APPLIED PHYSICS Baitor sal Meehunies Physics rwication Theory va to Modern Physics Volume 1 Volume 1 Physics tal Facts ‘ue aeries from its Inception in ting Eaitor from 1999 to 1946, Principles of Modern Physics ROBERT B. LEIGHTON Professor of Physice California Inetitnto of Technology McGRAW-HILL BOOK COMPANY, INC. NEW YORK TORONTO LONDON 1959 Pe8 Atomic Spectroscopy Of all the tools that have been applied to the study of the detailed structure of matter, it can fairly be said that spectroscopy bus been applied in more ways to more problems, and has produeed more fundamental information, than any other. It has been used, and is still being used, not only to extend our knowledge of the ultimate properties of matter, but also to provide accurate measurements of many quantities of q) tical interest to physicists, chomists, and engineers. It is also an pensable tool in the study of the chemical compasition and the physical condition in which matter exists in cortain situations which are inacees- ible to more direst observation—such as in astrophysics and stmospherie physics—and in situations of a highly transient character, as in fast, chemical reactions and electrieal discharges. In modern physics the term “'spectroseopy” is used in connection ith a great many quite different investigative techniques, e.g., optical spectroscopy (including infrared and ultraviolet atomie and molecular spectroscopy}, microwave spectroscopy, @-ray spectroscopy, y-ray spectroscopy. In each of these techniques the quantity that is directly measured is the energy, momentum, wavelength, or frequency of a photon or electron emitted or absorbed during a transition between two states of ‘an atomic, molecular, or nuclear system. From this information the characteristics of the energy levels of the system are inferred, and from these characteristics (spacing, angular momentum, multiplicity, ete.) certain basic parameters of the system can often be determined with considerable precision. In this chapter we shall examine some of the 4 ‘more important aspeets of the original form of spectroscopy—atomic spectroscopy. 24 sxe. 8-1) 8-1, General C From what ha should be aware stomie spectrost quantum mesh lave with the b certain simple fmprove our we ‘more complicate: Tn the precee Vides a beautif and of the grou visualized as o¢ Iying of the var in the field of due to the rex sussion was Bt requirement tt from the treatr some finer det the extent of t known feature Before act delineate the tatively the ve using for the} ously. ‘Thus visualized as» of a number ¢ of the electron ‘The most gen- importance) * any of the en range of the ¢ sion principle that in whieb when the ato may be comp ionized) and Even with th may fall into excitation wdy of the detailed ‘py has been appliod more fundamental ‘is still being used, erties of matter, but itities of quite prac- Te is also an indi on and the physical 3 which are inaceee- vies and atmospherie saracter, as in fast used in connection niques, eg., optical omie and molecular pectroscopy, y-ray atity that is directly ‘equeney of s photon etween two states of his information the » inferred, and from , multiplicity, ete.) be determined with xamine some of the seetroseopy—atomie seo, 8-1] ‘Anosic sPmerRoscory 8-1, General Considerations ‘From what bas already been said in the preceding chapters, the student should be awace of some of the more important historical facts conoorning somio epectroscopy and the part it has played in the development of the itmtusn mechanics. Having thus arrived at the eorrect mechanics! Heer Aith the help of our knowledge of the spectroscopic properties of vevtain simple atoms, we may now properly seck to ase these Tnws to Smprove our understanding of the epoca and the detailed structure of the ‘more complicated ators. ‘In the preceding chapter we have seen that, quantuan mechanies pro- vides n beautiful interpretation of the periodic system of the elements TE) of the ground state of au atom, wherein the electrons of the atom are sreuolized as oecupying-—subject to the exclusion principle—the lowest Iying of the various energy states that would oxst for an electron moving aie eijeld of Uae nucleus and the spherically syinmetrie average field ‘Tue to the remaining electrons. ‘The approximation used for that dis tee yas purposely kept a5 simple as possible consistent. with the Sauirement that the main features of atomic structure should emerge sr the trealment. Wo now wish to uilize quantum mechanics to add {rom tGner details to the above atomic model and to illustrate further The extent of the success of the Schroedinger theory in aesounting for the inown features of ordinary atoraie processes. ‘Dutore actually embarking upon this procedure, it is desirable to defmeate the present problem more clearly by first considering quali atively the various types of excited states in which an atom might exis aing for the present the came approximate model that was used prev! Gaalg: ‘Thus if, as indicated above, the ground stato of an aon, is srarStized as corresponding to the electrons occupying the lowost-lying Te pumber of posable energy slates, itis clear that, if any one of mors of te electrons were to occupy a bigher level, the atom would be excited. Tessar general state of excitation (which is of completaly mesligible Tnvortance) would then correspond to the various electrons being ip ape the onorzy states incuding the continuum which lies above (be range of the digeretestates-—subject only to the Fimitations of the od soe principle. By far the more common situation, on the other bend, i hak mn which most of the eleotrons are in the energy states they ocupy vie the atom isin its ground state, but in which one oF more electrons wr pe completely removed Srom the atom (that is) the atom is perhene ey lp aud one or two of the electrons aro in bound excited states erie th thie restriction the possible states of excitation of the stom vray fall into several broad classes according to the manner in which *e may guion wee produced. For example, we shall see later that the256 PRINCIPLES OF MODERN PHYSICS fone. 8 ‘oxcitstion of an atom by X-rays or by the impact of an energetic charged particle often results in the removal of electrons from an inner shell ‘This leaves the atom ionized and highly excited, and many interesting phenomena may occur in such a sitation. On the other hand the atom may be excited by rather gentler means—as in an electric are, spark, or glow discharge, or in a flame—in which ease only the outermost of the loctrons will be affected. Although ail such states of excitation are in a sense a part of the same general problem, it is desirable to separate the Giscussion into several different categories upon the basis of the toch- niques used in the study of the excited states. ‘Thus we shall study the states characteristic of X-ray and microwave excitation in later chapters ‘We are concerned at present only with the states of excitation in which tho radiation involved falls in the visible or near-infrared or -ultraviolet, regions of the spectrum; these are states of excitation in which only the ‘outermost, valence, electrons are involved. 