G. AruldhasATOMIC PHYSICS We discussed in Chapter 6, the application of quantum mechanics to several simple systems to obiain the energy eigenvalues and eigenfunctions. We now look more closely at what quantum Tnechanics tells us about the spectra of hydrogen atom and atoms having more than one eicctron, We noted only one quantum number in the simple Bohr theory. In quantum mechanical system of cone electron atom, three different quantum numbers were needed to specify each state. Soon the necessity of a fourth quantum number, called the spin quantum number, was felt to account forthe spectral features of atoms. We shall begin by studying the hydrogen spectrum and then the historic Stemn-Gerlach experiment which proved the existence of spin, the fine structure of spectral lines, the electron configuration in many electron atoms, and the angular momentum coupling schemes. The splitting of spectral lines in a magnetic field, referred to as Zeeman effect, is also discussed Finally, to obtain further insight on the arrangement of electrons in atoms, we shall discuss the characteristic spectra of X-rays. 7.1. HYDROGEN ATOM SPECTRUM We are now in a position to discuss the spectrum of hydrogen ace laws discussed so far. Every state of the hydrogen atom has a distinct wave specified by the quantum numbers 1, I, and m). Figure 7.1 shows the energy hydrogenatom. Though the different / states belonging to a given n have the same energ} to show them separately. Capital letters §, P, D, ... are used to describe the orbital angular momentis of atomic states and lower case letters s, p, d, ... to describe those for individual electrons: For hydrogen atom, this denomination is not important as it has only one electron. ording to the quantum mechanical function which is level diagram for y, we prefer Spectral Transitions On the basis of quantum mechanics one can evaluate the transition probabilities for of a system from one state to another under the influence of electromagnetic radiation the studies the transition depends on the interaction of the electric field of the radial electric dipole moment of the atom or molecule. The transition from state m to state n 1S the transition sn, In most oF tion with determit 0Atomic Physics 111 Enorgy (ev) _n . 0.8 4 15 3 D series ee 13.6 1 Fig. 7.1 Energy level diagram and some of the allowed transitions of hydrogen atom sition dipole moment Hy» defined by by the tra Han = J Vib Ya 4 a.) or for the dipole and #1 is the operat ition, if not, itis where Vq and Ys are the wave functions of states m and n, tis finite then that transition is an allowed trans moment. If the transition moment forbidden. Calculations give allowed transitions: .s, called selection rules, for the (7-1a) the following rule: ‘An = any value; Al= .s are less probable and are ci ‘also shown in Fig. 7-1. Since the state o! Tinear momentum and angular momentum. The selection va Mies one unit (7) of angular momentum. A close that many of the spectral lines are not single lines but 41; Am=0, 41 alled forbidden transitions. these rules f the atom changes during Transitions which do not follow # Some of the allowed transitions are possess energy, transition, the photon must rule Al = £1 strongly suggests that the photo! examination of the ‘emission spectrum shows t closely spac AGNETIC MOMENT OF HYDROGEN ATOM harge ¢ circulating around the tin the loop i 7.2 ORBITAL M. As a rou} the at nucleus with a speed It can be ci is the ratio of charge 10 the period T: an electron of cl om can be considered as ular current loop. The current hr model, e considered as a circ i we = - BF Tne ~~ 2ar (7.2)112 Modern Physics The magnetic moment /t of the loop is the product of current and area of the loop, and a : 4 Biven by ev 2 _€ =i — x ar? = -s—mrv Maixere-o7 2m am (13) where L= mur is the magnitude of the orbital angular momentum. ‘As magnetic moment Ht and angular momentum L are vectors, e “Im” aay Heo - ave only certain allowed values. The ‘As L can have only certain quantized values, 1 can also hi indicates that and L are oppositely directed. Using the quantum mechanical value negative sigi for L we can calculate the magnetic moment as; a [T+ = -up f1d+D as where eh (78) °° om is called Bohr magneton, a unit of magnetic moment. Substituting the values of e, f, and m = 46x10"? C) (1.055 x 10 Fs) 24 1 2x 9.11x 10! kg FT XO TS se Us From Eq. (7.4), (78) From Eqs. (7.5) and (7.8) we h: i . . ave the important result | ion i * HI> My, si : magnetic moment cannot align itself inthe z-direction. In i i ee Spee magni oe OF the atoms are randomly oriented. IMS OF 8 Rumber of atoms ‘onsider that a magnetic dipole havin, i goon a having a magnetic mom i i a ng to clasia Alectromagnetism (Example 7.2), it Senet oe aie A magnetic Tel B. eld gives rise to an interaction , V=--B If B is along the z-axis, we have (7.9) HB = LgB my, where Eq. (7.8) is used. (7.10) Since my is quantized, the potential energy is : s tantized, the ps rey is also quantized. Thus, i atomic state of a given 1 splits into (2/ + 1) different states ae in @ magnetic field, th D the magna ote Ménetic quantum number my.Atomic Physics 113 Example 7.1 A hydrogen atom is placed in a magnetic field of 3 T. Calculate the energy difference petween the m)=—I and m= -+1 components in the 2p state, Solution ‘The magnetic moment of the electron interacts with the magnetic field B and gives rise to the interaction energy [Eq. (7.10)] given by V=fgBm ‘The energy of m= -I state = -HpB The energy of 1pB ‘The energy difference = 2ftpB = 2(9.27 x 10 J/T) 3 T) 55.62 x10™ J 1.610"? TeV = 55.62 x 10 J = 3.48 x 104 eV 7.3 LARMOR PRECESSION Consider a magnetic dipole having a magnetic moment j4; placed in an external magnetic field B. ‘The dipole acquires a potential energy given by Eq, (7.9). According to classical electromagnetism, the dipole experiences a torque. This is expressed as T=W xB qn) which tends to align the dipole with the magnetic field. Since py and L are antiparallel, the torque ‘is perpendicular 0 Hy, L, and B, From the laws of mechanics, we know that torque is also given by dL 1% (7.12) Hence, dL/dr is also perpendicular to ty, L, and B. That is, the change in angular momentum dL is also in the direc- tion of 1. As the magnitude of the vector L remains the same, its direction must change to produce the change in angular momentum. Hence, as shown in Fig. 7.2, the change in angular momentum dL. requires the precession of the vector L about the magnetic field. Since vectors Hy and L are antiparallel, both H and L precess about the magnetic field. This precession is known as Larmor pre- cession and the precessional frequency, called the Larmor frequeney a, is given by _d 1 ab = ar = Tsind dt Replacing dL/dt using Eqs. (7.11) and (7.12) = pp sin o= HB = Tand MB sin O= —— (7.13) ae ae P = |. 