. ibid. For potassium the corresponding structure Is either absent or very much narrower. DOBBEZOV and TEBESX^. The value of / is inferred from hyperfine * SCETOLER. 43. Soc. A121. 735 (1929). 432 (1928). 761 (1933). . Zeits. 17. Natorwiss.3 18 is NTJCLEAB SPIN IX ONEELECTRON SPECTRA 423 lower In energy than the other. 16. and If f the displacements In energy being respectively. ffir Phys.) The four levels have the same kind of Interval 1= rule as with RussellSaunders terms: the Interval between adjacent levels is proportional to the value of the pair. ibid. larger F Let us now consider the application of these results to the alkali metals. 46. (For 1=1 there are but three levels. by and Urey from alternating intensities In the Na2 bands. Jf J. GBAJJATH and VAX ATTA. and Dobrezov and Terenin* find In 2fal that each of the Dlines components with a separation of G022A. the amount of the perturbation being given by (3) with r^ In place of TT ^ 2 (0). f In Rbl the second line of the principal series shows doubling as in sodium with a component distance of O02QA4 Jackson studied the first three lines of the principal series of Cs I and found that each component In all three lines showed a separation of 0300 cm". 43. level is split into two levels In the same way. JOFFE and UBEY. Naturwiss. 16. as I f Is Impossible. These observations are in accord with the view that the 2 $ level has been . since In any case the 2 level would be split into two levels.1 and that the two hyperfine components were of about equal Intensity. Rev. Boy. f ScHiiLEB and BBUCK. From the splitting one cannot find the value of I. 512 (1928). 582 (1933). Proc. Schiller. 121 (1929). and for  there are only two.
82. this not undertake a detailed review of the theory by which the nuclear magnetic moment is calculated from the data. 43. TABLE I ls .^ This paper includes a compilation of known values of nuclear moments. as does an independent paper by Goudsmit. Unclear spins and magnetic mommis. . Zeits.424 structure intensities NUCLEUS ES". f Rrom GEASATH and TAN ATTA (foe. t GOO&. The most thoroughly worked out case of hyperfine structure wliere there more than one * is electron outside closed shells is that of the ls2s^S and and SEsai. ( so that the reader may for himself the degree of consistency obtainable in the by different workers of development of the theory. For oneelectron spectra in particular this has been most carefully discussed in a paper by Fermi and Segre.gt.f Table I 18 is based on these two compilations and gives the values of the We moment in unite el 21fc from each paper.J and JF = / + 1). 636 (1933). fur Pfays. J for S and I for L. dL). Rev. The iiyperfine structure of twoelectron spectra. Thus in the splitting of a line ending 9 on the Z S level. . for evidently the 9 theory of RusseilSaunders multiple! intensities (2 ) Is applicable here if we write F for J. the two components have an intensity ratio of /: ( I fbeing the ratio of the two values of ZF f 1 for F= I. 4. ATOMIC SPECTRA gis by an application of the sum rales. 729 (1933).SMITS Fhys.
35. fur Phys. Rev. GOTTESQEB and PAULI. i) (i) components f f and f respectively. BBEIT and DOEKMAIW. H .F 3 f and f and f . Zeits. _ . Phys. for the oneelectron problem. . These are based on the use of a law of interaction of the electrons with the nucleus as used by Fermi in interaction. 67. 2 The fact that they are comparable that the nondiagonal matrix components implies of the nuclear interaction which connect different 3 ^ 3 levels of P are important. _ j H r detailed interpretation of the observed 18 hyperfine structure for the case of more than one Fig. Phys. 34. HABVEY and JUNKETS. fur Phys. ffip Phys. I 18 which shows how the magnitude of the 3 hyperfine structure in Pis related to the ordinary level intervals. J WUEM. 3 P1 becomes a group f of three levels with of four levels with level F=  . 42. * The and GtJmKGEB.* The hyperfine structure of the multlplet due to the combination of these terms is of particular interest because it is comparable due to spinorbit magnitude with the ordinary level structure of Li The theory is in good accord with experiment! when the value of / for Li 7 the most abundant isotope. This counts only the interaction of the Is electron with the nucleus. PJiys. f and f. 36. ment with the 3 ^ Pf f . . 1262. 64. 1286 (1929). i Hyperfinestructure of the ** P terai ** Li]L electron outside closed shells is complicated by the necessity of considering the state in intermediate coupling (Chapter xi) 749 (1930). energy diagram (after Giittinger and Pauli) is given in Fig. Zeits. 1018 (1930). These were considered 2 %  in the calculations of Giittinger and Pauli. 562 (1929). . together with use of appropriate twoelectron wave functions. Rev. 0(0) being here the value at the origin of the Is wave function. 5 F= . 58. ibid. although there are discrepancies in the relative intensities. for the three f.4 18 Is THE HYPEEPINE STBUCTUEE OF TWOELECTEON SPECTRA 425 3 2p P terms of Li II. The experimental data are ingood general agree theoretical calculations. 1732 (1930). 36. 789 (1930). 743 (1931). GRADATE. 487 (1927). For the 3 Sl level. Breit and Doermann find that the perturbation due to interaction with the nucleus is ioel^M^oHi. 3 P2 a group An 3 p = . Rev. is taken to be f This value is in accord with that from the spectrum of the molecule Li 2 J We shall not give the details of the calculations. The 3 P levels are split according to the laws of vector addition of angular momenta: 3 P is not split. Zeits. f SCHULKB.