8-2, The Hamiltonian Function of a Complicated Atom In order to deduce some of the finer details of the energy levels of = complicated atom, we proceed in a manner similar to that used in the tage of the one-electron atom: narnely, we consider frst a problem which includes the major terms of the Hamiltonian funetion and whose energy levels are therefore very closely the samo as for the complete problem. ‘We then stady the fine-structure splitting of these highly degenerate lovels that results when the next most important terms are inchided as perturbations. For the extremely complicated problem now being eon- sidered, our treatment must remain rather qualitative throughout, even though a certain amount of quantitative information can be obtained by the use of advanced techniques. We shall thus be obliged to place heavy emphasis upon the similarities between the present problet and some of the features of the one-electron atom discussed in Chap. 6. We first consider the various terms that should appear in the coniplete Hamiltonian fangtion of an atom which has a nuclear charge’ Ze and is surrounded by N electrons. We assume for the present that V < Z; that is, the atom is not negatively ionized. ‘The Hamiltonian function should thus be the sum of the following torms: 1. The kinotie energy of the electrons: sro. 8-2] 2, The electrostatic 3. The mutual elec 4, The spin-orbit ¢ 5, The spin-spin i va= 6. Interactions be 7. Wleetron spin Vee 8, Nuclear spin 9. Other terms of the electri: nucleus, inte: orbital motio Tn addition te tions, the Hami appreciable effe: action, such 3s 10, Terms to ecfouar. 8 energetic charged m an inner shel many interesting er hand the atom trie are, spark, or outermost of the ixcitation are in a to soparate the vasis of the tech- re shall study the in lator chapters. citation in which ed or -ultraviolet 1 which only the a nergy lovels of that used in the a problem which nnd whose energy amplete problem. ighly degenerate 8 are included as now being cou hhroughout, even ean be obtained obliged to place nt probleth and in Chap. 5. «in the eomplotec charge’ Ze and is cnt that N <2; Itonian function 886, 8-2] avomic sPEcrHoscory 267 2. The electrostatic interaction energy of the electrons with the nucleus: 3. The mutual electrostatic energy of the electrons: ‘om 2 Leer 4, The spin-orbit energy of the eleotrons: ah AV 2, mire dr 5. The spin-spin interactions of the electrons: eh iatiy eae] 6, Tntrston between the rita magnte moments ofthe dectrous vee Sean nuclear spin interactios Vu = Ht = 3 meted | 8. Nuclear spin-clectron orbital moment interactions: Van tt¥ & vest 9. Other terms due to nuclear clectrio-quadripole moments, modification of the electric field near the nucleus owing to the finite size of the nucleus, interaction between the spin magnetic moments and the orbital motion of other electrons, ete. In addition to the above terms which correspond to “true” interac- tions, the Hamiltonian function should also include terms to represent appreciable effects which do not correspond to a classical type of inter- action, such a8 10. ‘Terms to correct for relativistic effects, e-g.-258 PRINCIPLES OF MODERN PHYSICS fomar. 8 ‘The Hamiltonian function, when converted into an operator, will lend to certain wave functions for the energy states of the atom. According to the exchange-symmetry postulate of the preceding chapter, only those wave functions that are antisymmetric with respect fo the exchange. of all ire of electronic space and spin coordinaies are valid wave functions for the atom. ‘This restrietion upon the choice of acceptable wave fumetions has certain physically observable consequences, some of which have previously been desoribed. For the atomic systems now being con- sidered, the most important of these effects are, as was shown in the preceding chapter: 11. A tendency for electrons with parallel spins to avoid (or “ repel”) each other, and as a result of this and the cloctrostatie repulsion of the electrons, a strong “exchange correlation” between the spins which tends to align electronie spins parallel lo one another. ‘The discussion of the preceding chapter was based upon a model ‘which included terms (1) and (2) and a spherically symmetric “average” of term (3). We must now consider what effects the inclusion of the remaining terms will have upon the degenerate energy levels of that model, We are interested in tivo aspects of these effects—the qualitative character of each term in splitting a degenerate level into a number of distinct lovels of smsller degeneracy, each characterized by a different quantized value of some “constant of tho motion,” and the magnitude of each effect On the basis of the perturbation theory, one ean dedueo the approxi- mate magnitude of the various effects included in the above list. The analysis is too involved to be included here, but is quite straightforward for most of the effects. ‘The finsl conclusion, which is in agreement with observation, is that thore are two main eategorios into which most ‘toms should fall with regard to the relative magnitudes of the remaining effects:! 1. For most atoms, the nonspherically eymmetrie residual electrostatic effects of terur (3) and the spin correlations of (11) are the largest of the remaining terms; the spin-orhit term (4) is considerably smaller, and the remaining terms are quite negligible. 2. For some atoms, mainly the heavier ones, the spin-orbit term (4) predominates, ‘We chall now consider thece two cases separately. + Some of the effects, such os the relativistic eorretion terms, have & very Incge influence upon the lowest energy states, and muck less upon the higher states. ‘These correstiona wil thus appreciably affect the folal ground-state energy of the stom, but not the energies of the states available to the valence eleetrons measured relative to the ground-state anergy. sec, 8-3) 8-8. Russell-Saun ‘The first of the effects: of term (3) remaining terms, ¥ ‘Russell-Saunders o: effect these terms simple central-feld ‘We recall first th were degenerate wi of the various cleo central field and ne keeping device to ‘that is, the individ as well as the net or ‘tum, and the total the motion. Thus degenerate with re ‘equally well in tert » valence electrons @) —— Gadysum ©) MuhySader ()— (raghusiahs) @ — (mbar), ( The first two of = alternative quant electron energy st sions the natural tized angular mo electrons, In the numbers that def electrons, the squ: folal angular mom tum, respectively ‘used in the last combinations of ¢ ‘the same total mt If we now con we see that, sine nucleus, the orbi ‘will no longer be * Astvaplia. Jfouar. 