7.2. Precessional motion of a Replacing L with the help of Eq. (7.3), we get magnetic moment p placed in an extemal magnetic field B. The vectors (7.13a) py and L are antiparallel. Om114 Modern Physics The situation may be pictured as follows. When the field is applied, the dipole align itself along. B as that corresponds to minimum energy (Example 7.2) Tie align itself in a state of minimum energy along B results in rotational enery nee of 5 dissipated. But there is no process available by which it can dissipate the eneedy ich may? tendency of H to align itself with B results in the precession of pt, about B, keeping Tpetefoe hs nd e; loment, My 7 tendency of 0 constant, Netpy Example 72 A dipole of moment is placed in a magnetic field B. Show tat yy energy of the magnetic moment in the magnetic field is ~1-B © interaction Solution In the magnetic field the dipole experiences a torque =X B= UB sin 6 where @ is the angle that the moment }1 makes with B (Fig. 7.2). The torque tends to rotate the dipole in the direction of the field. The cl which results from the rotation is completely in the form of potential energy, to assume AE = 0 when HL is at 90° to B, To determine the potential energy at a to calculate the amount of external work to be done to rotate the dipole from some angle @. That is, hange in energy Ag It is the convention ny angle 8, we kaye = 90° (AE = 0) @ 8 AE= J 1d0= J HB sin-0 dO = -1B cos @ so o AE = --B For @= 90°, AE =0; for 0= 0°, AE =-1B, for 0= 180°, AE = 1B. In other words, 6= 0° corresponds to a position of minimum energy and @ = 180° corresponds to a position of maximum eneiy, 7.4 STERN-GERLACH EXPERIMENT The existence of space quantization of angular momentum of the electron and electron spin wis established by an experiment proposed by Otto Stern in 1921 and carried out in collaboration wih Walter Gerlach in 1922. The experimental arrangement is shown in Fig. 7.3(a). It consists of an oven which projects a beam of silver atoms into a region of inhomogeneous magnetic field obtained by making one of the pole pieces of the magnet as knife edge and the opposite pole with a groove. Te beam is then allowed to strike on a photographic plate which detects the electrons falling on it Magnet Field off rails : Field on @ ©) : Fig. 7.3 (a) Experimental arrangements of Stern-Gerlach experiment and (b) splitting Pattern of atomic beam of silver.Atomic Physics When a magnetic dipole is placed in a uniform magnetic field, the forces at the poles are e and opposite and this constitutes a couple. The result is a rotational motion of the dipole. Howe n inhomogeneous magnetic field (here along z-axis) the dipole experiences a force given in an av F,= i where V = potential energy @. substituting the value of V from Eq, (7.9) in Eq. (7.14) dB aB Frau, Ge ei em Me Gz = Hoos 0 @. where ; pris the magnetic moment of the atom, (dBldz) is the gradient of the magnetic field along z-axis, and 6 is the angle the vector |L makes with the z-axis, As a result of this force, the dipole makes a translational motion in the z-direction, Since tI net force on 11 is dependent on the orientations of 4, dipoles with different orientations are broug, to different positions on the photographic plate. The silver atom has only one valence electron. Hence, in its ground state 1 = 0 which give L=0 and j= 0. Consequently, the dipoles will not experience any force in the z-direction. In othe words, the silver atoms are expected to travel undeflected, giving only one line on the screen. Howeve. Stern and Gerlach in their experiment observed two distinct lines, one above and the other below th mean position, That is, the magnetic moment of silver atom in the ground state is not zero as expected The splitting patern of the atomic beam on the screen [Fig. 7.3(b)] clearly indicates that the magnetic moment takes two orientations in the inhomogeneous magnetic field corresponding to m values +1/2 and -1/2. In other words, for each atomic state described by the three quantum numbers 7, 1 mthere must be now a fourth quantum number m, which takes on the values +1/2 and —1/2. The experiment has thus conclusively proved the existence of an additional angular momentum vector which is quantized like the orbital angular momentum vector L we considered earlier. 7.5 ELECTRON SPIN s To explain the anomalous optical spectra, Pauli in 1920 suggested the existence of a fourth quantum number to the electron in addition to n, f, and m,. However, he was not able to explain its physical significance. In 1922, Stern and Gerlach from their experiment showed the existence of an angular Momentum in addition to the orbital angular momentum. In 1925, in order to explain experimental data, Samuel Goudsmit and George Uhlenbeck proposed that the electron must have an intrinsic angular momentum called spin angular momentum specified by the spin quantum number $= IN They also suggested that the spin angular momentum vector S is similar to the orbital angular momentum vector Land can have (2s + 1) values +//2 and—”/2. Thus, the magnetic spin quantum number m, can have the values +1/2, The spin angular momentum vector S has the magnitude |S |= /s(+D h = (/3/2)h. The energy of the two states corresponding to m,= £1/2 will be degenerate. When the atom is placed in a magnetic field (say along z-direction), the states corresponding to m,= 1/2 and m, = 1/2 will split into two distinct states as shown in Fs. 74. The state for which m,= 1/2 is called a spin ‘up’ state and the one for which m, = ~1/2 'Scalled a spin ‘down’ state. The magnetic moment associated with the spin angular momentum is w=-(4)s (7.16) m116 Modern Physics ‘The hypothesis regarding the spin magnetic moment was confirmed by Dirac’s relativistic wave equation. Equation (7.16) can also be written as (2.17) ‘The corresponding relation for orbital angular momentum is mental ot) ‘This relation is obtained by using Eq. (7.14). The numerical factor relating the magnetic moment in units of Bohr magneton to each angular momentum vector in units of fi is known as the gyro- magnetic ratio which is designated as g, for spin and g; for the orbital case. Then, we have Fig. 7.4 The quantization of S in an external magnetic field, HeS __ 8: HeS The z-component of S = £h/2, = (7.19) h Stel (7.20) This gives gi=1 and g,=2. 