results. We have a situation here. BBMT aad Wnxs. 663 (1931). Rev. In the ordinary of the Zeeman effect ( I 16 ) the theory interaction.t At present not enough is known about configuration interaction to make possible quantitative but Fermi and Segre show that qualitatively its effects account for a number of observed features of the hyperfine structure Trhich are otherwise without explanation.428 NUCLEUS IS ATOMIC SPECTRA 4 18 The effect of the Intermediate coupling has been considered in detail by Breit and Wills. 729 (1933). II (1933). . account of the results which have been ob tained for the perturbation by a magnetic field of the structure due to nuclear We shall not give a detailed Tie work is extremely important as indicating the essential correctness of the nuclearmagneticmoment picture.SH!3rs Sizber. Pliys. 37. Zeeman effect of hyperfine structure. Their developments agree experiment but there are many outstanding discrepancies. 502. 82. parable with the ordinary spinorbit and electrostatic separations. p. Bev.* while the importance of considering the interaction of configurations in this also the Influence of configuration interaction (Chapter xv). from the simple Lorentz theory arise because of the different values of the magnetomechanical ratio associated with the vectors L and S.f They have been discussed in detail by Goudsmit and Bacher j with satisfactory 5. J who first gave a general discussion of the interaction with the nucleus in the case of complex spectra by vectorcoupling methods. 44. 1832. Zeite. GOUBSMZP and BACHES. Rev. the need for further refinements of the theory. t Gorasnr. 48. The work of Breit and Wills is in extension of that of Goudsmit. For fields such that the ordinary Paschen Back effect is negligible we have a magnetomechanical ratio of the electronic represented by g(J) where this is the Lande g factor of the level in question. Aiad. PTCIBBB. This necessary more accurate calculations of the nuclear perturbation of the levels. Associated with the nucleus is a magnetomechanical ratio about I0~3 as great so the direct interaction of the nucleus with the external magnetic A direct application of the formulas of Chapter in then shows the split ting of a given hyperfine level to be governed by g(J) of the ordinary level to which the level belongs multiplied by the factor (I03 2a) which gives the * field is negigible. indicating In Hg A1II occur in which the hyperfine structure is com fairly well with. Pj. 894 (1933). allowance for its effects. Piijs. but presents no new theoretical problems. Pfcys. f3r Phys. connection has been stressed by Fermi and Segre. Empirically effects and their nature were recognized by Paschen. 470 f FXEMI and Src&i.
66. BACK and WULFF. Zeits. fur Phys. 66. Experimentally effect of the and theoretically this for Bi. EFFECT OF HYPEEFIHE STEUCTUEE 427 2 natrix component of Jz in a state labelled and Fz by precise values of Ihat is. BACK. fur Phys. Zeits. BACK and GOUDSMIT. The magnetic transformation of the I=f hyperfine structure in thallium has been investigated thoroughly by Back and Wulff. J breakdown of the coupling ofJ and 1. TMs is the PaschenBack tiyperfine structure. 47. 31 (1930). Just as in the discussion of 5 16 the difference in the magnetomechanical ratio of the vectors and /means that strong magnetic fields can produce a . ibid. ZEEMAN. 174 (1928). Zeits. the g value for a state of resultant angular momentum F composed of electronic J and nuclear / is F .5 18 ZEEMA25". fur Phys. 86. and GTOUDSMIT. 13 (1930). 2F(F+i) This result was first obtained by Goudsmit and Bacher* from vectormodel 3onsiderations. . has been carefully studied by Back and Goudsmitf phenomenon They find good agreement for at field strengths corresponding to various stages of the transformation of coupling schemes. 1 (1930).i * f J GOUDSMIT and BACHEE.
chosen that 1 cm 1 sec". MICHELSON. 10 gt cmi 1 sec". The choice of the basic units for these quantities is wholly arbitrary. is of the order of velocities of common experience. 40. . 1 . These great powers often are rather inconvenient in theoretical calculations. To recognize this fact is not to deplore it. 211 (1933). 1 (192% Phys. Mod. It is customary to build up the system in such. length. 1 . PEASE.". There is. and PBABSON. Bev. 100 (1935). and time. the general order of magnitude in the centimetregramsecond system being such that the numerical measure of quantities occurring in ordinary labora tory experiments is of the general order of unity. a way that the unit of any kind of physical quantity is defined in terms of three conventional units of mass.". Its basic units are of convenient magnitude common laboratory ap paratus. Light velocity: = 2&979B x 1C10 cm sec". For example*: Electron eiiarge Quantum constant: : e= 4770 1*043 x lO". The basic universal constants of atomic theory have values which are very large or very small compared with unity. 43. For later modifications see BIBGE. so ultimately the foundation is anthropomorphic since laboratory apparatus is built and designed on a scale convenient for manipulation and observation by a human observer. Phya. THs is in fact the case. Thus the Telocity of light in the cgs system is 3 x 10 10 cm sec* 1 The centimetre and second being so . Electron mass : 9035 xlO~ ffl g. . therefore. 228 (1932). the bigness of the number measuring velocity of light on this system is simply a statement that velocities of common experience are very small compared withthat of light. There aretwo ways of avoiding them which might be adopted. 1= ^L= c x 10~ S7 g cm 2 see". But the fact shows us clearly that a metric resting on such a basis will probably not provide units of convenient size for dealing with another branch of physics like the theory of atomic structure. One is the way which tie metric system has already adopted for extending itself to larger * We use the values of the universal constants as given by BIRQE after a critical surrey of all the relevant data: Rev. Phys. Science 81. Rev. nothing especially fundamental about the cgs for basis. 1.APPENDIX UNIVERSAL COXSTAXTS AXD XATURAL ATOMIC UXITS Measurements in physics are statements of relation of the quantity mea sured to quantities of like kind which are called units. Certainly the egs system is convenient for description of the macroscopic apparatus which provides the refined sensedata of physics.