8 perator, will lead tom. According apter, only those w exchange of all ave fumotions for e wave functions of which have now being con as shown in the oid (or repel") ostatio repulsion tween the spins rather. 1 upon model aetric “average”? inclusion of the wy levels of that Sthe qualitative ato a number of sd by a different od the magnitude ince the approxi- above list. The » straightforward agreement with, nto which most, of the remaining ual electrostatic ) are the largest ‘iderably smaller, n-orbit term (4) 5 have a very large ‘igher states. These gy of the stom, but neasured relative to sxc. 8-3] nromic sPpcTROSCOPY 8-3, Russell-Saunders, or LS, Coupling ‘The first of the sbove situations, in which the residual electrostatic elicots of term (8) and the spin-spin correlation (11) dominate the semmaining terms, was frst studied by Russell end Sounders" and is called Rosell Saunders coupling, or LS coupling, Let us now consider what eat these terms will have upon the degenerate enoray levels of the Simple eentral-field approximation. ‘We cocall first that tho various energy levels of the central-ield model wore degenerate with respect {o the orbital angular momenta and spins Whihe various electrons, since each oloctron was assumed to move In & Gratral feld and mo spin interactions were considered except 2s book coping device to prevent two electrons from being in the same state; that io the individual orbital and spin angular momenta. of the electrons, savell's the net orbifal angular momentum, the net spin angular momen fa, and the fotal angular momentum of the electrons, were constants of the mmotion. ‘Tvs the various orthogonal states of gion onerey wore oaenorais with respect to all of these quantities and might be deseribed Ceeally well in torms of various possible sels of quantum nuzabers for the 2 valence electrons, such as (a) Gulisuomsma), (ralaseamontans «+ + » (abe S Moe) (0) Gunnsidiman, (Madama), «+ « » (orrtedn ts) An (o)— Gaulinsihd, (Madatadehy «= 9 Ciodesrdds I Mr Gd) (nalisedy (adage), = =» (agete)y Lr Ss J Me ‘The first two of these expressions will be recognized as being just the ateenative quantumenumber designations for the various individusl one- Sinetron eneruy states as described in Chap. 5, and the last two expres Sone the natural extension of the law of addition of independent: quan- Goed angular momenta given in-that discussion to the case of several Ulctrons. In the last two expressions, L, S, J, and My are the quanturs setahers that define the square of the net orbital angular momentum of the Meatrons, the square of the net ¢pin angular morsentain, the square of the fotal angular momentum, and the component of the total angular momen- ine, respectively. (Note that; although fewer quantum numbers are Geel in the last thro expressions than in the first two, the various possible combinations of quantum munabers in each expression necessarily define the same total number of subsiates of the degenerate state.) Si we now consider the effects of the residual electrostatic repulsions ave sou that, since these involve forces that are not dirceted toward the Toclens, the orbital angular momenta of the individual valence electrons Tail! 'ne' longer be constants of the motion, Since the mutual repulsion 1 Aatrophye. J 61, 38 (1995)260 PRINCIPLES OF MODERN’ PHYSICS [emar. 8 between pains of electrons is directed along the line joining them, how- ever, the total orbital angular mementum will remain constant. Similarly, the spin-spin correlations given by (11) may cause the individual spin angular-momentum vectors to change, but the fotal spin angular momen- tum will be constant, In the case of the spin-spin correlations, the individual spin angular momenta cannot change their magnitudes, since the spin is an intrinsio, unchangeable property of electrons. ‘The directions of tho spins may change, however. On the other hand, in the ease of the electrostatic repulsions, the individual orbital angular momenta could change in magni ‘tude, but this te found seldom to occur. We thus find that the introduction of these two terms into the problem Jeads to situation in which only tho fourth of the alternative sets of ‘quantum numbers given above is suitable for deseribing the substates of the perturbed system, As to the quantitative effects of these two terms, the effect of the spin-spin correlation is usually greater than that of the electrostatic repulsion snd, for the reason given in Exercise 7-13 of the previous chap ter, gives the lowest energy for the state of largest possible S. Further, wo ean goe that the electrostatic energy will be a minimum if the valenen electrons remain as far as possible from one another. Wo thus expect ‘that the stato of lowest energy would be one in which the valence-electron orbite are arranged symmetrically around the periphery of the atom, and in which this symmetrical configuration “rotates” more or less as a. “rigid body.” | Since the individual electrons would all then be revolving in the “same direction” about the nucleus, we might expect the state of lowest energy to be the one whose quantam number L is as large as can be formed from the individual orbital angular-momentum quantum numbers This is observed to be the ease. The states are thus arranged in energy in the order of decreasing L, the largest Levalue having the lowest-lying energy. Finally, we must introduce the small spin-orbit term (4) as an uddi- tional perturbation upon the above eoparated but still individually degenerate levels. It is found that the total spin-orbit intornotion may be represented with sufficient accuraey by an expression of th form simple Vn = FQ)L-S (2) Using this expression for the spin-orbit interaction, we can deduce an important semiquantitative rule governing the fine-structure splitting of 8 given level. We follow a procedure exactly similar to the ease of the one-electron atom except that the rdependence is now so complicated that it cannot be evaluated analytically. We represent it for eaeh given | | sze. 8-3] unperturbed level b but in practice mut ‘cases. ‘The angular tated just as for the and so that ‘Thus the average by the quantum. Be SE since [, IEP, and ‘unperturbed systen We thus see that J, L, and 8 have di 'S, proportional to. 1 multiplet is Bay — Bam ‘Thus the spacing & proportional to the Landlé interoal rade of observed energy To illustrate the specific case of ar ap Uncartrbe "sate + Fra. 1, Eebematic sponding to a 4p am the spacings of the &{omar. 8 sining them, how- ‘slant, Similarly, te individual spin angular momen- ual spin angular in is an intrinsic, af the spins may tho electrostatic ‘change