7.6 THE VECTOR ATOM MODEL ‘The concept of spin was postulated by Uhlenbeck and Goudsmit. Stern and Gerlach proved its existence. The introduction of the concept of spin into the formalism led to the vector atom model. We now discuss how the two momenta combine and how this changes the spectral features of a one electron atom. ‘As discussed, the electron in an atom has both orbital angular momentum L and spin angular momentum S. These two angular momenta together give a total angular momentum vector J to the electron. The vector model of the atom suggests that J is the vector sum of Land S. That is, J=L+8 (7.21) Like L and S, the magnitude of J is given by J=|Sl= JIG a (7.22) where j is the total angular moméntum quantum number. In analogy with the components L, and S,, the possible values of J, are J.= mh (7.23) For a given value of j, m; takes the (2j + 1) values Li 724) When we add two vectors, the vector S can be added to L either parallel or antiparallel as in Fig. 7.5. The total angular momentum quantum number for the single electron can have the values (7.25) KPSince s = 1/2, this reduces to jel or If P= 0, j will have only the value’ 1/2. If number j = 1+ 12 = 32 orj=1-12 1, j = 5/2 or 3/2. The angular momenta L and $ show space quantization. Hence we expect that J will also show space quantization, The situation may be pictured in the following manner, The internal magnetic field causes the vectors L and $ to precess about J as shown in Fig, 7.6(a). However, in an external magnetic field, J will precess about Bey as shown in Fig. 7.6(b). The precessional motion of L and $ about the precessing J is quite complicated. The notation commonly used to describe the different states (7.25) 1, the quantum 2. For |= 2, s is nly where n refers to the principal quantum number, jis the total angular momentum quantum number, and Atomic Physics 117 U s L 4 Jel+s Jel-s (@) (b) Fig. 7.5 The vectorial addition of Land S to give J when (a) L and S are aligned to give j = 1+ s and (b) L and $ are anti- aligned to give j= /- s. L represents the orbital angular momentum quantum number. (b) Fig. 7.6 (a) Precession of angular momentum vectors L and S about their total angular momentum vector J and (b) precession of vector J about an arbitrary axis. Different values of L are represented by different symbols that denote the energy states. L =] 0,1] 2]3/]4 Symbol] | s | P Thus, for the ground state of hydrogen atom n=1,l=0,s=12,j 1/2. The state is denoted as 1Sia.U8 Modern Physics For the first excited state, 1, j = M2. Therefore, the state is 282 72, j = 32, 12, Therefore, the states are 2Pypy 2Pya- For n = 3, the involved states are 3S yp; 3Pxa 3Pinai 3Dsv 3D all states except the S states are doublets for n= Next we shall evaluate the angle between the vectors Land $ and that between J and the z-axis. From Eq. (7.21), we have (L+S)-(L+8)= 1? + S?+2L-S= L2 + S?+ 2LS cos 0 Thu or popes cos 0= ST where @ is the angle between the vectors Land S. Since, J? =j(j+ IM, L2= M+ 1A, and S? = s(s+ yr iG+D 10+) - ss +1) © afte) fsG+0 If Q is the angle between the J vector and z-axis J, mjh eee mens” fraepa Jided Equation (7.26a) shows that J ean never align along the z-axis since the maximam value of my is {j which is always less than 7 G*D- cos @ (7.26a) Example 73. For the d-electron of the hydrogen atom, calculate the values of L, S,and J and determine the possible angles between L and S. Solution Fora d-electron, |= 2, s = V2, j= 2+ V2 = 5/2 or j are denoted by Ds and Dyp. Therefore, = 1/2 = 3/2. These two states For the Dsq state: J JUD h= For the Dyz state: J= | 2 3 he ‘The angle between L and $ is given by Eq, (7.26): _ G)GD=Ax3)-WDEM _ yang 2x46 (3/2) For Dp state: cos @_ Atomic Physics 119 or 0 = 61.87" For Dyg state: cos @ = (2/2)(5/2)- 6- G/M) 2x J (3/2) Vz or = 135° 7.7. SPIN-ORBIT INTERACTION AND FINE STRUCTURE of hydrogen spectrum showed a doublet In section 7.1, we mentioned that the emission lines Jet structure. The electron in the hydrogen structure. We now examine the reason for such a doub! sam moves ina central potential V(r) that is produced by the nucleus. The interaction between its orbital angular momentum L and spin angular momentum S is called the spin-orbit interaction. This Frteraction is of the form L,-S and its effect is to make the states j = I~ 1/2 to have a slightly lower energy than those with j=1+ 1/2. These doublet levels constitute the fine structure of the hydrogen ftom spectrum. For s-electrons, the orbital angular momentum is zero and hence there is Be spi Grbit interaction, The spin-orbit interaction is more prominent in heavy elements because the spi orbit energy is proportional to Z‘. The doublet separation decreases as ! increases. Also, the 2p doublet separation is greater than the 3p doublet which is greater than 4p and so on. The d-electrons energy level splittings are also similar. Figure 7.7 shows the energy levels of hydrogen atom including the splitting due to spin-orbit interaction. i i i 312 52 4s 12 4p 92 4d = 32 52 3s 112 3p 2 30 3/2 32 2 4 12 2s ——— 1/2 1s 4R Lower energy levels of hydrogen atom showing the splitting due to spin-orbit ) and 1s > 2p and 1s — 3p transitions Fig. 7.7L interaction (splittings are not to scale!i — 120 Modern Physics The theoretical calculation of spin-orbit correction is somewhat complicated. Due 10 the spin angular momentum, the electron behaves like a small magnetic dipole, According fo 9 semiclassical approach, this small magnetic dipole imeraets with the