1 3 so the velocity of light and the quantum constant have the numerical values 299796 and 1043 respectively. namely to choose another system of fundamental units related to the metric system by conversion factors which are powers of 10. This kind of arbitrary choice merely alters the place where the pure number 77 appears in the calculations and is analogous to the difference between the Heaviside Lorentz units and the older set of electromagnetic units.UNIVERSAL CONSTANTS AND NATFBAL ATOMIC UMTS 429 or smaller units. 27 2 1 in the expressed as (1043 x 10~ )a:gcm Therefore the length expressed as la in the Hartree system cgs system. made in this respect. Denoting by a and r the Hartree units of length and time respectively this means that JJL From this standpoint the numerical values of the universal constants e. it is still more convenient to introduce a system of units in which certain of these universal constants are set equal to unity. 89 (1926). PMl. Thus it is a matter of arbitrary choice whether we set h or Ji equal to unity. 9 new system electrostatic unit of charge becomes 10~ giem*sec~ 1 .2 cm. Quite a variety of such systems have an equal claim to use so far as general convenience is concerned. so we adopt that one. . of velocity is 10 9 cmsec* 1 and of angular momentum 10. There is not much point in debating which of is the choices most convenient. however. ft and \L given in the c g s system are the conversion factors by means of which quantities expressed in Hartree s system are to be expressed in the egs system. which _ works out to be la = 528 x 10 8 cm where x is a pure number. 24.(4770 x 10~ 10 ). From this standpoint the numerical values of the universal con stants become the numerical conversion factors which connect this system with the ordinary c g s units. and ft have each the numerical value unity. For theoretical purposes. and 10".27 gcm 2 sec. the 10* em. By taking as our units of mass. 27 2 2S 1 is expressed as (1043 x 10~ ) (9035 x 10~ ). Hartree s atomic units are such that e. so that it is not possible to assign the numerical values of more than three of the universal constants choice is different systems arise according to which choice. . As it happens one particular 3 recom mended by Hartree * has already been quite generally employed in theo retical work. ^ * HA&TBEE. is sec". sec. Similarly the new unit . Proc. length and time lO^g. Camb. Soc. so in this the electronic charge has the value 0*4770.". Another arbitrary element lies in the fact that there are only three fundamental units at our disposal. Thus an angular momentum expressed as xK in the Hartree system.
The fact that the numerical magnitudes of c 2 and of JI in this system of units compared with unity is of fundamental importance for the c 2 is what makes the relativistic corrections small and the largeness of 31 makes it a good approximation to treat the nucleus theory. R. Another important parameter of atomic theory is the mass of the proton. which is 11=18383/1.. hence the velocity of light has the value c= 13729 ar The reciprocal of the pure number which gives the value of the velocity of light in these units is known in the theory as the fine structure constant. the other units have simple physical interpretations in } s the theory. have simple numerical magnitudes in system of units. Unit the electron in the first and unit velocity is the velocity energy is the potential energy of Hartree unit. known to an accuracy of about 6 parts system in 10 million. Thus unit length is the radius of the first orbit in Bohr s theory of hydrogen for an infinitely massive nucleus.430 Similarly the value of T in the APPENDIX IT = 241 9 cgs system is xIQ17 see. The quantity whose relation to the cgs system is known most precisely is the combination aa1 The combination aa1/^ is known as the Rydberg constant. the accuracy with which the values of a and of a although separately are known is much less. Its value is . readily found. The theoretical energy levels of atoms is Its relation to the c gs thus . Bohr orbit and hence the ionization energy is half a Numerous other examples are to be found in the table in this We shall not discuss the precision with which these quantities are known in terms of the cgs system other than to say that it is quite generally that associated with a probable error somewhat less than 01 per cent. Aside from the fact that this e R and p. appendix.006 cm1 ~ 4?r . for example. This is usually defined by the equation a = e 2/cl. R = ~ a1 = 10973742 4. of the electron in this first Bohr orbit. 1 . It appears. as a parameter of the relativityspin structure of the hydrogen spectrum in Chapter v. From these basic conversion factors the value of the Hartree unit of any is derived quantity in the cgs system 1 1 ai Thus unit velocity is = 2. are both large The largeness of as a fixed centre of force.1 8 x 10 8 cm sec* 1 .