in magni- into the problem Iterative sets of ing the substates the effect of the the electrostatic xe previous chap- 2S. Rurther, we m if the valence ‘We thus expect valence-electron of the atom, and ore or less as a hhen be revolving pect the state of ‘as large as can be antum numbers ranged in energy the lowest-lying (4) as an addi- till individually interaction may vm of the simple e) ean deduce an ture splitting of the ease of the s0 complicated + for each given swe, 8-3] ATOMIC SPECTROSCOPY 261 unperturbed level by 2 constant @ which ean in principle be ealeulated Dut in practice must be evalusted empirically for all but the simplest cases. The angular part of the spin-orbit energy can, however, be evalu ated just as for the one-electron atom by writing J=L4s @) and Up = [EP + 192-4 20-8 @ 0 that 168 = 34(UP = IEP = IS?) 6) ‘Thus the average of V., over the unperturbed wave function described by the quantum, numbers (Id) is equal to ce 8) 4 WOU +) -LO+N-SS+H) » & since |J[ [Z|*, and |S|* are all quantized constants of the motion in the unperturbed system (C" = Ch). ‘We thus ser that, just as in the one-clectron atom, states of different J,L, and $ have different energy. ‘The shift.in energy is, for given L and SS, proportional to J( + 1), and tho spacing of eonseeutive lovels within multiplet is Bin ~ By = KO + DU +2) -JT + DI- CUED @ Thus the spacing between consecutive levls of a fine-siructire mitiplet ia proportional to the larger of the two J-values involved. This is ealled the Landé int Tt can be of great help in determining the J-values ‘of observed energy levels. ‘To illustrate the results of the discussion up to this point, consider the specific case of an atom having two valence electrons and suppose.a s=1 rats a Unported Spin sia eid Spinorit ioe 4 Serotonin gnc ‘cer rey Pra. $1, Schematic diagram illustrating the fie-stsacture spiting of » leve-corre= sponding to a dp and a 4d valence elstron. The Lendé-intorval ral i lutrated in ‘ae spacings of the triplet level,262 PRINCIPLES OF MODPRN PHYSICS lonar. 8 certain unperturbed exited energy state of the atom correspands to ane of these electrons being in a 4p level and the other in a 4d level. The ‘effect of the three perturbations is shown schematically in Fig. 8-1. ‘At the Joft is the unperturbed level. ‘The spinrapin correlation splits this level into two levels, the upper: one having $ = 0 (inglet state) and the lower level having S (triplet state). The electrostatie- nergy term then splits exchof these states into three states having Le ‘values ranging from [2 ~ 1) to Q@+L, thot i, L=1 (P-state), L=2 (Dstate), and b= 3 state). Hach of the triplet levels is then further split by the spin-orbit nergy into three levela having J- values ranging in each ease from |b —1|to(Z +1). Thefinal spee- troscopie designation of the various states is also indicated in the figure. Fie, 82, A diagrammatic illustration of _To illustrate the procedure by ike seuitant op quantan munber for which the expeoted fine-structure 0, 1, 2, 3, 4, and 6 independent electrons. character of a level having more ere ort than to electrons in waflled shells en tke nunber opin ooubinnsons can be deduced, consider the case of three electrons, and for deiniteness let their configuration be 2p 3p 4d. We first find what spin combinations will be present. This is most easily done by first combining the spins of ‘ovo of the electrons and then combining the third spin with each of ther. Figure 8.2 illustrates the possible spin quantum numbers which can be obtained by combining several independent electron spins. We thus find that there will be two sets of doublet states (S « }4) and one get of quartet states (S = 34). ‘Next, we must combine the three orbital angular momenta, If we first combine the two p states, we see that these will lead to an S-state (L=0), « Pestate (L = 1), and a Dstate (L = 2). Combining the state with each of these in succession then leads to S+a5D P+d>P,D,F D+d~+8,P,D,F,G Finally, the introduction of the L- $ coupling splits each of these levels. into an appropriate number of separate levels having different J-values. 1 | see. 83] ‘The two sets of do and the set of qua Su to make a total of 2 speotrum ean K name doublet oF ¢ ponents, respectiy ‘The fine-struct may be generaliz configuration is 1, The unperturt a number of © values of the ¢ electron spins subshell is mor filled, the pos: number of ele Of these level 2. Bach of the « effects into a of different vi L that can b of the » elect ‘any fwo or me the level hav 3, Bach of thes into 28 +1 interval form ‘of these mul multiplets re multiplet, th configuration the largest J ‘The above ¢ energy level itfouar. 8 sponds to one d level. The in Big. 81 relation splits ‘os, the upper ‘singlet state) hnaving $= 1 electrostatic seachof these tes having Z- a 2=1) to = 1 (state), ab=3 @ riplet levels is the spin-orbit els having J- ch caso from Che final pee- of the various in the figure procedure by fine-structure having more unfilled shells ler the ease of + definiteness combinations x the spins of each of them. which can be «We thus rnd one set of ent. If we to an Sstate ombining the € these levels ant J-values, sec. 8-3) Avontc SPRCTROSCOPY ‘The two sets of doublet levels will thus each have as members "Dass Pugs Diss Free Sy Puse Das Fan “Grow and the set of quartot levels the members “Dyan Puss “Diesen Frise Sy Pras Dusen ‘Passn ‘Grrr to make a total of 65 distinc! levels in the multiplet. (Little wonder that fa spectrum can be complex!) Note that, although all leyels bear the name doublet or quartet, some of them have fewer than two or four eom- ponents, respectively, because Lis less than for these levels. ‘Phe fine-structure splitting of a level in the case of ideal LS c may be generalized as follows for the ease of » valence el configuration is mil, mala, - - «tale: 1. Tho unperturbed level is split by the spin-spin correlation effect into a. number of well-separated levels, equal to the number of different values of the spin quantum numbers $ that can be formed from the.» leetron spins, allowing for exclusion-principle limitations if any given ubahell ie more than haij filled. If a given subebell is more than half filied, the possible values of S are the same as would be obtained for a hhumber of electrons equal to the number of vacancies in that subshell. Of thece levels, the one of highest: multiplicity Qargest $) lies lowest. 2, Bach of the above levels is further split by the residual electrostatic ‘effects into a number of loss well separated levels, equal to the number of different values of the orbital angular-momentum quantum number [L that can be formed from the individual orbital angular momenta of the » electrons, again allowing for exclusion-principle limitations if ‘amy two or more electrons are in the some subshell. For each value of S, the lovel having the largest Z lies lowest. 