internal magnetic field produced by the hiucleus and gives rise to a potential energy of the electron. This potential energy is different for the electrons with j= 14 1/2 and j = 1 — 1/2. Hence, the fine structure, : ‘Transitions between different energy levels give the spectral lines. The selection rules for aq one electron atom, Eq, (7.10), have to be modified. ‘The modified selection rules are An= any value At = #1 Aj=0, 41 Any = 0, #1 (7.27) Figure 7.7 also shows the 1s -» 2p and 1s -> 3p transitions, IF spin-orbit interaction is, not considered, the transition from 1s — 2p is a single line which will be the first line in the Lyman series. However, it splits into two lines when spin-orbit interaction is included (Fig. 7.7). The situation is similar for the transitions 1s -» 3p, 1s -> 4p, and so on. Each line in the Lyman series thus splits into a doublet, often called fine structure doublet. The transitions between 2p and 3¢ levels give three lines (Example 7.4). Thus, the inclusion of spin-orbit coupling increases the complexity of the hydrogen spectrum. Example 74 Sketch the hydrogen atom energy levels for 2p and 3d electrons and mark the allowed spectral transitions between them. Solution Due to spin-orbit interaction the 2p and 3d levels split into doublets. The possible j values for the 2p level are j = 1/2, 3/2 and for the 3d level j = 3/2, 5/2. The transition corresponding to Aj =0(j= 3/2 j= 3/2) will be the lowest in frequency. The next one will be the one between j= 32 j= 5/2 (Aj = +1). The transition j = 1/2 + j = 3/2 (Aj = +1) will be the highest in frequency, ‘The transitions are shown in Fig, 7.8. Under low resolution, the three lines appear to be only two because two of them are very close, Hence, they are often referred to as a compound doublet to indicate that they involve doublet energy states. i — re S00 a eee 32 2p 2 a Fig.7.8 Energy levels for 2p and 3d electrons and the allowed spectral transitions between them.Atomic Physics 124 7.8 PAULI'S EXCLUSION PRINCIPLE ANI CONFIGURATION ee ee cies tive charge of an atom is concentrated on the Z protons in the nucleus. A neutral atom has electrons interacting with the nucleus and also with each other according to Coulomb law. The Senridinger equation for a many electron system is not exactly solvable and there is no general expression for the energy levels. Hence, the atomic spectra of many electron atoms ee cat od straightforward as that for the one electron system. However, one can explain number of aperimental results even without compating the wave functions. As a first step towards this, we Gieeuss the arrangement of electrons in many electron systems. : , Shells and Subshells We have seen that the quantum state of an electron in an atom is completely specified by a set of four quantum numbers 7, 1, my, and m,, Another equally valid set is given by the quantum numbers n, k.jand m), The use of hydrogenic quantum numbers for other atoms implies a hydrogen like Central potential for their outer electrons. In any atom, the electrons that have the same quantum number n are said to be in the same shell. Each shell is given different letter codes as follows: n 1] 2/3) 4] -]-]- Letter code] K] L]}M}| N} - | + |< ‘Thus, n = 1 is called the K shell, n = 2 is called the L shell, and so on. For a given n, the electrons that have the same /-value are said to be in the same subshell. The subshells are described by the nl values. Thus, we have 1s, 2s, 2p, 35, 3p, 3d, ... subshells. As already seen, in any shell there are r different quantum states since for a given /, m can take (2 + 1) values. Pauli Principle Next, we consider how electrons in many electron atoms occupy these subshells and shells. The question that arises immediately is whether there is any restriction on the number of electrons that can occupy the same state. The answer to this was proposed by Pauli in 1925 in his famous exclusion principle. The basic rales which determine how electrons in many electron systems occupy orbitals are: (i) Pauli’s exclusion principle: In any atom, no two electrons can have the same set of quantum numbers (n, 1, my, m,) or (ry 1 js my). ) The electrons in an atom tend to occupy the lowest energy levels available to them. tals singly with their spins i) Hund’s principle: Electrons tend to occupy degenerate orbit parallel. Pauli’s principle limits the number of electrons in each orbital to two corresponding to “+1/2 of -1/2. Hence, the number of electrons in a given shell is given by 2n? and for a given [here are 2(21 + 1) electrons. Therefore, there will be 2 electrons in the s-subshell, 6 in the pesubshell, 10 in the d-subshell, and so on. A superscript is used to denote the number of electrons in each subshell. Thus, the symbol 1s? is used if two electrons are there in the Is state, 2p" is used if four electrons are there in the 2p state, and so on. To apply the second rule, one should know= 4 122 Modern Physics i ven by Bohr's the energy ordering of the subshells for the outermost electrons in subshell. This is given by aufbau principle, The aufbau order is noes ls < 25 < 2p < 35 < 3p < ds < 3d < dp < Ss < 4d < Sp < 65 < Af < 5d < Gp ia= = 184 Modern Physics : ment, ‘2p*. As there is no valence clectron, neon is chemically inactive. Hence, it is an inert ele! ‘The nl value of the last electron isn = 2,1 = Ie Pelee tron has nNa—Out of the 11 electrons, 10 completely fill the subshell 2p. Therefore, the 11" elect n= 3,1 = 0 and the electronic configuration is 1s72s*2p%3s'. : S, there are 25 + 1 values of J. However, for L < S, the number of possible values of J are 2L + 1. The value of 25 + 1 is called the multiplicity of the state. For a two electron system a. AEAtomic Physics 126 (51 = 52= 1/2), the total spin angular momentum quantum number S = 0 (spins antiparallel) or 1 (spins parallel). When S = 0, we have 25 + 1 = I and such states are referred to as singlet states. On the other hand, when $= I and 25+ J = 3, these are referred to as triplet states. Often the singlet and triplet levels are grouped separately. To describe states conveniently, one requires a notation. The symbol nL, used for a single electron is changed as follows. State symbol or Term symbol = n **!L, (7.33) where the superscript 25 + 1 represents the multiplicity of the state, subscript J is the total angular momentum quantum number, and L stands for S, P, D,... representing the orbital angular momentum quantum number which has already been discussed. This way of representing states is known as the term symbol of the state. ‘Thus, if S = 1/2, L = 1, J = 3/2, 1/2. The corresponding states will be *Py and *P,p, read as doublet P three halves and doublet P half. Multiplicities associated with different number of electrons in the outer shell are given by the rule which states that the terms of atoms or ions with even number of valence electrons have odd multiplicities and vice versa. The selection rules for the LS coupling case are AL = +1, AS =0 (734) AJ = 0,41 UV =0 > J = 0 is forbidden) The selection rule AS = 0 does not allow transitions between singlet and triplet states. 