The effects of oc and ft/If we are not hampered by the uncertainty in their values in making com parisons between theory and experiment. and the quantum numbers labelling the level in question. by c2 in classical radiation . particular number Z. The precision of knowledge in R is much greater than the accuracy attained in the calcula perturbation theory tions at present. This is the reciprocal of the quantity often denoted theory. Of these Z and the numbers are quantum so there is no uncertainty in their numerical values. p/M. This factor has the i value j^= 0698 cm1 deg. In using the energy levels to predict the wavenumbers of spectral lines.CONSTANTS AND NATURAL ATOMIC UNITS are given in terms of the Hartree 431 energy unit and the parameters like a.1 . E^Jic^m what enters. so that the comparisons with experiment are not at all hampered by the inaccuracy in the Rydberg constant. on the energy are usually in the form of small corrections. the wavenumber equivalent of the energy given by Bohr s relation. which measures the relation between thermal energy and the thermodynamic temperature scale measured in conventional 5 Centigrade degrees. As we nearly always express energy in terms of equi valent wavenumbers in cm1 . so the atomic integers exactly. directly the which when multiplied by T in Centigrade degrees gives wavenumber equivalent of the energy JcT. em1 without The only other universal constant of interest for spectroscopic theory is the Boltzmann constant i. the important conversion factor is not k itself but A/Ac. For that reason we cgs units is the may express the results of the theory at once in terms of paying attention to the uncertainties in R. As the wave number equivalent to one Hartree unit of is 2R it follows that the greatly energy 5 principal factor needed for passing from Hartree units to one known with the greatest precision.
ea Moment first by hydrogen atom in 252xlO.1 electron. a e*/a Ekctrit ctergc: Atomic Potential: unit. 1 ^sC^f~". . a H Wavelength 1 a".18 esTicm Bohr Magnetic fdd: Atomic first unit.ar 10973742006cmrl 15233cm. 171x10* gauss 7283 Field at nncleos doe to motion of electron in 1245 xlO5 gauss Bohr orbit. i Mass of proton. twice the unit. e. ei/2jiC= xlO^18 erg gauss". jf5 R H Hydrogen doublet constant. e /j^c =. A ngidw Basic quantum unit. a=F t la scat 00004} xlO". 2.1 20 lO". IOL*T*= ie*. xlO8 cm1 Rydbeig constant. I ionization energy of hydrogen with infinite nacSe&r = f 4304 erg =:21947484 j cm1 mas 18859 jiaV* Energy equivalent of electron mass. 4ira". 1043 Planck constant. 1 sec". r transition in hydrogen 1 ar".1 03636 iOOOOecnr1 xKT5 a 1 81063cmrl (9035 1661 of electron.x a 1 of limit of Lyman series. Force: ic:2707 electron volt 7 810 erg xir Force of attraction toward nucleus on electron in first 819 xlO~a dyne Bohr orbit. 09174 x 1 erg gauss". Magnetic momeM: 252 Atomic unit. by Compion 00458 a 212x10*". i^&^ Bohr magneton. Wavenumber of 0807 4281 1 lftSxlO. cm tering through TT. 1 fcs/xaV". e/a J OO [272 volts Eltciricfidd: Field strength at atomic unit distance from 8 (171 xlOSgcm sec. negative of charge on election Potential of electron s field at atomic unit distance. 531 280xiO13 cm 1722 a 910xlCT 8 cm 1893 Atomic unit. ar^r". 27roca (TMs is also the wavelength of yradiatioa associated with annihilation of an electron) 2 2 2 Electromagnetic radios of electron. Atomic 2Rfe. 1 sec". y*R E jlft Wavenumber associated with one electron Tolt 581 xir* a1 x!Q* 1 a". 2d!=& 2 6547 x!0~27 gem2 xlO~27 gem3 11 xlO". orbit* Momentum: Of electron in first jn Bohi 1 orbit. Mean life for 2p! Velocity: Speed of electron in first Bokr 1 Speed of light. 8 cm Shift in Xray wavelength. 1 sec". R^o first Balmer line. 1966 13729 juaT 1 /lar". e/a 1513 x 10s volt cnr 1 Ekdrie mmmt: of dipole formed orbit. if Time: 0010} xlO^g xlOg Time for electron to go 1 (Sir) revolutions in 2419 xir17 sec 662xi07 r l6xlOrfleo 218 xlO8 cm sec1 10 1 (299796+ 0*00004) x I0 cm sec first Bohr orbit. Basic quantity of relativistic theory : 270 xl(r19 g cm xlO~17 gem 1 sec".432 APPENDIX Values of some Important Physical Quantities Value in atomic units Kind of quantity Length: Value in c g s units (05282 Radius of first Bohr orbit.
LIST OF PRINCIPAL TABLES INDEX OF SUBJECTS INDEX OF NAMES .
................ 241 . ..... 2 14 1 15 Tlie normal electron conlgnrations of the elements Lande g factors for RusselSaonders terms .............. ... .... ...... .. PAGE 76 76 76 77 117 117 F 2s 3 S S Xonnalized radial eigenfunctions for nydrogen Mean 4 S values of r* for hydrogen Taliiraof r(I}fi( iI)drforliydrogeii ... .. 424 432 ..251 ....equivalent Matrices of spinorbit interaction Tlie transformation from jj coupling to 513 1 14 The Xeneigy levels of the Tie periodic table . atoms .. . ........... .................... nlx 133 178 2 s a^Zntj^X) .. .... ISO F 1 s KussellSamiders terms and Lande factors for Line strengths in RusseHSannders mnltiplets 3s 4* Relative multiplet strengtlis in sereral taBnsition arrays Strength of qTiadrapolemultlplet lines 2 ie 1 11 1 12 Allowed J values for groups of ^"..... configurations ..... .. ......... ...... . . ........LIST OF PRINCIPAL TABLES ABLE I3 U\J^i2iMJ m ) 2? i^lm^m^ljm) OilaMfL.. 208 253 263 electrons 268 294 LS coupling 320 332 333 382 1 1S Xndear spins and magnetic moments Values of some important physical quantities .... .iiJ) ) 3s ... ... .......... . .....
