No two electrons in an atom can occupy the same quantum state. Since an atomic state can be described by the four quantum numbers 2, f, m, and m,, the exclusion principle may also be stated as ave the same values of all four No two electrons in an atom can h quantum numbers (7, I, my m,). The Pauli exclusion principle has a more general and much deeper significance than what is apparent from the above discussion. Physicists have divided all particles into two classes: fermions and bosons. Particles having half-an-odd-integral spin are called fermions because a system of such particles is governed by the Fermi-Dirac statistical distribution law, Electrons, protons and neutrons are the most important examples of fermions. Particles having zero or integral spin are called bosons. A system of such particles is governed by the Bose-Einstein statistical distribution law. Photons and alpha particles are examples of bosons. It is found that only the fermions obey the Pauli exclusion principle. Thus, a more general statement of the exclusion principle is: No two identical fermions in a system can occupy the same quantum state, 14.3 SYMMETRIC AND ANTISYMMETRIC WAVE FUNCTIONS: THE GENERALIZED PAULI PRINCIPLE Before proceeding with the upplication of the exclusion principle in determinin, the electronic configuration of elements, let us see what are its implications bd constructing the wave function of a system of identical pareles At the microscopic level, the identical purticles are literally indistinguishable from oneNT en eg ee, Le A particle s¢ yn another similar particle. This fact has to be 10 that it may be distinguished {ro ‘ons atit " q taken care of in constructing ihe wave functions of identical particle systems, For simplicity, let us consider siwo particle system. The particles are assumed to be noninteracting. Suppose particle | is in the state labelled a and particle 2 is in the state ubelled b. Then it would be natural to think that the two-particle wave function might be written as PCL. 2) = wal) yp(2) (14.3) Here the letter a or b represents the set of all the quantum numbers which define a particular one-particle state. For example, if the Particles are electrons inan atom, then a or b represents the set (1, [, m, m,). The integer | or 2 refers toall the coordinates of a particle. On the other hand, if particle 2 is in state @ and particle 1 is in state b, then the two-particle wave function would be YQ, 1) = v2) yw) (14.4) Now, since the particles are indistinguishable, neither of these wave functions is satisfactory because we have no way to find out which of the two describes the system at any moment. In fact, both the situations are equally Probable. Therefore, the proper description of the system would be a linear combination of ‘¥(1, 2) and ‘¥(2, 1). Two such combinations are possible. The first is the symmetric combination Ws(1, 2) = wee 2) + ¥2, D) van Yol2) + vol) oCI)] (14.5) Tre other is the antisymmetric combination ¥,(1, 2) = wen. 2)- #2, D1 = zn Wo2) - ve) VAD (14.6) bes factor 1/V2_ in front is the normalization constant, Ys(1, 2) remains nt when the two particles are exchanged while W,(1, 2) changes sign Such an exchange. That is, ang Pus, 2) = ¥s(2, 1) = WoC, 2) (14.7) PyAPACL, 2) = P,(2, 1) = - WAC, 2) (14.8) Where Key 2 is the particle exchange operator. The overall sign change is Want because physical probabilities involve only the absolute squares of Ye functions, which remain unaffected by a change of sign,Now comes the important question: Which of the two wave functions, '¥, or Y4 must be used to describe a system of two identical particles. The answer is provided by the Pauli exclusion principle which says that no two identical fermions in a system can occupy the same quantum state. If, in violation of the Pauli principle, we put a = b in the right hand sides of (14.5) and (14.6), we find that ‘4 becomes zero whereas ‘¥; does not. Thus, the Pauli exclusion principle requires that only an antisymmetric wave function be used to describe a system of fermions, which includes electrons, the particles with which we are mainly