7.9.2 j-j Coupling This coupling predominates in atoms where the interaction between each L; and S; is considerable. In this scheme, each L; combines with the corresponding S, to give a J,, the total angular momentum of the i electron. The J,'s then couple and give the total angular momentum J of the atom. Jy = Ly + Sy Jz = Ly + Sys Jy = Ly + Sy. (7.35) Jed (7.36) ‘This coupling scheme is applicable to heavy elements. 7.9.3, Hund Rules We are led to a number of possible values for L and S, when the angular momenta of a number of electrons are combined. Of these values, which one has the lowest energy and the order in which the energy increases are governed by the two Hund’s rules: (i) The total spin angular momentum § should be maximized in accordance with the Pauli principle. Then, S= Ms, max (737) (ii) For that S, L should be maximized in accordance with the Pauli principle. Then, L= M1, max (7.38) ye V5126 Modern Physics interaction sPIits west in enerBY: We have already mentioned the first rule in section 7.8, Often the spin-or the energy levels corresponding to different J values. The lowest J value will be the 101 shell. Obtain the Example 7.6 Consider two electrons, one in the 4p and the other in the 4d sub: L, S, and J values and the spectroscopic symbols for this two electron system Solution For the two electrons, fh = 1, [2 = 2, 5 = W2 $2 = V2 The possible values of Li h+ ly y+ h-1| 4-212 32! Similarly, The possible values of J: L=3,5 L=3,5 L=28 The corresponding spectroscopic symbols are listed in Tuble 7.2. Table 7.2. Spectroscopic symbols for two electrons—one in 4p and the other in 4d subshells Ss L Tr Spectroscopic symbol 0 (singlet) 1 1 4'Py 2 2 4'D2 3 3 4'By 2 4P, 1 (triplet) 1 1 4P, > 4Paio ° 4Po 3 4D; 1 (triplet) 2 2 4D2¢ Daa i #D, 4 OF, | Griplet) 3 3 OF} VRa2 2 aR, Example 7.7 A state is denoted as *Dsp. (i) What are the values of L, S, and J? (ii) What is the minimum number of electrons which could give rise to this? (jii) Suggest a possible electronic Solution (i) For the state *Dsp, 25 + 1 = S232, L=2,J=52 (i) Minimum number of electrons which could give $= 3/2 is 3, since each electron has s = 1/2. (iii) The possible combinations to get L = 2 with 3 electrons are h=0Qb=0h=2 ond h=Oh=1 a1 aa. yp)Atomic Physics 127 ‘These Wo correspond to the possible electronic configuration s%l' and s'p2, Out of these two, 5%! js not possible since the net spin is 1/2. Hence, a possible clectronic configuration is s!p?. Example 7.8 Find the values of Land § of the ground state of nitrogen. Solution The electronic configuration of nitrogen is 15?2s*2p*, Therefore, the maximum possible value of M, = 3/2. To maximize My, we assign the maximum value of my = 1 to the first electron, The maximum value of m, lefi for the second electron is zero. Then the maximum value of i left for the third electron is 1. Hence, Mim =1+04(-1I)=0 or L=0 For the ground state of nitrogen, L = 0, 5 = 3/2. 7.10 ENERGY LEVELS AND TRANSITIONS OF HELIUM The Ground State ‘As an example of L-S coupling consider the energy levels of helium, which is a two electron system. ‘The ground state configuration of helium is 1s, Both the electrons are in the 1s state and therefore according to L-S coupling scheme, L=0+0=0 _ fu2ti2e1 © [v2-1/2=0 Since for both the electrons m, = 0, their m, values have to be different. ‘nd for the other electron m, = -1/2. Hence, though $= 1 and zero are possible, the allowed value is $= 0. Therefore, for the ground state L=0, S=0,and J=0 1 one electron m, = 1/2 (7.39) The ground state is then denoted as 'So. Excited States To excite both the electrons of helium, energy more than the ionization energy is required. Hence, all the excited states of helium are one electron states. We expect 1s!2s! to be the lowest energy level, the next level to be Is!2p!, and so on. Is'2s': L=0+0=0,5=1,0 If 5 =0, J =0, the state is represented by 'So If S=1, J =1, the state is represented by *S, Out of these two states, Hund’s rules have to be applied to find the lower one. It is then obvious that the >S, is lower in energy than the state ‘Sy. Is'ap's L=O+1 s=1,0 If S = 0, then J = 1 + 0=1 and the state is 'P). If S =1, then J = 2, 1, 0 and the states are Po, >P,, 3P2.Ss 128 Modorn Physies 3 he lowest in energ: : ; , state 2Py is tl y ‘The three states together are sometimes written as Po, 1,2. The sl and triplet levels are not followed by 4p), 9P,, and 'P,, Since AS = 0, transitions between stv 7 the allowed transitions. For allowed, Figure 7.10 shows some of the low-lying energy levels on the triplet states, the thee Convenience, the singlet and tpt levels ate separately shown. 1" We TIPAN Sen Ut iiee Wansitions 38) — Fg, 38, — 3P,, and 3S, > 2P, are allowed. As they Wransition is shown in the figure. et lovels Singlet levels Triple : 's Py 'D, *8y Paso D324 0 $88 J) 1s5s—— 1s5p === 186d 1388 1s8p-—— 135d —_4y 15s Isds 4 1sdd 14s4s— 1s4p 1s4d —— el ' 1s3p A530 } ts3s— i 1s//p' 182s | 1 182s: 1st ft Fig. 7.10 Some of the low-lying energy levels of the electrons in the helium atom along with some of the allowed transitions, 7.11 ALKALI SPECTRA Hydrogen and the alkali metals Li, Na, K, Rb, and Cs form group 1 of the periodic table. The electronic configuration of these atoms are: Hydrogen Z=1 1s! Lithium Z=3 is?2st _ Sodium Z=i1 1572572p%3s! Potassium Z=19 1572572p%3s?3p%as! Rubidium Z=37 — 1522s22p83s?3p%qs?3d!ap 65s! Cesium Z=55 15?2572p63573p4s73.d!4p® 5574d!