3, Bach of these resulting lovels is again split by the spin-orbit effect into 28 +1 or 2L +1 levels, whichever is smaller. ‘The Landé- interval formula governs the relative spacing of all levels within each ‘of these multiplets, using approximately dhe same value of C for all ‘multiplets resulting from a given wnperturbed level. Within @ given multiplet, the term having the smallest value of J lies lowest unless the configuration involves a rore-than-halfflled subshell, in which case the largest J lies lowest. ‘The latter are called éweried multiplets, ‘The above description shows that the fine-structure splitting of an cenorgy level in LS coupling can be quite complicated if very manysnc. 8-3) late the various poss electrons; first_ treatin take account of the ex electrons by'striking 0 and by eliminating du 1, 4, 17, 20, 83, and ramte BL my AN Fra. 8-8, Schomatio illustration of the LS fne-struchure ppltting of a configuration i involving two p electrons. The dashed levels are missing from the multiplet i the ‘leetrons are equivalent (n= 1). valence elotrons are involved, ‘This eomplerty is somewhat reduced, of course, if some of these aro ia the some subshell. Bletrons whieh in the sgine subsbell are called equivalent elecons; the eachision le mat always bo taken info account in analysing the fino truce” | '@ Configuration involving equivalent electrons. } In case a subshell is more than half filed with electrons, the applicas | + Sn ft ection pine ads nthe mpora el at le | |3 | a] 0 combinations of L and S available to these electrons are exactly the same as if only a number of electrons equal to the number of unoccupied subsiates in the subshell were actually present. (Thus if five electrons were ins certain P subsholl, the sumber of J; and S combinations would be exactly the same as for one electron in this subshell, namely, $ = 14 and L = 1.) ‘The most complicated fine structure therefore is associated with those clements having approximately half-illed subshells, As an illustration of the effect of the exelusion principle upon the fine struclure of a level, the fine-structure splitting is compared schematically in Tig. 8:3 for two equivalent and for two nonequivalent p electrons. ‘The levels missing from the fine structure for the equivalent electrons are |p of states as 2 8 fhown dotted. > | numbers 1, 2, 3 ete This figure indicates that the *D, "8, and 'P terms: that are found combinations of Mi in the fine structure of a configuration of two nonequivalent p electrons shown in Table 8-2 are missing from the corresponding multiplet for equivalent electrons. + with, the states expt ‘These terms are eliminated because of the exclusion-principle requirement Dye OF these, w that no tro electrons may have the came set of quantiam numbers m, 1, present, since this w ‘my and m, and because only physically distinguishable slales can be : rules out the. presen counted. of a given L aid § ‘The general case of any number of equivelent electrons is best treated requires the presen: by the use of group theory, but unfortunately this method is beyond the available combinati seope of the present work. We can, however, deal with the particular more, state 1-can case illustrated in Fig. 88 by a more elementary method. Let us tabue froin this we conclu1g of a configuration athe multiplet if the omewhat redueed, Electrons which ans; the exclusion jing the fine strac- bons, the applica ab result that the saclly the same asf ried eubstatos in the “were in a certain ald be exactly the = Mand L = 1) ociated with those siple upon the fine ared echematically valent p electrons. ‘alent electrons are 1is-thab are found ivalent p electrons aivalent loctrons. ciple requirement tum numbers n, 1, able staiee can be ‘ons is best treated thod is beyond the vith the particular rod. Let us tabu- suc. 83] ATOMIC SPECTROSCOPY 205 late the various possible values of ry msi, Min, and ma for the ove uit tone, fist treating, them as novequivalent (Table 8-1), We then eeerrverant of the exclusion psiniple and the indistinguishability of the arrctrons by sizleng Gut Uiose states fr which fn = Ma and ma = M2, Sod by eliminating duplication of indistinguishable states. Thus eve ty 4, If, 20, 83, and 86 are removed by the frst criterion, ‘and such ‘Tanue 8-1, mi ano m, Vators vor Two Eauwatewr p Bincmons batt rere ree out tt our 5 and 13, 8 and 15, éte., are Jabeled with new parsers 1, 2, 3, ote. For two oquivalent p electrons, only the Fifteen wer vations of Mi, = ma + min, My =a + mand My = Ma + Ms Shown in Table 8-2 ate possible. ‘We must now compare those sates eer tho states expected in the LS spultiplet: ‘Se *Pi, ‘Da “Sie ‘Pain sane Of these, we ean immediately vee that the *Ds stato canna De present, since this would require My values of 4-3 and —3. Thin W% Prerant the presence of D1 and *Ds; since if one possible combination sre given D and 8 is pressnt, all must be, On the other hand, tate ® seduafos the presence of an LS term with Z > 1 and 82 1. Of the eatrable combinations, this requires that: "Po... bo present.” Purthes: ree atate. Loan come’ only from an LS tern: having Li2 2.and:S 2:0; from this we conclude that the *Ds term must be present, pairs of states as 2 and 3,266 PRINCIPLES OF MODERN rHYsiCS fenar.'8 ‘Tapie $2, Mi, Ms, axo My Vators ror Two Equrauswr p Enwernows If we now count how many independent LS terms are known to be present, we have, from *P:, *Ps, and *Ps, 6 +3 +1 = 9 states; from §D., 5 states, or @ total of 14, Furthermore, those states require I, values of $2, +1, 0, —1, ~2; +1, 0, —1;0; and +2, +1,0, —1, —2, respectively. | These account for all of the Jf, values in the table except for one, whose M, value is zero. This then both permits and requires 3, to be present. By this procedure we have found that the fifteen independent states of two equivalent p electrons are to be identified with the fifteen LS states contained in °Ss, "Ds, and *Pexz2. By a similar procedure one can deduco the fine-structure terms for other configurations involving equivalent electrons, with the results shown in Table 8.3. If @ given configuration contains both equivalent and nonequivalent electrons, one can analyze the LS coupling fine structure by starting with the equivalent electron terms and combining the other electrons, ‘one by one, with them, ‘Thus for the configuration 4p? Ss, the LS terms would be a __ 8S +52 Sy D +s Diese P+ 82 Py, Prue EXERCISES. 