concerned. The antisymmetric wave function for a two-fermion system [Equation (14.6)] may be written conveniently as a 2 x 2 determinant: liv. y,() YC, 2) = = ‘ V2 |val2) 92) This form can be immediately generalized to write the antisymmetric wave function for any system of N fermions as an N x N determinant: (14.9) Va) Wa) We, a2) Wagl2) Wa yl2: Ya) Wei) Ver | aga Voi(N) Wag(N) os Way(N) This is called the Slater determinant. The other class of particles, bosons, have wave functions that are symmetric under exchange of any two identical particles. It is found that it is more fundamental and useful to classify particles according to the symmetric or antisymmetric nature of their wave functions rather than according to whether they obey the Pauli exclusion principle or not. The generalized Pauli principle may be stated as: The wave function of a many-particle system is antisymmetric under the exchange of two identical fermions and symmetric under the exchange of two identical bosons.Spin wave functions and the role of the Pauli exclusion Principle Until now we have not Ken into account the spin of the two electrons. In the case of one-electron atoms we have seen in Chapter 5 that the electron spin only affects the fine and hyperfine structure of the spectrum. On the contrary, for two- electron utoms, we shall see that spin effects directly infuence the because of the requirements of the Pauli exclusion principle Since we are dealing with the Hamiltonian (7.2) which is spin-independent, the atom can be completely described by specifying ils spatial eigentuncuon, together with the components of the electron spins in a given direction, which we choose spectrumas our Z axis, Thus the full cigenfunctions of the system must be products of the spatial eigenfunctions y(r,, r)) satisfying the Schrédinger equation (7.3) times spin wave functions (1, 2) for the two-electron system. That is, (qi. 92) = wri, )ZC, 2) (78) where q, denotes collectively the space and spin coordinates of electron i. Spin wave functions The spin wave functions x(1, 2) are easily constructed from our knowledge of the spin wave functions x,2,(1) and 7i2,,(2) of the individual electrons. Let us denote by S, and S, the spin operators of the two electrons, and by (S,), and (S,), the components of these operators along the Z direction. We also write the basic spin functions (see (2.209)) of the two electrons as a(1), B(1) and a(2), B(2), respectively. We emphasise that S, only acts on a1) and f(1), while S, operates only on @(2) and B(2), so that the two operators S, and S, commute. The total spin angular momentum of the two electrons is represented by the operator S=S,+S, (15) whose z component is 5S, = (Si). + (Sz); c (7.10) Because $? = $3 = 3/4 (in a.u.) we have S? =Sj +S3+2S,:S, =++28,-S, (7.1) Since there are no spin-dependent interactions each electron spin component in the Z direction can be directed either up (1) or down (1) independently of the other, and we have four independent spin states each of which can be represented as the product of two individual spin functions. That is, H(A, 2) = a(1)a(2) TT 721, 2) = a(1)B(2)TL 7001. 2) = BO) a(2)LT 24,2) = BL) 2) (7.12)BROORMIE DACK at the four spin functions (/.12), we also see that both Y, and Y, are symmetric in the exchange of the labels of the two electrons, while neither x: nor y; is symmetric or antisymmetric. As we shall see below, it is essential to deal with two-electron spin functions which are either symmetric or antisymmetric in the interchange of the electron labels. Fortunately, it is easy to form linear com- binations of y, and x; which are respectively symmetric and antisymmetric in the exchange of the electron labels 1 and 2. That is, “(1 2)= pa (7.16) and 201.2)= EL, 9-002] oan y2 where the subscripts + and - denote the symmetnc and antisymmetric functions, respectively, and the factor 2'” has been introduced so that both x, and x. are normalised to unity. Using the results of Table 7.1, we see that the symmetric spinTable 7.2 Values of the quantum numbers 5 and M; for the antisymmetric spin function (7.18), and the three