°5p%6s! All these atoms have a single s-electron outside a closed shell. This s-electron is called the valence electron since it determines the chemical characteristics of the atom,130 Modern Physics Binding energy, eV 0 % Paz 3p 3s Ai 5.13 cs Ground state (a) (b) Fig.7.11 (a) Energy levels for sodium without spin-orbit interaction and (b) the prominent yellow lines of sodium. ‘The general features of the spectra of all alkali atoms 5° similar to that of sodium, However, the doublet separation increases markedly with atomic number. The separation in the first principal series doublet of lithium is about 0.2 ‘A, the corresponding separation in sodium is 6 A, and the one in cesium is 422A. LL TERMS OF EQUIVALENT ELECTRONS this case, some of the terms is a consequence of Pauli's 7.12 SPECTRA valent electrons are thos« + derived for non-equivalent el principle. Equivalent electrons mus and same / values. In Teetrons are-no longer possible, which t iffer in their values of my or m, since 7 and Tare the same for them, Terms of equivalent electrons can ‘easily be obtained using a scheme proposed by G, Breit. ‘The method is illustrated with an example of two ‘equivalent p-electrons (p?). For the two electrons ..LDLrCUL SF 0, cls mig = 1s 051s min = 12s 12s ma= 12, “yp. The my and ma values are Tabulated one in a row and the other in a column as shown in having the sameAtomic Physics 129 7.11.1 Shielding by Core Electrons In all these atoms except the hydrogen, the valence electron moves in a net field of the nu le of positive charge +Ze and the core of electrons with negative charge —(Z ~ I) e surrounding the nucleus. These electrons act as a shield between the valence electron ‘and the nucleus. Owing vo tis shielding of the attraction ofthe valence electron by the other electrons, the effective nuclear charge is not Ze but a lesser value Zu. The energy is then given by , ° RheZ? Rhi y= = IE oP 1X where n value of n and @ is a screening constant which is different for the different /-states of a givel R is Rydberg constant. Hence the L-degeneracy is removed. The value of Zu is largest for 3s and hence it is lowered the S state has less energy than the P state, the P state much more than the 3p state. For a given 7, tess energy than the D state, the D state less than the F state, and so on. With increasing n, the energy difference between states becomes less and less. For sodium the 5d and Sf levels almost coincide. Figure 7.1 (a) shows the energy levels for sodium without the spin-orbit interaction. It may be noted that this type of shielding will be there in all atoms except the hydrogen atom. ‘The spin angular momentum of the valence electron combines with its orbital angular momentum and gives the total artgular momentum [7G 4D h. If 1# 0, the total angular momentum quantum sn have the values j= 1+ (1/2) orj =1 ~ (1/2). That is, each of the [ levels (I # 0) in kes the only value 1/2 and therefore the S states remain number j ¢ Fig. 7.11 splits into a doublet, If! = 0, j t as singlet. The selection rules for the transit ‘An = any value, Al = #1, Aj =0, 21 jons are (7.40) following four series: ‘ons may be classified into the n=4,5, 6, doublets Different trai Sharp series ns > 3p Principal series np > 3s n= 3, 4, 5,» doublets Diffuse series nd > 3p n= 3,4, 5, -- triplets nf 3 3d n= 4, 5, 6, «+ triplets Fundamental series series are observed somewhat diffused. “fundamental’ und to be sharp. The lines in the principal ‘e the namie, The diffuse series lines are s The lines in the sharp series are fot Jose to the frequencies of the both in emission and absorption, henc ‘The frequencies of the fundamental series are very © hydrogen atom and hence that name. The first member of the principal se 3x92 3°P in’ = 589.0 nm (D,) and 3Pip 2 FSind= 589.6 nm (D1) jum, Since the doublet separation of P states diminishes as the the principal series doublets decrease towards constant as the initial energy from doublet levels and end ly three such lines ries doublet, Fig. 7.11(b), which corresponds to low lines of sodi +r increases, the spacings of in the sharp series, the doublet separations are gets. The diffuse and fundamental series start re triplets a5 the selection rules allow on are the prominent yell principal quantum numbe the series limit. However, states involved are all sin on doublet levels. Still the lines a (Example 7.4).Atomic Physics 131 jg. 7.12(a). Calculate the M; values (mj; + mp) as given in figure. Similarly compute the M, values (Fig. 7.1200) The M, values are grouped by dotted line as 2, 1, 0, -1, -2 which corresponds to L=2and hence a D term. M, = 1. 0, -1 corresponds to L = 1, giving a P term, Mf, = 0 corresponds to L = 0. giving an S term. Similarly, Mf, = 1, 0, -1 corresponds to a multiplicity of three, giving 4 eiplet term and M, =O gives a singlet term. Ifthe electrons are non-equivalent all the combinations are allowed giving 'S, 'P, 'D, >, °P, and °D terms. Fig. 7.12 Magnetic quantum numbers for two equivalent p electrons. In the case of equivalent electrons, the situation is different. For the values of M, along the diagonal (2. 0, ~2), my and mp are equal. Similar is the case with M, values. Hence, if my, and mys fre equal (M, = 1 and -1), the values of M, = 2, 0, -2 are forbidden. Since the values in the lower left of the array are the mirror images of those in the upper right half, one of these groups must also be left out from the calculations. Leaving the lower left half of the array, the remaining values are: @ M =k M, = 1,0,-1 i) M, = -1, M, = 1,0,-1 On the other hand, if we allow the my values to be alike, the values of M, = 1 and -1 are forbidden. The remaining values are (ii) Af, © 0, My = 2,1, 0, =I, -2 (iv) M, 20, M, = 1,0, -1 v) M20, M20 ‘The rows (i), (ii), and (iv) together give the complete set of the quantum numbers for a?P term. The row (iii) gives a 'D term and row (¥) gives a 'S term. Thus, the allowed terms in the case of two equivalent p electrons are 'S,'D, and ’P The terms 'P, 45, and 'D are excluded by Pauli principle. 