8-1 Add up the degeneracies of the various LS terms appearing in ig. 8-1 and thus verify that this is equal to the degeneracy of the 4p 4d level, Ans. g = 2X 3X 6 = 60, 8-2. Add up the degeneracies of the various spin states appearing. in Fig. 8-2 and thus verify that this is equal to 2", where 1V is the number of electrons whose spins are to be combined. (Bach electron can inde- pendently have either of two orientations.) ‘This expression is of course valid only if the exclusion principle does not limit the possible spin: orientations. snc. 8-3) or example, (% "Phe exponents that appear multe multiplicity and Z value having the given ran uze the total number 0 o proveding upersorpis are tune 83. LS Teaus Anreie reox Equwvasent Euxcrnonst the number of distinot trme bers in th Sst eo five 2D states, ete ‘inthe third column, In this table the ‘the second column, theses for felestrons oremesremnannienenennrtnens sree TT {acer ops ‘oe “oar ‘tBu FommAK Pe“soaTEA “*AAEO 4 Be GMOAGADe (NI 61 eR LD 6 aCe Sh (00 aN WV ST OM el wD wl Cad Sh eave) “ge (G5 hE oD od CLES) (ON DN TIL oT LoD ok Toe (0 oN WBE TL a LD 0 2h (e008) (Gee Ged aoe ed a 0D ni eC sy (ON oDW eT BL aE BL oD a ol vcs (coon) odds), ONT sM a oH oD vA oleae (NC FDS eT eH Dd (oon) ‘ (IML all 19 ed ee | (ae (tay: (198): (18) a ; oD E (Ody UOADS)« (Aa (HDAGA« Ge § ‘ds (HOSGaNe (OAC) a (Udy (HOAA: Ge 5 i g juopwmagueg | sovese dopey sum 7 ayo e0nvi® Ce 289 ‘SOV le duns 10g “ones/7 pov Anpydnes won oy Rosey ean oxy 30 ogee 28 HONEST} 9 SS tony oe spdouedi Supecond ov Sampo PEN ogy UE “wumgoe POND ‘ ene depet Yo seq re a} ore oUTfoo wy OY TF Gun ow SAW SEY MT rary SHOE, $7 “ES ETO ano} 029 0% Tease op apieuy seadde porn swe OHLL, Toad suopyeandyee 993 0 Suspodses109 foxourmig cxwrvainda wows 0 Ta 258 a 4952 g228 SR ab age. ae TEcte ges £533 ee wEE ge i ggaTs! 2355 223e as aes Als[reersze [28899 438. 25] BRB & £2 So 2 eS 35 Slslrevsove [altaeh BESESE S25 Aieio268 PRINCIPLES OF MODERN PITSICS fonar. 8 8-9. By gonsidering the combining properties of the spin angular momenta of: a number of electrons, establish the lax of alternation of ‘multiplicities for LS coupling: “The spectral terms of successive elements in the periodic table alternate between even and odd multiplicities.” 8-4, What spectral terms result from an electron configuration 3d 4f, assuming LS coupling? Indicate on a sketch the expected spacing of the various components of the multiplets. 8-5. What spectral terms result from an electron configuration 2p 3p. 4p, ascuming LS coupling? What degree of degeneracy is possessed by each of these levels? 8-6. What spectral terms should be present in the configuration 2p* 3p? ‘The foregoing description of LS coupling provides a basis for predict- ing the spectroscopic character of the ground state of a given atom. The ground state ought to possess the highest values of Land S—and if the valonce subshell is Jess than half full, the smalles¢ value of J—that are possible under the limitations of the exclusion principle. (If the valence subshell is more than half filled, the largest value of J will lie lowest.) ‘When the exclusion principle limits the possible combinations of [1 and 5S, the ground state is found to bo a state of the highest multiplicity (largest value of 8) that can be formed under the exclusion principle. If more than one value of L is possible for this multiplicity, the largest ‘of these values determines the ground state, ‘Then, depending upon whether the valence subshell is less than (or more than) half filled, the smallest (or largest) value of J for this combination of S and L completes the identification of the ground-state term. ‘These rules, which almost, without exception are observed to hold, show clearly that the spin-spin correlation effect which tends to make the spins line up parallel to one another is the largest of the perturbation terms, followed by the residual clectrostatic effects which tend to line up the orbital angular momenta, ‘and then by the spin-orbit term. BXERCISE 8-7. Show that the following ground-state terms satisfy the above rules: BCP), Se*Dy), SePP,), ZCF2), Nb(Dy), Pr(‘ly), TaCEs) 8-4. j-j Coupling Although the LS coupling scheme described above provides a suitable description of the fine-structure splitting of most of the energy levels ‘of many atoms, there is another type of coupling which occurs for some atoms. In its ideal form, this second type represents an opposite extreme to ideal LS coupling in the sense that the fine-structure splitting of any sec. 8-4] igiven level oan be des of the two extreme t ‘ocears in its ideal for the residual_clectros! in this case the lan analogous, for each Fic, $4. Schematic i coupling Chap, 6 for the one tions in splitting the 1, ‘The spin-orbit ¢ spaced levels, ea the possible. js Eq, 5-8(6) itioll toall of the elect number of level orbital angular principle, and i 2. "The dlectrostati split each of t by different val ‘exclusion prine! We thus see th of the individual various levels are ‘As an illustrati ease as was dese schematically hor produced by the Fovalues 36 of 34, spin-orbit effectfouar. 8 ‘pin angular Hternation of ‘ive elements Aicities.” ration Bd 4f, d spacing of ration 2p 3 possessed by ation 2p? 3p? 3 for predict- 2 atom. The sand if the 1 J—thet. are {f tho valence ie lowest.) ions of Land & multiplicity principle. If yy the largest dending upon naif filled, the AL completes whieh almost, the spin-spin snrallel to one y the residual Jar momenta, ay the above », TaC'T) ides a suitable energy levels ‘ccurs for some posite extreme plitting of any sue. $4] [amoMic SPECTROSCOPY 269 von lvel can be described in terms of 2 coupling which sa aixiure” sere wo oxtreme types. ‘Tho second type is called jj coupling. 1% See nite ideal form ifthe spin-orbit energy {term (4)] greatly exceed fhe residual elestrostatic eneray and the spin-spin coneiation nett” Pe Eke the largest part of the fine-structure epliting is exactiy cnalogous, for each electron, to the spin-orbit splitting deseribed in baal 9 * arasians foe [i230 omgges 4 Stagt +t Fre. $4, Sohematieillastration of the fine structure of « Pa courting: Chap. 5 for the one-lectron atom. The effets of the various perturba Rane: splitting the unperturbed energy level can be described as follows: 1. The spin-orbit effects split the original evel into a number of well ruc Teves, each of which eorresponds to diferent combination of Tee possible’ jevalues for the individual. valener_electrons, sore iq, 5-8(6) it follows that the lowest-lying of -gals will orrespond easyer the electrons having thei smaller j-value (je = & ~ 4). The +o ar of levels depends upon the number of walends electrons, thelr venitel engular momenta (only one j value if | ~ 0), and the exclusion principle, and it cannot exceed 2”. 