symmetric spin functions (7.19). Each of these spin functions is a simu taneous eigenstate of the operators $ and 5, with eigenvalues given respectively (in a.u) Cm 5(5 +1) and M,, The antisymmetric spin function (7.18) corresponding to 5=0M,=Oisa spin singlet, while the three symmetric spin states (7.19) corresponding to 5 = 1 and M, = 1,0, are seen to form a spin triplet Spin funtion 5 M, $lac1ye2) ~ Baa(2)) 0 o a()a(2) 1 1 la)Be2) + BAYa(2)] 1 ° BO)B(2) 1 =I function x, is an eigenstate of both operators $? and S., with quantum numbers given by and M, = 0, respectively. The antisymmetric spin function x. is also an eigenstate of both S* and S,, with corresponding quantum numbers S = 0 and M,= 0. In what follows, and by analogy with the one-electron case, we shall write the eigenstates common to both operators $’ and S, as x.y, So that in this new notation we have Yuu = YX. ¥11 = Zn Hand Y= A. The foregoing discussion shows that. starting with the four independent and normalised spin functions (7.12), we can construct four normalised and mutually orthogonal spin functions which are cigenstates of both operators $? and 5. and ‘ss a definite symmetry in the exchange of the two electrons. These are the mmetric spin function Hoo .2) = J betuy62) ~ ayaa] (738) Vv and the three symmetric spin functions Hall. 2)= a(1)a(2) ll. 2)= T[a(1)B2) + B(A)ar2)) a9) R % a0, 2) = BOB) The antisymmetric spin function (7.18) corresponding to the quantum numbers S=Oand My=0is called a (spin) singlet, while the three symmetric spin states (7.19) corresponding to the total spin § = 1 and to the quantum numbers Mg =1,0,-1, Tespectively, are said 10 form a (spin) criplet (see Table 7.2), The role of the Paull exclusion principle Let us now return to the equation (7.8). AL first sight, it would appear that by combining the four spin states (7.18) and (7.19) with the spatial eigenfunctions v(t), 12), we could obtain four times as many eigenstates ¥(q,, q;) for an atom (oFion) with two spin 1/2 electrons than if the electrons were spinless. However, this isnot the case because, as we have seen in Chapter 2, the Pauli exclusion principle requires that the total wave function ¥(qy, qa... , dy) of a system of N electrons must be antisymmetric. In other words ¥(q,, g>,--., gy) Must change sign if all the coordinates (spatial and spin) of two electrons are interchanged. Hence, in our two-electron case, we see from (7.8) that in order to obtain total antisymmetric wave functions ‘¥(q;, g2) we must either multiply symmetric spatial (para) wave functions y,(r,, r) by the antisymmetric (singlet) spin state (7.18), Y va, 92) = W(t, 2) a: [a(1)B(2) - BA) a(2)} (7.20) 2 or multiply antisymmetric spatial (ortho) wave functions wr, Ff) by one of the three symmetric spin functions (7.19) belonging to the spin triplet, V/ @(1)a(2) ¥(gs.42) = voles 8) x | fet) BQ) + B(1)A2)] (723) V2 B()B(2) Thus para states must always be spin singlets, while ortho states must be spin triplets, so that the Pauli exclusion principle introduces a coupling between the inline af the alactranepoelechons In an phm ton fove alt thi Aner try ord my, tdenknnl (5 (jae, Wi Alm eondow fn amg tein deveiowa (alemic) i cheveensed bg rincipet OY order fer a dhe, velo 4 very fore 0 tt sve 4 OL UTE b choveckeritts pvbsbolis. Fer a oean L , Waar igner) parsible voles AP omy 8 ME -h, Atty: / platehe EOE yg dhe ote shop parern— von OM Tere fre razimum— 1 sf clecten 2 amon he +8 “1 2. 2b) =2 [rsaece- sro 4 $ ee Rfet (m-D2Y pears an ° gucher— dibibns riaehon in on éAall( ne 2 fone parcibs rstnn fb ote bee ard Let ee ee 2 Tw te tran yordig te OE = Tr th $ etechons ' sy. > 2 1 5 Ke ofy ' sy. oN © The ute hha In an alew—- ome filed te Me dermvig ert oP, 25. Bb, ae, Sarah G8 2 OAR 6 USApene 207) Vo Wemember jy, ardey f Sub-glalt : Po BP se Ne Wd Sts st = bE ba bd . ' Bb otc. dm me echo Ongiguralton—tp 6 Sedtum (a, abr — tn RE Qoumd Sint - ee ait mye. etethon! isos" Spo act conbiqyrehion— toil fe — ERR Write don iz spechos copra terms devon adow— having Competel, pied sual ord gebabelt (ie. Ho 72 actine— elechon , £4. He, fre. ote } D> Mere -bLeo, S20 , fo Delreso only perible fern 5 "$5 x © fund’ Rules for an phon — Comalties f Aenevel achat stechons a urdee LS- Compr. scheme , Vie _(prourd Abbe 5 Pat by $2 twd’6 rule wo folios + xs 1) Tie Aiehso dati higleok omlti tty (261 mr dy lohich- one —b Under or ofevmige— ast! Ht Seb ard ES apt Nf LSS) Wil koe Andoh exergy and Ke tere #e enc inenesa 00 Ie mul tipl cite tecvenaes “é i) Pre thehin of w ainere twull pci, Ris mot enwrty see wit ve HF bghsol 1 Uo lun Fee bith fe Phir Lond SAE 5) melts Robet i) mitibek Ee fol 4 Lptich J-vralus- bo er ae ae oo Jordi in bald filed er laa Hon alg iis pai te ee Ge NE Re cles te dubia mate tpn big tiledTon = Bel eve Lenk elect — Pome PIOHECR - Aa de—.. ee far piechon Ort grration im ap k Hy Poli’ exclusion frinciple , fo fred one Fee olied terms . = te cetothons Row Some. £ valt— (44) but Hey cea In pba ith diferent n. So powtid are fanci pe— wl mo ba violated 2Ker— in ens eaithona hav Lone— volte ot tm, ork - ueta. Hee chochens ote epltad rons Sarssvele® i yaadie— value + Loot aye ane fee, Ged fred, ByeNer CF Va pea, 4.0 & $24 “Dsl \ ‘De 3 3 By, Dir “Pr 4 twe wetechony tn ee twe - ou mye bs ee, he 5 cotirg > y Fink persis Valin 4acég. oe ponaiki values 4 I> ads a (en -2016) ogEe pen owe J Tivo eochons Love different n ard “ae Bil vine) Le So powtla grctualon fdirdpu— wilt. rok Viatadd Gc vohon tig Wwio howe. ows ty, 4 Wey Shae oA hon— anjvivelat- crechowr, Co pl peroible— elteo 7 % i Ord § ane allowed. pene, 28, yet; Aeh, 4th2 Tigo _—Bepaivatank elethond Sr b oth nelurs pon ard L ne? eiechen + Ieee ' | etechome tem the | @ne— darotad bye, nS rm pp ana ete | |) cone net \ gn Beebo — confiave shin ner, /elechor? howe | on ork (22 °)+ pr bed , mer Oe Pee anno weverhom | how here eae afnonkim nu mbem (rt ws) ; hy nn peeo bing pow > qeciuaton grin PIE > foe Be nyweer™ MS must As Serer der hee iecher? « =0- So, maz he ot yw wo _ £0, § pairs Mekn= © qin LPO! onde etce mo bo thee a a eno paavibl2— term tog. seen yh? 2p ims nay ene? = b) abe DPS thi PO? nord be pine Heh atthe me 00% dn | pee jo paullé pecs ion ee yyenen— fre te we ve ues comiaeer ath pancetta umn? mae b % im, wie pa Aisfener by two amps -3 5 dae ot erectrons (Lent 2 m= 2 woe oe me 20 7 wn bee wd $20 puch ine tp (1 L wil ( >.) eo fee MFO0 SP Date m 120 rh God ‘ A Ge touch Ginn Ie ('s, — (i) fel farsi comin fp ferment Ome - (+ a. meet, Mea ro, omg 4, Met 7h Fer YAR Cone mse dr two exethion = Gan be. Aame| or da ffeme ot Hexe, mye 1,0 4. Me = 6.444 = gat, whick gm 2 Let in man © 0.4, 2, Shs be, @ Ground Sister crue, fuer Stehe— Wo dts peur dl go urA hugheot Spin melt pd Joh des doueor erm, Heme - Bp, Hed Bp sinke— fag free jousla dr [20.t, > i Aba ee) Wr Hon half - fille, (e829) BH | e pe outer moar ato. wily Anear a value hoe 3 “ qo Behe + corton (4S) ho In th Dev = fillaek exe mat Shot ian wrth higher ve (2°) in teh OAD. a peo bed t— qeourd prete. ONE Vand mp 5 np hen ote a Fe ine taanteal ie ETT slaved 1S ee Te re werD Bye) 422) ——— = ajye-1)0)4 yMI2 27 be J apAy > eich ms, eeh espegs 5 pope [ate— in 3 ad 5; in is oe Toot, ee wl are a chain [eur 2015) | 2 &bed nem,@ Gmed Abbe fr os opel cae elechn @ ns! crevton + 12D, 22¥2- which dime Deb + Spechoaceple 2oy, lh — ore gnhe— 4 po ground Arle. She only 2, Hwa, K ete ®) ap! win 5 giechon: fea, 62M whch eer. de Afr BH fem ke 2 Spechea ob a” Fy gubax most Pho & ° Wei Hor rena foc np! jeaa ton fof fled. £0 qrovnl BHA wi be pope We Py, cg. (BM ha 2H) pus © pans, gute mast fal » prone Porm hall He! fo eteurd, Atebe— wu howe, hsqbtor J valus—+ Here, Pay, a (4 F ete) Be wb ports re FO pa Aster ocr po enegye Us 4 Urbon (> 6) dor In HE Tore ftehe— elether — Configure ation , > ¢ for qed Arte etechoric— confi pret, ro oP aceundig fe Poi exclubion brindp te 2p ‘ate. SO do ablswed Ate— wil howt— mye o ™ clidferent dre two -excchons . dhol ek He alrwed harms 16, Ip ond 'D._-3°Explanation of the Broad Features of Alkali Spectra An alkali atom (of atomic number Z) consists of an inert-gas core composed of the nucleus and a few completed subshells having Z— 1 electrons, plus a single valeaceelectron in the outermost subshell. lectron bs For example, the ground-state configurations of Li, "Na and 9K ore [=]. 