7.13. NORMAL ZEEMAN EFFECT In 1896, the Dutch physicist P. Zeeman observed that the spectral lines emitted by atoms placed in a magnetic field broaden and appear to split. The splitting of the energy levels or spectral lines of a substance placed in a magnetic field is called Zeeman effect. In certain cases the line is split into Unree lines, called the normal Zeeman effect, which could be explained on the basis of classical laws. In the more general cases, the observed splittings are more complex. This is called the anomalousASE Modern Physics Zeeman effect, which could be understood only on the basis of quantum ideas and spin. In this section, we discuss the normal Zeeman effect on the basis of quantum ee having onk Normal Zeeman effeet is the study of the spliting of energy levels of an atom having only orbital angular momentum L in an external magnetic field. The spin ee ey vucll atoms aero toms having vo valeneectecttons (He, ZC, Hay.) with spins oppositely oriented have S$ = 0. When S = 0, the multiplicity of the state is 1, Hence the normal Zeeman effect applies to transitions between nglet states only. 7.13.1 Early Experimental Arrangement ‘The experimental arrangement used in the early days is shown in Fig. 7.13(a). An electromagnet NS having a hole drilled along its axis and producing a strong magnetic field is used. S f N No field | WW II yy oN toniuanai| “| view | ; \ Tanevere | { @* Ll] @ ) Fig. 7.13 (a) Experimental arrangement for the study of normal Zeeman effect (Sy, Sp are spectrograph positions and L is the light source and (b) observed spectra, A source of light such as a mercury are of a helium discharge tube which emits line spectrum is placed between the pole pieces. The spectral lines are observed with the help of a high resolution spectrograph. The light can be viewed parallel to the magnetic field (through the hole in the pole piece) or perpendicular to the field. With no magnetic field applied, the lines observed are unpolarized. When the magnetic field applied and viewed perpendicular to the field, a spectral line is found to spiit into three lines, the central one appearing at the same position as the original line [Fig. 7.13(b)]. It is plane polarized with the vibrations parallel to the field and known as the m-component. The outer components, called the components, are symmetrical about the central line and plane polarized with vibrations perpendicular to the magnetic field. The spectrum when viewed parallel to the magnetic field is found to split into two lines, one on the higher wavelength side of the original line and the other on the lower wavelength side. They are found to be circularly polarized in opposite directions. 7.13.2 Theory Consider an atom having orbital angular momentum only, placed in an external magnetic field By along z-axis. Let the quantum state of the atom be specified by the orbital quantum number 1 and energy Ep. The interaction energy (AE) of the atom in the magnetic field i AE = ~~ By = — Lt) Bo cos 8 4nAtomic Physics 188 where 0 is the angle between the L, vector und By. 2 mh since Weng Land eos = wh 1.42) cL By ( ag = SEh eh amy 143) am Lm ‘The factor eh/2m can be replaced by Bohr magneton fly, ‘Thus, the energy of the state given by E= By + AE = Ey + Hn Bom (7.44) sre fnetor my has QU-+ 1) values, namely fy —F+ Uy oes Or soos = Dy be Hence, the energy E can have QL + 1) values, Thus, if 1=0,m=0 => E= Ey P= 1, m=0, 21 => & 122, m=0, £1, £2 => E = Ey, Eo Hy Bo. Fo + 2HaBo Figure 7.14 shows the splitting for the / = 0 and f= I slates. Transitions occur between states raving different Fevalues and the selection rules for these transitions are Al=tl; — Amy=0, £1 (7.46) (7.45) Fig. 7.14 Spliting of energy levels in a magnetic field for the 1 = 0 and / = 1 states of an ‘atom having orbital angular momentum only. The involved transitions are also marked. Consider the transition between the energy levels E' and gf E! = Eh + MpBomi (7.47) Bf = Eh + UpBomt (7.48)“suonoa|a jo uids ap Jo asnud9q st waned uewsaz, 2 i J pte See SIME snojouoUT sty -229/f2 unuaaz snopruoun ay payrd st UoUDrWoudyd su, i 7 ie Wunou ayy ur paazasqo sou sax amp urip xajditod o1out Udyo st pjayy snouzeur e J HUE winuswow seindue uids oxszuoU BuLAcy stuore Jo sous endRds Jo Funds Nf 103443 NVW33Z SNOIVWONV P12 “WOT UiNIWIPED OU Jo 'g,5 — %q,9 voNISUEN OW 10) WioNed UOWOOZ |OWION SPZ Bia way uty ae Sly Sao a0 "ieee ‘ o I Tas t z ie 0 3 Zeal i = oe o=e “SIL “Sig Ur parensnyt axe suonssuen pur sjarc] £8209 Surpuodsanioo ain pur [= “0 = hwy “LE = JV axe pamoljos 2q 0} sojny uoNa[9s atl] ‘play Sneuseur B Ul Sag] ¢ OUI sds YoY Q = 5 pue*T =f ‘T= 7 soydu tg, ‘pury sayIo ay) UO “Sirs aay ory siyds yaaa] sip ‘pyayy onouSew v jo souasasd ayy uy -Q = Ss ‘T=/ T= 1 SoNdWE TG, vemos ‘wore ummupes sip Jo 14,6 <—q,9 wontsuen oxp Joy woned ueweIz ay MEIC 6'L aIMuexaT “pre “Bt UL payseus osje axe suomsuen ayy, way soy 2th sn “ye th pur Ma, St SOUI] 2aNp ap Jo sajsuonbasy ayy 198 aM [Ns UOHOITOS uy ayy Surk\ddy =% uxt paca rn wae * tug 9g rl + AY = AH mug og trl +97 — 27 = 1-7 sory WipOW, HETAtomic Physics 136 Lande’s g-Factor Consider an atomic level specitied by its electronic configuration and by the values of the angular momenta L, S. and J. In the absence of a field, its energy be Ey which is (2/ + 1) fold degenerate. When placed ina weak magnetic field By along z-axis, the interaction energy AE = ~(Hy + Hy) + By (7.51) Since on 2m = AE = 5 (L + 2S) - By (7.52) and As the field is weak, L +S =J coupling will be very strong and therefore we cannot break (L + 2S) - By into two terms. Based on quantum mechanics (Wigner-Eckart theorem), we can write L+28S=g] (7.53) where g is a constant known as Lande’s g-factor. Taking the dot product of this equation with J J-(L + 28) = oF (7.54) The operator J-(L + 2S) can be simplified as follows JL +28) =F +S) = L4+I-S Since L = J - S, we have ? = J? + S?