2, The clectrostatio energy and spin-spin com split each of the above levels into a num! by different values of the total angular moment exclusion principle may act to limit the number We thus cee that a given final lovol is characterized by the J-veles of whe Indfeidual valenge electrons and by the total value of J. ‘The ot ane ovels are commonly deseribed by the notation Judo - ale ona illustration of the j,i coupling scheme, lot us"consider the same case ae was describod in Hig, 8-1 for LS coupling. Figure $-4 shows case ee ceally how the expeoted fin structure for ideal -j coupling i rodtced by the perturbation terms. The 4p electron can Sve the Pirates 34 or 34, and the 4d electron the j-values 94 0 4 “Thus the. ‘m-orbit affect splits tho unperturbed level nto Jour levels, of whieh relation energy then further ber of levels characterized Hero again the f possible values of J. configuration in fj270 PRINCIPLES OF MODERN FITYSICS fenar. 8 a1, {—— @n2,112), a & \— aaa, eet 279 ‘Yoo. £5, Dhustesting the gradual trend from ideal LS coupling in the ight elements toward jj coupling in the heavy elements, (Adapted by permision from HB. White, STutredustion to Atomic Spectra,” McGraw-Hill Book Compeny, Inc, New York, 1884) (4, 34) lies lowest and (84, 34) highest. ‘These four levels are then farthor split by the electrostatic and spin-spin correlation energies into ‘the new levels shown. In each ease the number of levels is equal to the number of integrally spaced values of J that ean be formed out of the two Sevaluee. ‘Note that the tolal number of final levels is the same as for the LS coupling scheme and that the J/-value designations are also in one-to-one correspondence for the two schemes. Because of the highly schematic nature of the above example, itis not possible to define which of the above levels corresponds to each of the levels in the LS coupling scheme. The gradual shift in the coupling for certain levels from L$ coupling for the light elements toward j-j coupling for the heavy elements has been studied for several groups of elements. One of the best illustrations of this is provided by the carbon grotip of elements. Figure 8-5 shows sche- ‘matically this change for the lowest-lying ps excited level in each of the members of this group. Tn actusl fact, one seldom finds that the fine structure of a given con figuration is exactly describable in terms of ideal LS or j-j coupling, because the relative magnitudes of the spin correlation, electrostatic, and spin-orbit energies do not satisfy the requirements of the idealized theory. Fortunately, by far the majority of cases are sufficiently close to ideat LS coupling that the LS notation is appropriate bath qualite- tively and quantitatively. Several cases falling between the ideal limits have been successfully treated, so that the observed departures from ideal LS or j-j coupling are well understood theoretically. Accounts of such treatments ean be found in advanced textbooks on spectroscopy. 8-6. Selection Rules ‘The two coupling schemes described above produce a quite satisfactory semiquantitative basis for intorpreting the energy levels of multielectron sec. 85] atoms, In order tov tions between these 1 rules govern the most given below are thos: ‘be derived by using © eigenfunctions and d functions. A few dey have only a weak int closely similar to th electron atom. A. Selection Rules i, Transitions occur changes its state. 2, ‘The Lvalue of the ‘This is a special ware function m rising from cont soript 0, that is, 8, For the atom as change as follow 88 AJ = 0, AM; = 0, + B. Selection Rule 1, Transitions oc changes its state 2. The Lvalue of more generally, 3. aj =0, £1 fo electrons. 4. For the atom a Ay = 0,4 AM, = 0,4 ‘The above selec majority of trans rules involve tran or (in LS eoupliny than one electror of the individual ¢[cuar. 8 672,112), Gr2,112), 2,112), 72,172), elements ‘om H. E. White, Ine,, New Yerk, vols are then | energies into is equal to the ‘out of the two as for the LS im one-to-one shly schematic hoof the above scheme. The upling for the as been studied sions of this is 5 shows sche in each of the of a given con- , dloctrostatic, if the idealized ficiently close > both qualita- the ideal limits epartures from ‘Accounts of ‘pectroscopy: site satisfactory if multielectron ssc. 8-5) ATOMIC SPECTROSCOPY m1 atoms. In order to understand the spectral lines that result from transi- tions between these levels, however, we must also know what selection rules govern the most common types of transition. Tho eeloction rules given below are those for eleciriedipole transitions. Most of them can be derived by using only the genoral proper ¢ angular-momentiim eigenfunctions and do not require a knowledge of the complete wave functions. A few depend upon the assumption that the valence electrons have only a weak interaction with each other. Note that they are very closely similar to the selection rules derived in Chap. 6 for the one- electron atom, A. Selection Rules for LS Coupling - 1, Trunsitions oocur only between configurations in which one electron changes its stato, (Only one electron “jumps” at a time.) 2. The E-value of the jumping electron must change by one unit (Abs #1 ‘This is a special ease of the goneral requirement that the parity of the wave function must change in an lectriodipole transition. Terms arising from configurations of odd parity are so designated by a super setipt 0, that is, *Py 3, For the atom as a whole, the quantum numbers L, S, J, and My must change as follows: O80) Ab = 0,41 as = 0,41 bubs ©0—>/ = 0 forbidden aif; = 0, but My = 0— My = 0 forbidden if Ad = 0 B. Selection Rules for ii Coupling 1. Transitions occur only between configurations in which one electron changes its state. (Only one electron “jumps” at a time.) 2. The Evalue of the jumping electron must change by one unit; oF, more generally, the parity: must chang. 3. Aj = 0, £1 for the jumping electron, and aj = 0 for all the other electrons. 4, For the atom ass whole, AJ =0,41 but J =0->J = 0 forbidden AM, =0,41 but My "The above selection rules are observed to be in operation in the vast majority of transitions. The commonest violations of these selection rules involve transitions in which more than one electron. changes its state, or (in LS coupling) in which dhe spin changes by one wnil, Tn case more than one electron jumps, the selection rules still require that the sum of the individual orbital angular-momentum quantum nusnbers change bym2 PRINCIPLES OF MODERN PHYSICS fenar. 8 ‘one unit for an electric-dipole transition, since the parity of a state is just that of the sum of the Z quantum numbers of the electrons. 8-6. Energy-level Diagrams for Complex Atoms One of the most satisfactory ways of describing the character of the spectrum of a given atom is by means of an energy-level diagram similar to that used to illustrate the fine structure of hydrogen (Fig. 5-6). snaters TRIPLETS Spee aoa SOs "Faas ycronerd 4 He 1 4 a- | (round state: 15? 