104.2 Quantum Theory of Diamagnetism Inamagnetic field, the generalized momentum Pof a particle carrying a change ¢ is Pam? teh =m +ed yas eX" aoa) here A is the vector potential defined through Eq. (10.17). Scanned with CamScannerMagen 284 ang with a velocity @ in an electric ang ‘The force F acting on the charge o moring me field is known as Lorentz force and is given : Fee[B+ (@~ | ay ‘ehere E and H are eletric and magnetic Held strengths respectively wy The electric and magnetic fields satis Maxwell's equat oB=p a v.B= 2 (ng VxE= =F (1015) FxBams (ann From Eq, (10.14) it follows that B can be expressed as the curl of a vector, ie. ads de 20 H>_B-9x8 pomnes Bha deereyin where 7 is the vector potential. OA ‘Thus, Eq. (10.18) takes the form ¥x#=-3 (Vx 2) vx ( + #) =0 (10.18) > Hence, we may set 2424 __W (vxl9-e) (4049) where ¢ is known as scalar potential yA 4 pA 4 Ae (10.20) ot ue oN, We, therefore, get Lorentz, foreé, given by Eq. (10.12), beo™™ Ponte ae- Ve Been] Now, xx?) = OAr _ OAz 02) (x9 an (ee) a(t) Sen (A) = 2 det dy toed) wos! Scanned with CamScanneragnetism we? 285 gad 4s Oe 9, Oy ta (10.24) dds _Ods a4, a de “Be = Ge ty SA yy Ode Fars (10.25) eocting EA (10.26) from Eq. (10.23), we get si! 8 (yf) — She Ode _, (8d5 BA, aA, eT (8) ae ay ay (10.26) conpating Ea: (10.22) with Eq. (10.26) we find that (992) -2 (aq) 3,96 (10.27) Using Eq. (10-27) the components of Lorentz force \given by Ea. (10.21), along the three cqordinate axes may be written as . 7 =mie__,06 dA, 8 > Beam = eas ae tea (2-4) vu (10.28) (10.29) its (de 8 : rn meas a tex, (7-2) (10.30) The above three equations may be copfeniently put in the following compact vector tation: ’ 2 (nbred)=V[-e(D] Yanai Wenow put the above equation in the Lagrangian form d (aL) _ ab ai ae Ber 7 10.32) a (i) > ee ce > where L is the Lagrangian and q1 = 2, d2 =y and qs = 2. at VN zi ae Clearly, if we assume the Lagrangian to be of the form po & AME Lajmd-V-ebte a? ‘ad substitute it in Bq, (10.92), we get Bq. (10.31). Hamiltonian is given by ‘ BoP Yt Meteo tail . “2k @-ajon@-] taal fain ea? a= (#-ed) +8 os (10.34) Scanned with CamScannerMa 286 etl where we have used (7- eA) m Ree eae state Schrédinger equation describing the motion of a Don-relativigt terial particle is given by material pee Hy = Eb (03s) Using Bq, (10.34) and making the substitution?” + in, the Schrédinger alla takes the form 2, ( weal ldabre | ¥. (dv) = (9-2) v4 2-ve From Eq. (10.36) we see t that the effect of the magnetic field is to add to the Hamiltonian the terms (9 244-V)+ oe (1031) m HW For an electron these terms may be treated as small perturbation. If the magnetic field B is uniform, we may choose AatBx? = as (10.38) If the field vector B is in the z-direction then we have B, = By =0;B,=B and Eq, (10.38) may be written as df Ra=tloos zy ez - This gives th ives the component of Z aloug the three coordinate axes as & weal 1 Ar= 5 Bu Ay= 33a AL=0 we Scanned with CamScannerLa 2 pssagnetsi s 287 all Va =(2+ 2 2 Gb Os 4 Aegis RF 3 - 10 18 28 “Ws (iA +jAy +k) (72 452 442 ( JAy ) (+52 +42) 2 A af 58 By+j- 5B: pS 492482 y}-hpe48)-(2 452 +42) 2 De Deters’. 25 + Bay AV 7 oe 10.40) 3 (-Z- 7) (10.40) a 1 T Aa ALY AS + AD = GBP + Bea? i 1 A= Pe +y’) (10.41) Using Eqs. (10.39) to (10.41), Eq. (10.37) takes the form ,_teh B/ O98 2 124 H =i (ag 1%) +e zB @ +") (10.42) The first term on the right-hand side of Eq. (10.42) is proportional to the orbital angular ‘momentum component L,. In mono-nuclear systems, this term gives rise to paramagnetism. The second term gives for a spherically symmetric system a contribution 20 ne Es B= meet +y¥ 3 'y fast order perturbation energy. The associated magnetic moment is diamagnetic: OB PB, OB Gm i “tee, the atomic susceptibility xat is given by 2 ‘a= 4a -(#2)z, as B= oH (10.43) and is ‘Sin agreement with the classical result. Scanned with CamScannera 288 Meret 10.4.3 Discussion On the basis of quantum orbital theo nuclear charge Z is given by ry the mean value of? for an orbit about an gp in, K ) (to4y) adivs of the innermost orbit in hydrogen atom, » i . * q muthal quantum number. st o the gram atomic diamagnetic SUsceptbi y where ao(= 0.528 x 10-1 m) is the ra radial quantum number and k, the azimutha’ ‘This gives for the contribution of the orbit xa = -2.83 x 10°77 = a [n? (5,23 xa = 0.785 x 10-* | (9 — 3 (io If the effective nuclear charge is calculated from this expression for helium with two len. trons from its observed susceptibility (xx = —1.9 x 107°), it comes out to be 0.93 which i too small. ‘To make the expression for susceptibility more accurate, van Vleck and Pauling mocifei the above expression as 2 (5 3i(i+1)-1 xa = —0.785 x 10-% [= (sr) (1048) where J, the orbital quantum number, is equal to (k ~ 1). Pauling’s calculations necessarily involve a number of approximations. For spherically symmetric atoms, Hartree has devised a method with which the charge distribution satistying the Schrédinger equation may be worked out more precisely. He has given tables and curs for a number of ions and atoms showing the charge per unit radial distance in a spherical stl of unit thickness. i a be the charge in electron unit per unit radial distance, then the number of electros in the ions is equal to / ( 2) dr. dr 0 For the diamagnetic susceptibility, he obtained Xa = -2.83 x 0 [ (¥) ae (i057) 0 This integral can be evaluated graphically (Figure 10.2). Using atomic units for distan the susceptibility is given by 0.785 x 10-® x area under the shaded portion of the curve XA= For helium this gives Xa = —1.89 x 10-5 a value which agrees remarkably closely with the observed one (—1.9 x 107). — Scanned with CamScanner—+r Figure 10.2: Variation of 1 (dN/dr) with r. Scanned with CamScanner