-25-S P+9-C 2 JS= Equation (7.54) can now be written as Bae 5 Pe ose =e (1.55) In this equation J, L, and S$ are operators. Taking the average value on both sides of Eq. (7.55), _ 2 pn UU+h4sS+0 LED gg yet JUN +S (S+N-LIL+N 756) 250 +1) Lande’s g-factor is a dimensionless number which varies from state to state. galt Splitting of Energy Levels in a Magnetic Field We shall now investigate the effect of a weak magnetic field By along z-axis on the energy levels of an atom. In.a weak magnetic field, the energy due to the external magnetic field is small compared to the spin-orbit coupling. The energy due to the interaction of By with the system is given by e oe! 57) 5 pBycos 8 (7.57) AE = -Hy-Bo e mst B136 Modern Physics Were O is the angle between J and No, Since cos O= Ja/J and Je = mah et pany = ghtnBons use) 2m ‘The energy of the state E is then given by + gtlyBony (759) The quantum number m can take the (2/ + 1) values mys Sd thee Consequently, we get (24 + 1) equally spaced Zeeman sublevels. Denoting the initial and final levels by single and double primes respectively, we can write the energy slates as El = £5 + g'MaByn} (7.60) E" = ES + g’gBony G61) tions are The selection rules for these tran Am, = 0, +1 my =0 > my is not allowed if AJ = 0. The emitted frequencies are FS HaBo Cort — aft > Foe + HAO Gens — gm) lp Bo yy sy oe vey BHO ying ~ gn) (7.82) Thus, it can be concluded that the anomalous Zeeman effect is a direct consequence of electron Spin. Example 7-10 Evaluate the Lande’s g-factor for (i) pure orbital angular momentum, (i) pure spin angular momentum, and (iii) the state >P;. Solution (i) For pure orbital angular momentum case $= 0, Hence J = L. The Lande’s g-factor is then L(L+1)-LL+) 2L(L+l) Gi) For pure spin angular momentum case L = 0 and thus J = S(S#N) +S ($+) 2S(S+1) (iii) For the state 3P,, we have $= 1, L=1,and J =] 14 GXD+CX2)=0x2) _ 3 20x2) 2 gels 1 galt 2 8g Example 7.11 Draw the Zeeman splittings of the ground state level 3% un ‘Sip and the excited state levels 3°Pyg and 3°Pyp of sodium. Also, draw the transitions allowed by the selection rules. aa.Atomic Physics 137 Solution For the Sip. level, J = 1/2. Hence, it splits into two levels corresponding to my = 1/2, -1/2. The 7Pip level also splits into two levels while the 2Pyq level splits into four corresponding to m= 3/2, 1/2, -1/2, ~3/2. The single spectral line (Dy line) in the field free case splits into 4 lines and the D; line splits into six lines. (Fig. 7.16) my 32 2, ie 12 12 ~w2 Pra 58964 12 7819 “12 Fig. 7.16 Zeeman splittings of the D, and Dz lines of sodium. 7.15 PASCHEN-BACH EFFECT ‘The anomalous Zeeman effect discussed in the previous section is valid provided the magnetic field By is weak. When Dp is strong. the spin-orbit splitting would be small compared to the magnetic splitting of the energy levels and can be neglected to a first approximation. In such a case fi, and 11, precess separately about the field direction. Hence, the two can be treated independently. Then the interaction energy AE in the fickt By is given by DB eo -y By pyBy (7.63) ‘ =n ao£80- We have We-sGL and p,e-£S 0-55 28 Hence, LL By + 2 28-My © SLB cos (LB) + 5&25Bo cos (SBo) Im 9" Im Im 2m ely ely = Shue Shes, (7.64) where we have used the result cos (LBs) = L/L and cos (SBq) = S/S. Since L, = mjh and S, = m,h, Eq, (7.64) reduces to AE= $m, 4 2m,) = plpBo(my + 2m,) (7.65) Including the interaction energy, the energy of the level becomes (7.66) Es Eo+ AE = Ey + MyBolrm + 2m,)198 Modern Physics Since m, = £172 E+ pyBo(iny #1) = Ey + flpBo my HaBo (7.660) the same as the one for normal Zeeman effect, Eq. (7.44), excent for the additional constant term ftyBy. When we apply the selection rules, the sic onal term is cancelled. Consequently, the pattern for the strong field case, known as the Paschen- ch effect, is a triplet as in normal Zeeman effect, except that cach line may have a fine structure due to the negligible spin-orbit term, The expression for energy is 7.16 STARK EFFECT The Stark effect is the electric analogue of Zeeman effect. In 1913, Stark demonstrated that every line in the Balmer series of hydrogen, when excited in a strong electric field (100000 V/cm), is split into a number of components. When viewed perpendicular to the field, some of the components are found to be plane polarized with the electric vector parallel to the field and the others polarized with the electric vector normal to the field. The interaction energy of a hydrogen like atom in an electric field can be given by an expression of the type AE= AF + BF*+ CF? (7.67) icients A, B, C have been calculated from end on the quantum number n and some where F is the strength of the electric field and the coeffi Quantum mechanical considerations and are found to dep. other new quantum numbers, The first term in Eq. (6.67), involving F to the fi the secorid term, involving F to the second power, is called the second order Stark effect, and so on. If the field is not too large (F < 100000 V/cm), the lower states of the hydrogen atom (n small) would be expected to show only a first order Stark effect. In the first order Starke effect, symmetrical spliting of the energy levels about their field free position is expected. The second order effect becomes appreciable for higher states and higher fields. The second order effect produces a unidirectional displacement of each line. Measurement of Stark components gives a very accurate method for the d: moment of atoms and molecul rst power, is called the first order Stark effect, letermination of dipole les which is a very important electronic property. 7.17 CHARACTERISTIC X-RAY SPECTRUM When a beam of electrons accelerated through a a target, X-rays are produced, In section 2.5, we have spectrum which depends on the accelerating potenti target material are also emitted. These are referred to as characteristic X-ray spectrum, ‘The accelerating voltages are of the order of 10000 V and therefore the bombarding electrons will have energy sufficient to knock off an inner core electron, say a 1s electron, from the target material As an electron from the 1s subshell is removed, an electron from a higher subshell will make a transition to fill that vacancy. The excess energy will be emitted as an X-ray photon in the process. If the X-ray emitted is in the process of filling a vacancy in the K shell it is called K shelh X-rays or simply K X-rays, To fill the vacancy, the electron ean come from the L, M, N,... shells, bt they already discussed about the continuous X-ray jal. In addition, X-ray lines characteristic of the