5, / is mo Ie nd io, 86, Term diagram for novtral helium, the following pages, diagrams are given for a number of atoms, In A partial energy-level diagram for relatively simple “complex” atom is shown in Fig. $6 or helium. This element has, in its ground state, two ‘equivalent electrons in the 1s subshell. ‘Thus from the foregoing con- siderations we expect the ground state to be a 2S) state. The lowest excited states involve the elevation of one of these electrons into a higher see. 8-8) shell, so that the ex two electrons only si Lo group to the othe: is shown in Fig. 8 in the spectrum of of one group may getting to the gro dipole or electrie-«fowar. 8 rity of a state is Jectrons. character of the 1 diagram similar n (Pig. 66). In | ae ne is mp Is nd cr of atoms. A omplex”” atom is sround state, two ve foregoing’ con- ate, The lowest ‘ons into a higher sec. 8-6] ATOMIC SPECTROSCOPY 278 shell, so that the exclusion principle does not affect these states. For ‘wo electrons only singlet and triplet states can occur; and because of the selection rules AS “= 0, it is convenient to represent these states in ito separate grousi mitted transitions occurring only within each ‘group. A transition which violaies this selection rule then goes from one snGLETs 2g My *0R oy Yet fey ts) We fie ti | or Ground sates Mato’, 4 Fis. 87. Torm diagram for noutral carbon, group to the other and is called an intereystem fransition. One of these is shown in Fig. 8.6. Tt often happens that some of the strongest lines in tho spectrum of an atom are intersystem lines, because the lowest level ‘of one group may lie above the ground-state level and the only means of getting to the ground state from this state may be through a magnetic- dipole or olectrie-quadripole transition. ‘Thus even though the probabil-am Puivcirins oF MopERN suaccs {ona oua.ers cuarers eae he ET | SE Gast Hae SDSS “tata ei alter = 7 yc ~y NI round state: 1stos%ap! S95 acted tes = | stage, roles | wl pa cee . nou 4 Fic, 88, Torm diagram for neutral nitrogen. ity of such a transition is many times smaller than that for an electric dipole transition, itis still possible to have a strong spectral line, because ‘atoms will continue to fall into this state from sbove until the number of atoms in itis so great that mnany transitions will ocour per second in spite of the low transition probability per atom. In Fig. 86, it should be noted that the higher excited levels approach those for neutral hydrogen quite closely. The transitions between these levels would thus approximate the corresponding transitions of hydrogen, except that the helium lines would show different fine structure. Energy- level diagrams for other eomplex atoms are shown in Figs. 8-7 and 8-8. 8-1, Regularities in Complex Spectra From tho earliest investigations of atomic spectra great effort was spent to discover quantitative or qualitative spectral regularities and to sec. 8-7] relate the spectra of spectral regularities v problem of determi: various energy level vided an exceedingly and has itself aided elements. We have derived from the 9 atoms. There are s ined, however, and i principal regularities A. The Rydberg-s tive relationships be were discovered by in Chap. 2, expresse from the Schroeding have a form similar able from the stan already been points electrons of a neutra an inverse-square fix oxcited states of a ‘excited ought to Fig. 8-6 for helium ‘of the spectra of th Of course the lo hydrogen levels ve: of small total angul nearly “circular” fon the basis of tt momentum toware electrons is smalle spectra, B. The Hartley Rydborg’s work in covered that the st plet line in the va ‘measnrod in terms doublet or triplet + ‘This law is an obv Binstein condition energy difference ¢ then all transition. 4 state ation Se atts: | fant | | Sapterso)4 np 8 = for an electric- ‘al line, because silthe number of second in spite Levels approach 1s between these ions of hydrogen, aeture. -Energy- gs. 87 and 8.8. ‘great effort was sgularities and: to see. 8-7] svomie spmeTRoscoPY 275 relate the spectra of neighboring elements in the periodic table. Many spectral regularities were found empirically and were used as an aid in the problem of determining the correct spectroscopic designations of the various energy levels in an atom, Modern quantum theory has prov vided an exceedingly satisfactory theoretical basis for these relationships and has itself aided greatly in the task of mapping the spectra of the elements. We have already soon how some of these regularities ean be derived from the spplication of the Schroedingor theory to complex toms, ‘There ato several regularities that we have not explicitly exam- ined, however, and it is thus worthwhile to tabulate in a single place the principal regularities that can be observed in atomic spectre ‘A. Tho Rydberg-series Relationships, The earliest gefioral quantita tive relationships between certain lines in the specteum of many elements wore discovered by Rydberg. Rydbere’s series, which were described jn Chap. 2, oxpressed empirically a fact that can also be soon to follow from the Schroedinger theory, namely, that many atomie spectral series have a form similar to the Balmer series of hydrogen. This is reason- able from the standpoint of the Schroedinger theory because, as has already been pointed out, the olectrie field felt by a single one of the ‘electrons of a neutral atom at large distances from the nucleus approaches fan inveree-square field due to a singly charged nucleus. Thus the higher ‘excited states of any neutral atom in which only 2 single electron is excited ought to approach those for hydrogen. This is illustrated in Fig. 8-6 for helium, and it constitutes one of the most striking features of the spectra of the alkali metals Of course the lower excited states of an atom do not approach the hydrogen levels very closely, especially in the cases of the lower orbits of small total angular momentum. ‘This regular progression of the more nearly “circular” orbits toward the hydrogen levels can be explained ‘on the basis of the greater penetration of the states of low angular Inomentum toward the nucleus, where the shiclding effect of the inner clectrons is smaller. This effect, too, is quite prominent in the alkali spectra. 'B. The Harlley Law of Constant Doublet Separation. Keven before Rydbere’s work in oxpressing series in analytic form, Hartley (1883) dis- covered that the separation between corresponding members of armulti- plot line in the various members of a spectral sories was when measured in terme of reciprocal wavelength; that is, the components of a doublet or triplet series are separated by the same frequency difference. ‘This law is an obvious consequence of the idea of energy levels with the Einstein condition relating the frequency of emitted radiation to the ‘energy difference of two levels, since if one energy level is, say, a doublet, ‘hen all transitions that begin or end on this level will yield two sets of