182s 2p%l35, and 1s 2s'2p%3s23p*| as, respectively. It is seen that, except for Li , the completed highest subshell is a p subshell , and the next s subshell is the outermost onc. In the optical (low-energy) excitation processes , only the valence clectron is excited which alone i responsible for the optical spectra®. The inert-gas core having a spherically symmetrical distribution of charge does not play any part / Let us take up the case of sodium (''Na). Its normal outgr configuration is 3 s , and the corresponding crm is an_S-term. The various possible excited configurations and the corresponding terms are : 4s, 55,65, S-terms 3p. 4p. Sp, . P-terms 3d, 4d, Sd, D-terms 4f, Sf, 6f, Feterms. In excitation, the total energy of the core does not change. Therefore, the total energy of the atom is a constant plus the energy of the optically-active (valence) electron. For convenience, we take this constant as zero so that the total energy of the atom in a certain state is equal to the energy of the optically-active clectron in that state. Let us compare the energies of the alkali (sodium) atom in the various states with those of the hydrogen atom in the corresponding states. In hydrogen atom, the electron in an orbit m (say) moves in the ‘coulombian’ field of the nucleus (point charge), and its energy is given by m(Zey € (3 we 3 (Z = 1 for hydrogen) 5, = - Or 8 which depends upon n only. In alkali atom, on the other hand, the electron moves in the ‘central’ field of the nucleus plus core electrons, and ils energy is given by 22 m(Zpeye? (1 tun “lee (at) where Z,e is the effective charge of the nucleus for the orbit n. The quantity Z,¢ is always greater than ¢ because the screening of a nucleus of charge Ze by the charge (Z=l)e of the core electrons is not perfect. Hence the energy of the alkali atom is more Regulive than the energy of the hydrogen atom in the same state n. This means that the energy Jevels of the alkali atom are lower than the corresponding levels of the hydrogen snus toadily give up one electron to form positive tons. The energy ‘ ve eet voone sein vom those aloms is small (5 1 eV in caso of Na), but that required to Tee eee crtron ia much lergor (47-3 6V}. This suggasis that of al the electrons in an alka Glam one anon le Igosely-bound 10 the atom. The spectral ines ol an alkall atom arise cue to the Vansitions of this electron only which Is called the ‘optical or the ‘valence! electron.172 Atomic and Motecutar Spectra : Laser atom, However, as » increases, the alkali levels approach the corresponding hydrogen levels because the screening becomes more and more perfect (Z, ¢ — €). Secondly, in contrast to hydrogen, the cnergy of an alkali atom in a certain state depends not only upon 1 but also upon the f value of the optical electron. This is because the probability of finding the electron near the nucleus (r — 0) is wye and is largest for | = 0 (s-electron), and decreases very rapidly with increasing !. Thus, for a given nm, the energy is most negative for the s-electron which spends more time near the nucleus and feels almost the full nuclear charge (at r — 0, Z, —> Z); and becomes less and less negative for the p.d.f. clectrons. The I-dependence of energy is so important that in sodium the 4s level is more negative than the 3d level. Thus, all alkali levels of a given 1 are shifted lower than the corresponding levels of hydrogen; the shift being greatest for the s level and becoming smaller and smaller for the p. d,f....... levels, This is illustrated in Fig. 1. Yo HYOROGEN S P D EE -y “2 DIFFUSE x3 s S 5 | m2 $ 2 é =f PRINCIPAL 0 opium ("Na) -3 34 ob (Fig. 1)When the sodium atom is excited by some means, the (optical) 3s electron is raised to any of the excited levels 3p,3d, 4s, 4p, 4d, 4f, 5s, 5p etc. from which it jumps back through any selected path allowed by the following selection rules : An = any integer Ale=ysglie The observed series in the emission spectrum arise from the following transitions : np 3s, n>2 — Principal Series ns > 3p, n>3 Sharp Series nd—>3p,n>2 Diffuse Series nf 93d,n>3 Fundamental Series A practical sodium source contains numerous atoms so that all possible excited states are available for the transitions which take place through all the allowed paths. Hence all the four series are simultaneously emitted in the spectrum. Since, ultimately, the electron retums to the ground state which involves the principal series, the lines of the principal series are mosti F For hydrogen atom, the energy in different states S, P, D,........ of the same n is same. Hence the four different series observed in the spectra of alkali atoms become identical in the spectrum of hydrogen atom. The other observations in alkali spectra are also obvious in the energy level diagram (Fig. 1). The sharp and the diffuse series have the same convergence limit (3 p_level)*. The wave number difference** between this limit (3 p level) and the principal series limit (3 s level) is equal to th wave number of the first line (3 p — 3 s) of the principal series. This is Rydberg-Schuster law. Similarly, the wave number difference between the diffuse series limit (3 p ‘evel) and the fundamental series limit (3d level) is equal to the wave number of the ficst line (3d — 3p) of the diffuse series. This is Runge’s law. _~et Fine Structure in Alkali Spectra : The Spinning Electron When the spectral lines of an alkali atom are seen under high resolution, each of them is found to be made up of two close component lines, that is, each line is a close ‘doublet’ For example, the yellow D-line of sodium consists of two close lines of wavelengths 5890 A and 5896°A. This is called the fine structure in alkali spectral lines. The nature of fine structure is, however, different in the spectral lines of different serics. All lines of the sharp series are close doublets having the same wave number separation. Similarly, each line of the principal serics is a doublet but in this series the wave number separation between the two components decreases rapidly toward the lines of increasing wave number The lines of diffuse and fundamental series show « three-component fine structure and are called ‘compound doublets’ (not triplets). The fine structure in the lines of the fundamental series is, however, negligible. In general, the fine-structure splitting of spectral lines is small for the lighter atoms. but increases rapidly with increasing atomic number. Explanation of Fine Structure on the basis of Electron Spin : The line-splitung (fine structure) in alkali spectra is traced back to level-splitting. An analysis of alkali spectra shows that the S-levels are single, but all others P, D, F, ... are doublet levels. The level-splitting is the result of the “spin” of the electron. The spin magnetic moment of the optical elecuron interacts with the internal magnetic field arising due to the orbital mouor of the electron in the nuclear clectric field. This is known as spin-orbit interaction.* Due © this interaction, the orbital angular momentum of the optical electron is coupled t0 the spin angular momentum 5° to form a resultant F’about which both Fand s°precess. J is also the total angular momentum of the (alkali) atom because the angular momentum of “The relativistic effect which is equally important in explaining the spectral fine-structure 9 !P case of a one-electron atom, is negligible (compared with the spin-orbit interaction) for the optical active electrons in aif multielectron atoms,Spectra of Alkali Elements 1” the core is zero. The quantum number j , called the ‘inner quantum number’, can take the following two values jrlts=lt }. according as the spin and the orbital angular momenta are “parallel” or “antiparallel”, The double possibility for the setting of the spin with respect to the orbit results in a splitting of cach energy level (I-level) into two, one corresponding to j = 1 + $ and the other 2 corresponding to j =! - i, with the exception of S-levels for which f= 0. The complete notation of the levels will be as below ; Level 1 a OLE j(=lts) | Full auton | s 0 in| 2 an as P 1 1n 2 372, 12 2p. Pir D 2 12 2 5/2, 372 206.9. 