dynamical. 1*4. 333 selection rules. 168 interaction. 26 Eigendifferential. rales (cont. 337 matrices of 48 Diagonalsum Dipole electric. 22 21 Eigen^r s. 19 JL and/2 2 113 . 173 Dispersion theory.) 14. see Mean 262 RusselSaunders terms. 46 Almost closed shells. spin. 43 see Equivalent electrons 282 . 428. 295 Equivalence degeneracy. Component (of a line). 183 Equivalent electrons. 179.INDEX OF SUBJECTS line shape. 83 Electron spin. and Combination principle. 321 Dynamical equation. 166 Brackett series. 90 orbital. 177. 226 Doppler effect. 376 Stark effect. 54 Electrostatic interaction. of elements. 369 Average. 3 Even states. 432 Antoionization. 8. 53 Alkali spectra. ICfc. 141. numbers. 263 Allowed levels in LS coupling Commutation Commutator. 46 m commutators. 56. 29. 103 54 transformation amplitudes for vector addition. 167 Allowed levels mjj coupling for nl\ 263 for nljx. 87 Critical potentials. 46. 160 8 function. rule. 159. parity operator. 15 of angular momentum. 85. 114.F J2 = J. see Allowed Twoelectron configurations levels. 113. Chapter xrv Centralforce problem. 220 xm Angular momentum. 9. 9. moment 90 see Magnetic moment Dipole radiation. Chapter xn. 25. 58 number of electrons with various values. 137 Bose statistics. 186 43 16. 162 Balmer series. 14 of a function of an observable. 15. 59. 50. 14. 14 dosed shells. 5 for nLx. selection roles. Chapter vin simultaneous. 26. eigenstates. 20 Electromagnetic theory. 10$ perturbed intensities. 25. 18 168 Complete set of quantum. 168 Correspondence principle. 14 Antisymmetrizer. 20. Chapter allowed values. 284 jj coupling. 222 Diagonalization of a matrix. 263 method of obtaining. 97 Configuration. 183 oscillator strengths. 258. 186 AntiHermitiaa matrix. 161. 64 matrix of (Ji+Ja) . Diagonal matrix. Chapter xv normal. 208 method of obtaining. 73 Anticommuting observables. 165 Antisymmetry of T. Complete set of observables. 185 Exchange integral. 216 Allowed values. 259. 20 Conventions concerning quantum numbers. 190. 7. 137 Central fields. 141. 67. 112 Characteristic values. 164 Atomic units. 160 Equivalence. 6. 46 matrices. 415 Allowed levels. 20 Diagonaiization method of obtaining eigenfunctions. 96 Direct integral. eigenfunctions. 73 transport in radiation* 92 t 96 use of operators to get RusselSaunders eigenfunctions. 109 Absorption Addition theorem for spherical harmonics. by FermiThomas method. 139 Doublet intervab alkalis. 61. vector addition. 17 Eigenvalues. 3. 166 Commutation rules angular momentum. almost closed shells. 144 Xray levels. 236 Continuous eigenvalues. 14 continuous. 16. of the electrons. 173 Exclusion principle. 60 coordinates and momenta. 19 Commuting observables. 19 where JJ. Chapter Degeneracy.
114 relativistie theory. 144. 86. 4. 108 in alkali spectra. normal Stark effect. 19 Hermitian matrix. 291 Lagnerre polynomials. 14. 216. 388. 278 Jgroup file. 193 absolute. 18 conjugate. 321 Intervals in RnsselSaunders terms. 99 see Strength Interaction between configurations. 300 Isotope effect. 97 Inequivalent configurations. 19. Normal. 287. 147 Odd states. 137 Magneticdipole radiation. Chapter xvm magnetic moment. Chapter Noncommuting vectors. 14 J file. 27 Maxwell s equations. 188. see Strength g factor. 15 complete set. 424 spin. 237 Natural excitation. 97 Fermi statistics. 197. 420 due to. 176 Level. 152. 216. 291 Lynian series. 236. 93. 52. 123 Stark effect. 13 allowed values. 19 Hennitlan operator* 14 Hicks series formula. 303 Parity operator. 6. 14 realitv condition. 344 effects Observable. 285. 100 Mean value of an observable. 8. 281 jj coupling. 137 Hydrogen and hydrogenlike ions experimental results* 137 radial functions. 390 in hyperfine structure. J group. 113 Oscillator strength. 174. 6. 214 intensities. 278 sum rale. 189 selection rule. 27 Matrix mechanics. 90 atomic unit. 426 Paschen series. 217 Multiplet. 54 of proton. 276. 210 Hermitian conjugate matrices. 25 Legendre polynomials. 245 see Inverted. 237 PaschenBack effect. 4. 114 Lande interval Laporte rule. 282 Ftype operator. 158. 109 LScoupling scheme. 25. 168 Induced emission and absorption. 80 in hydrogen. 334 Forbidden lines of astrophysieal interest. 193 see Intervals in MnssdlSaunders terms 236 Parabolic coordinates. 300 Nucleus xv Intermediate coupling. 301 Intervals. doublet. 109 strength. 171 HamDtonian operator. 136. 421. 166 FermiThomas central field. 117 Monad. Cnapter si. 10. 432 of electron. 385 Grtype operator. 375 Matrix. 83 Mean life. 422. 119 spinorbit interaction. 211 Helium and heliumlike ions excited levels. 23 states. 418 Individual set of quantum numbers. 237. Magnetic moment. 195 Lande rule. 97. 219 Inverted multiplets.381. 264 qnadrupole. Strength Multiplicity. 183 Orbital angular momentum. 82. 252 snpermultiplet. 137 . 424 Numerical integration of the radial equation. 2S1 sum rule. 283 grsmn role.436 INDEX SUBJECTS Lavs of quantum meenanics. 151.426 gpennanenee rule* 390 Group theory. 108 in alkali spectra. 97. 248 247. Chapter v. 147 shape in absorption. 422. 185 Oneelectron spectra. 143 Hilbert space. II width. 144. hydrogen. 146.384. 169 /value. 14. 86. 398 Hyper&ie structure. 432 Manvelectron jumps. 6. 422. 8. 98. rale. 278 sum rule. 43 Normal multiplets. Chapter x. 193 nlx configurations. 50. 122 see Allowed levels Line. 186 selection rule. 125 relativity correction. 15 of * in. 208 terms of coupled groups. 424 Magneton. 418. 421 of the nucleus. 398 Parents of a term. 348 345 413 triplet terms.