2Dya F 3 12 2 12, 52 2 Fan CFs In each doublet level the component corresponding to the smaller value of j lies deeper (more stable). This is because the more stable state is one in which the spin magnetic moment jf, of the electron lines up in the direction of the magnetic field B produced by the orbital motion of the electron inthe electric field of the nucleus, and Bis in the same direction as the orbital angular momentum I” The spin magnetic moment wv, is opposite to spin angular momentum #7, because the electron is negatively charged Since in the more stable state pi? is in the same direction as 7, the vector Tis opposite to vector =? and the quantum number j is of lower value, j = 1-5 (Fig. 2 a) Obviously, the higher value of j corresponds to less stable state (Fig. b). OF course, exceptions do occur. & @ uy t 1? iy 4 gel-4 grlts (@ tb) (more stable) (less stable) (Fig. 2)igcular Spectra : Laser ‘uh’ ar = 584—2=2— wi(l+ 1) “This formula gives doublet separation in remarkably good agreement with experimental observation. It shows that the level splitting for an alkali atom (i) increases with increasing atomic number, (i) decreases with increasing m (for the same {) and also (iii) decreases with increasing 1 (for same n). As already seen, the splitting is zero for 1 = 0 (S-levels) Z The relative splitting of levels Yo 2p 2p, 2 of a given n value is illustrated in Fig. 3. fn Fig. 4 is shown the splitting of alkali levels involved in the emission of the lines of the four series, The 25 levels are single components 75,2. The 7P levels are splitted as cm (Fig. 3) % (Fig. a)Spectra of Alkali Elements 179 FPyn and P,,,, the latter (7P\,2) being deeper, and the splitting decreases as increases. Similwly, the 7D and 7 tevels are splitted as 7Ds.2Dyy. and AE, 9, *F sy but these splittings are much smaller, a The selection rules in operation are An = any integer including zero - Al=+1 o,+1. ? 3°p, These rules explain the simple and compound 8 Pf fe 2 3 doublet structure of spectral lines. For example, a the principal resonance doublet of sodium (D, and Dz lines) arise from the transitions 37P + 37S, which is cquivalem to the 2 4 following two transitions 3s 3°Syp 3Pin > 37512 (D) 5896 A) 3°Pyp 9 37Siq (D2 5890 A) The wave number separation between Dy and D, Da D, lines is equal to the separation between —v 37Pyq and 3 *P3, levels (Fig. 5). (Fig. 5) The other lines, of higher wave numbers, of the principal series owe their doublet structure to the doubling of higher ?P levels such as 4°P,57P,.... levels. Since the splitting of these levels decreases with increasing _n, the wave_number_separation between the doublet components of the principal series decreases in_the lines of higher and higher wave numbers. nd aghec wayexnunaben The doublets of the sharp series are formed by the transitions n*Si2 > 3 "Praia. where n=4,5,..... In this series the wave number separation between the doublet components of all the lines is the same and equal to the separation between 3*Py and 37P,,2 levels on which all the transitions terminate. 2 iY 3°b., sof se The lines of the diffuse and the fundamental series show a three-component structure and are called ‘compound’ doublets. This is illustrated in a. 3p. Fi i aP Fig. 6 for a diffuse line arising from the { uansition 3°Ds2,32 3 Py2.ia- Here both the 7D and 7P levels are splitted and the selection rules allow three transitions, as shown. ——v (Fig. 6) ‘The splitting of the 7D level is, however, so small th (under ordinary resolution only {wo components appear, If we ignore the 4D-splitting, then all the lines of the diffuseseries have the same doublet separation as the lincs of the sharp serics, that is, equal to the separation between 37Py2 and 37P,, levels. Although the lines of the diffuse and the fundamental series have three components but they are called ‘doublets’ (nat triplets) because they arise from transitions between uublet Tevels. The name ‘doublet’ refers to the multiplicity of energy levels, and not to the The name ‘doublet’ refers to the multiplicity of energy lev: “fumber of components in the spectral lines.