123. 193. Chapter iv nv Stark effect. 114 Radiation theory. 12. 91 of quadrupole radiation. 9. 3. 34. 432 Poisson bracket. almost closed hydrogen. 37 theory. 209 perturbation of doublet intensities. 162 Allowed levels. 20 Probability interpretation of (F ).21 Ritz combination principle. 168 almost closed. 90 2 Spectroscopic stability. 48. 14 j configuration. 432 retarded. ix RussellSaunders case. 211 intermediate coupling. 84 scalar. 26 335 Statistical interpretation. 8. 327 Periodic table. method and laws. Chapter ix Stark effect. 149 Principle of spectroscopic stability. 240. 354. 97. Zeeman effect. 159 in Xray levels. Polyad. 236. Proton magnetic moment. 249 Spectroscopy. 81 quadnipoleradiation field. 93 Raman effect. Chapter for hydrogen. Strength Rydberg constant. Chapters vn. Intervals. 411 . 93. 100 376 316 dipole multiplets. 362 Shell. 125 Potential atomic unit. 103 Sehrodinger operator. observables. 131 intermediate coupling. 252 Zeeman effect. 83 Scattering of radiation. 55 Spinorbit interaction. 395 Chapter n Quantum number. 282 alkali spectra. 421 mass. 177 Spectra. 245 parity. 2 line. 315 Real observable. 66. 257 LS coupling. 432 Quaclrupole moment. 312 in helinm. 245 Positron. 358. 96 Zeeman effect. 60 Stark effect.INDEX OF SUBJECTS Pauli exclusion principle. 333 Permutation operator. 376 spin of one electron orbit of the other. 125 Stationary states. 112. 5 Ritz series formula. 1 Spectrum of an observable. 380 see Pentad. 159 almost closed shells. 21 Scbrodinger s equation. Representations of states 15. 117. 54 Pauli matrices. 345 and 264 manyelectron jumps. 237 forbidden lines. 14 Relativistic theory. 266. 115. 282 line strengths in quadrupole multiplets. 30. 400 386 angular momentum a 61. 375 quadrupole multiplets. 99. 142 radial. 90 of Dirac. Spinorbit interaction. 21. 320 Secular equation. 268 jj coupling. 143. 1 banded. 332. 89 of dipole radiation. line). 83. 85. 236 multiplicity. 120. 252 RussellSaunders case. 98. 154. 30 277 caused by a single state. 275 jj coupling. 367 Ritz variation method. 24 Statistical method of FermiThomas. 113 Radial functions. 277 Planck s constant. 217. 35 Perturbed series. 237 parent terms. 29 Selection rule. 137. 306. 20 applied to multiplet strengths. choice of. 26 Screening. 4. 301. 23. 24 Proper values. 52 Spin. 103 Raregas spectra. Strength (of a spectral shells. Chapter xvii 5. 131 total. 122 classical electromagnetic theory. 18 effective. 270. 273 Quadrupole radiation. 166 see Equivalent electrons 437 vm. 52. Satellites. 25 Polarization. 295 closed. 83 correspondence principle for emission. 5. 67. Quantum mechanics. 430. 299. 125 Relativity correction. 87 dipoleradiation field. 217 Periodic system. 14 Spherical harmonics. 401. 147. 432 Perturbation. 292 Phases in the matrix of S^. 237 Self consistent fields. 323 Scalar potential. 2 continuous. 83 vector. 367 Phases. 67. State. 27 Schrodinger representation. 95 Xray. 195. 6.
56. 424 hyperfine structure. interaction of the spin of one electron with the orbit of the other. 281 Supermultiplet. 231 eigenfunctions. 8 Vector potential. 3. 148 in hydrogen. 390 gsam rule. 189 Term energies.nebulram*. Chapter xn Wavenumber. 109 in Can. 19 Valence electron. 5.438 Strength.348 Twoelectron configurations absolute term intervals. ionization potentials. 220 allowed levels. 108. 237 Term values. 322 Zeemaa effect. 279 J group. 109 Xray spectra.) INDEX OF SUBJECTS Twoelectron configurations (cont. 165 Symmetry of $. 149 Zeroorder scheme. 237 Universal constants. 432 Term. 339 Width of spectral lines. 278 /group file. Triad. 238. 183 Vector addition of angular momenta. 263 Zeeman effect. 232. 273 line strengths. 122. Xrays. Symbolic algebra of states 12 Ultraionization potentials. 245 267 transformation from jj coupling to coupling. 346. 164 System of terms. 432 Transition array. Chapter xvi in hyperfine structure. 83 Vectors. 385 J file. 287 . 426 in oneelectron spectra. 100. 322 satellites. 0$. 7. 228 model of atom. 36 Trace. 73 Vector coupling. 18 Symmetrizer. 316 line strengths. 167. 43 Transformation coefficients or amplitudes. 247. 191 Term intervals. 247 ^permanence rule. 264 matrix of spinorbit interaction. 79. 244 Transition probabilities. see Intervals Term system. 217 323 TVoelectron atoms. 246. 213 method for RussellSaunders eigenfunc tions.) 229. 283 WentzelBrilouinKrarners approximation. 373 Unitary transformation. 136 in ". 82. 56 in antisymmetric states. 428. noncommuting. 294 LS and observables. 71. 18 for vector addition. 8. 386 Sum rales. (conf. 73 Transformations betveen different coupling scliemes.
198. 423 Compton.. 427 Back. 358 Cady. 423. 264. 358. 373. 276. Brinkman. 403 Gibbs. 362 Blaekett. 368. 424. 128. 405. 105. 140.INDEX OF NAMES Albertson. 138 Chalk. 351 Beutler. 249. Drayvestyn. C. 375. 176. 238. 254. 282 Boyce. 418 Bateman. 131. 56. 7 et seq. 417 Gamow. 140 Catalan. 104 Bouma. 6. 3 Banerji. 219. 10. 256 Bocher. 355 FukusMma. 323 Anderson. 16 Gumev. 359. 132 Bartlett. 131. 208 Ginsburg. 4. 79 Mason. 358. 9.424. 338 Bakker. 28. 335 efe Blaton. 358. 4. 415 Bothe. 371 Bacher. 375 Gross. 415 Dirac. 423 Burger. 366. 337. 423 Doermann. 200. 282. G. 339. Fiiippov. 131. Esmarch. 157. 211. 282 Breit. 423 Fock. 209. 426. 376. 394 Goldberg. 149. 138. 148.. 358 Eckart. 28 Bohr. 60. 326 Courant. 423 Grotrian. 81. 141. 394 Franck. 322. 402. 5 Frenkel. 238 et seq. 103. 10. 390 Darwin. 115. 326 Dnane. Chapter xvi. 197. 394 Gropper. 337. 394 Darwin. 81 Dewey.. 420. 402 Cohen.. 372 . 283. 282. 252 Gordon. 387. 211. 310 Gmelin. 104 Estermann. 240 Engwicht . 342 426 Brickwedde. 325 Baker. 125 Armstrong. 352. 54. 335 Allen. 8 Chaffee.375. 126. 352 149.402 Dorgelo. Frisch. 131. 421 Fermi. 8. 322 Dunn. 274. 327. 5. 140. 390 De BrogHe. 203 Caldwell. 61. 301. 374 Birge. 396 Balmer. 425 Doi. 55. 244. 43 Gibbs. 397 et seq. R. 192. 413. 322 Auger. 182. 396 Carst. 7 Debye. 304. 10. 125 Blair. 209. 406 . K. 140 Granath. 322. 128. 271.406. 195. W. 419 Briick. 425. 401 Born. 416 Guillemin. 245 Epstein. 97 Brown. 61 seq...354 Foster. 374 Allison. 415 Bethe. 189. 124 et seq. 84. 226 Green. 276. 147. 17. 425 Gray. 147. 132 Becker. 407 Gaunt. 147.240 Dobrezov.421 Fues. 120 Frerichs. 357 Gebauer.417 Coster. 149. 131 Bechert. 349. 146.426. 400 Bowen. 427 Grace. C. 206. Chapter n. 87 et seq. 138 Brillouin.428 Black. 37. 387 Bush. 422 et seq.. 132. 107. 400 Goudsmit.&. 169. J. 198. 396. 126..gt. 104. 427 Backlin. 358 Campbell. 349. 10. 418 Einstein. 229.
9 365 Inzils. 387 KufaiClOS Kiipper. 8. 387 Oseen. 274. 125 et seq. 16 Lannor. 4 Majorana. 401 Lysnaai. 189. W. 3 Hartree... 336 Perry.. 2. 394 Lozier. 208 Kirchner. 219 Hund. 259. 342. 396 3kOflikan. G. 390. 61. 369 Hartley. 425 423 Johnson. 367 Langstroth. 416 Lanczos. Land. 149. 10. 336 Hyileraas. 8. 2&. 97. 9. 64. R. 322 Payne.390 Hertz. 428 Peieris. 401 Kiuti. 282 Pearson. 70. OF 425 Hamilton. 341 et seq. 278. Kramers. 336 Leiy. S. 148. 406 et seq. 164. 319 Mott.350. 339. 338 MinkovsM. 400 Kayser. 278. 10. 41 S Humphreys. 310 Isfida.. 220.240. 238. 422 Harms. 373 Mark. 322 Pauli. 276 Micheison. R. 354 et seq. 132 3. 140 Haraeaves. 429 Harvey. L. 64. 3 Kellner. 103 Lawrence. 304 . 373 LennardJones. 107 Korff. 236. 342. Oppenheimer. 325. 108. 140. 358. 239. 346 Kelloscr. 28. 7 Hansen. 386. 245. 97 Hughes. 254 Merrill. 336 Giittinger. 381 et seq. 103. 428 iliiiancziik. 403 Kopfermann. 138. 149 Moseiey. 3S7 Houston. 244. 417 Jackson. 5 Hertz. 323 Jordan. 425 Pauling. 403. 44 Kagaoka. 397 Kronis.. 2 llarweH.. 420 Newton. 107. 9.. 379 Loring. 245 Menzd. 406 Omstein. 390 Joffe. 282 Menifl. 213. 421 Kent. 104 Limeland. 141 MoDougall. 281. 10. C. 193. 368 Ladenburg. 254 Morse. 358 Locher^ 371 Lodge. 369 Jonsson. 140 Pease. 369 Pincherle. 1 OccMalini. 146. 132. Sfas^en. 141. 420 Mitchell. 146 31ilne. 239. 428 Pearson. 111. 415. Lancrer. 372 Hiyama. 7 et seq.gt. 88... 240. 425 Heisenberg. 28. 421. 390 et seq. 104 Ostrofsky. 400 Minnaert. 79 Lorentz. 283. 245. 402. 138 Kirschbaum. 97 Moore.440 Guth.9. 200. 111 Mishima. 295. 35S. 10 Mulders. 166. 81 Jenkins. 304. 402 Martin. 211. 219. 415. 147 Pasehen. H. 138 Phillips. 107. 359 McLennan^ 395 Meggezs. H. 368 Laporte. 281 Lindsay. 138 Kamijima. 423 Jeans. 111 Murphy.. 55. A. 4.300. 1S2 Honl. 153 Kimball. J. 211. 244. 348 Limdblad. 140. P. F. 339. f 2 Hilbert. 140. 8. 271 Hsiek 140 Huff. 78. 107. 415 Kassner. 10. 240. 169. 403 Hobsoii. 266. 149. E. 426 Patterson. 415. 372 Harrison.
INDEX OF NAMES
Planck, 4 Preston, 152, 381
441
Takamine, 403
Taylor, 140 Terenin, 423 Thomas, 108, 120, 335 Torrance, 358
Prokofjew, 148, 254, 256, 342
Rabi, 421, 423
Racah, 420 Ramsauer, 416 Rasmussen, 369
Trampy,
147, 148
Turner, 1S8
Uffoid, 53, 77, 233, 235, 249, 252, 367
Rausch von Traubenberg, 403 Rayleigh, 81 Reiche, 111
Richtmyer, 326 Ritz, 3, 4, 345 Robertson, 405
Rojansky, 399, 415 Rosenthal, 420 Rozental, 310
Uhlenbeck, 8, 54, 126 Undheim, 348 Unsold, 111, 132,139,415 Trey, 10, 138, 342, 423
Ruark, 10 Rubinowicz, 93, Runge, 3, 381
94, 253,
256
Van Atta, 423, 424 Van der Waeiden, 11 Van Geei, 387, 390 et seq. Van Milaan, 244 Van Vleck, 6, 89, 117,
402
Vinti, 109
192,
276,
369,
Russell, 8, 187, 188, 200, 208, 236, 239, 245, 367 et seq*
Voigt, 390, 397
Rutherford, 4
Von Neumann,
Waller, 402
10, 12, 27,
262
Rydberg, 3
Sadler, 359
Sana, 132 Sanford, 254 Saunders, 187 Schlapp, 399
Sehrodinger, 7, 9, 27, 116, 131, 398, 400 Schiiler, 423, 425
Schiitz, 111,
Watson, 114, 340 Weisskopf 82 Wendt, 400
,
Wentzel, 323, 325, 339, 371, 372, 402 Wetterblad, 324
240
6,
Weyl, 11 White, 10, 208, 235, 240, 369, 374 WMtelaw, 369
Sehwarzschild,
Seitz,
397
Segre, 396, 424, 426
WMttaker, 114 Wien, 402
Wierl, 401, 402
76 Seward, 246 Shane, 140 Shenstone, 188, 367 et Sherman, 322
Wigner,
seq., 373, 374,
11, 75, 76, 82, 169,
262
394
Wilber, 208 Williams, 140
Wills, 226,
426
Shortley, 44, 53, 197, 206, 213, 233, 244, 310 271, 279, 281, 284, 295, 304, 306,
Wilsar, 401
Shrum, 395 Siegbahn, 316, 322, 323 Sjogren, 400 Slack, 132, 401 Slater, 139, 158, 352, 354 Snoek, 140 Sommer, 395 Sommerfeld, 6, 10, 132, 139, 239, 319, 322, 390 Spedding, 140 Stark, 397, 400 et seq. Stenstrom, 322 Stern, 421 Stevenson, 256, 282
Stewart, 111
Sugiura, 132, 148, 342
Wilson, A. H., 36 Wilson, E. Bright, 351 et seq. Wilson, Edwin B., 43 Wolfe, 273, 326
Woods, 336
Wulff,427 Wurm, 425
Young, 338
k,
322
Zacharias. 421
Zeeman, I, 378, 395, 427 Zemansky, 97
Zener, 352, 353 Zwaan, 148, 392, 393, 412
.
.
.
TJ .P ^3 CO ".2 C ^^ fjj QQ 106 091 ?5 rn .
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