Contents Introduction and orientation Rotational motion and the hydrogen atom Angular momentum Group theory ‘Techniques of approximation Atomic spectra and atomic structure An introduction to molecular strueture ‘The calculation of electronic structure Molecular rotations and vibrations Molecular electronic transitions ‘The electric properties of molecules ‘The magnetic properties of molecules Scattering theory0 Introduction and orientation 0.1 Use E = hv Js, v=1/T (1: period] (a) E = 6.626 x 10" 38)/(1.0 x 10-1 5) =6.6 x 10-3 = 6.626 x 107 () E=h/(1.0 x 10“ s) =6.6 x 10-™ 5 (© E=hf(10s) =66 x 10-5 2p = eqn 0.4] (Behe /A8)\(he/AKT) MAT e nel AT =0 (ett — 1 SAT At short wavelengths (hc/AKT >> 1) <1, which implies that 277: he/Sk SKF Exercise: Confirm thatthe e femum of pis in fact a maximum. 03 Let 4 = c/v, so dd = ~cdv/v*; then the total energy density is em fom ["( Lee eeeleney2 INTRODUCTION AND ORIENTATION INT ‘Sh co yBdy N(hy) () ‘S There are three modes of Write x = hv/kT; then dv = (kT/h)dx and as in eqn Sa and the total energy density is proportional to T. The value of the integral is 4/15; Exercise: Derive therefore as a function of temperat oe (BY a &=(Ben)™ 0.6 Use eqn 05a f = (G/T a (a) When T « 6, ¢4 f 0.4 Use Wien’s law: Anas? = const. const. = he/Sk [Problem 0.2] = 2.878 mm K (End paper 1 of text), Hence T = (2.878 mm K)/(480 x 10°? m) ~ 6 x 10°K (6) When T > 6, <8 1 (Oe) 0.5 ‘The Boltzmann distribution is and f? > 1 an 0.7 As T + 0, 05/T = 00; Hence om o-Eme (9) frre] In this ase, ¢, > &y = (0+ hv, s0 To evaluate the numerics energy, which inthe Deb Un and to note that Therefore, Hence ‘and consequently Nale) _ Nate) 48 ___N dle) Exercise: Confirm nume a "ap ‘arINTRODUCTION AND ORIENTATION Nk(G6/T)eh%# Me/ Te (66 = hy (FI t a ‘There are three modes of oscillation for each atom in a solid, so /T)ehPt Crm = 3K G2 f= CLD as in eqn 0.Sa, in expression for the heat capacity of a two-level system, and plot it as a function of temperature, 06 Use eqn 05a f = (H:/T)e*/™ /(1 —e/7) (a) When 7 « 4,7 > 1; hence (I — e/7 "Then, FR —Op/THMMeHIT) = (05) Tye him, =o. [sin se = 0] (b) When T > 65, e/T ~ 1 + 66/7. Then, 1+ Ge/2 co/7){ = ~(6e/T(T Ie) = i 1-@ mil “ oo and f? > + 0, 6/T — 00; therefore To evaluate the numerical factor, we need to start from the expression for the internal energy, which in the Debye approximation is Un vaio) =9er(2)' f Co Um —Un(0) > 3x4RT4/63 a5 T +0 and to note that Therefore, and consequently Cum > Bx*RT/03 a8 T+ 0 Exercise: Confirm numerically that f tends to the approximate value as T + 0,4 INTRODUCTION AND ORIENTATION 0.8 For sodium p/T = 0.50; for diamond @p/T = 6.20. If we use the Einstein formula (with 6 ® @p), then (a) Na(s): f? = 0.979; hence Cy m/R = 2.94 (b) C(d): f? = 0.078; hence Cym/R = 0.23 The Debye formula can be evaluated by numerical integration but itis also tabulated. See the American Institute of Physics Handbook, D.B. Gray (ed.), McGraw-Hill (1972), 4.113. Then (a) Nats): f @p/T = 0.50) = 0.988; hence Cy.m/R = 2.96 (©) CA): f G/T = 6.20) = 0.249; hence Cyim/R = O74 : Evaluate Cy.q at 300 K for the Group 1 metals. Exerci 09 Su= ["(Cua/ Tat =3R [7/77 (eqns 7 our - 2 =n [osmrarn{ lar Set x = 6¢/T, dT = —T7dx /Op; hence Sa/aR= [™ (rete Jar B= yl | Therefore, when T S_/3R = [ * fret /(1 —e?) dx = 1.048 [evaluated numerically] Hence, S/R = 3.144 Exercise: Evaluate Sq for metallic sodium and for diamond at 300 K. 0.10 Each photon carries an energy E = hv = he/A = 3.37 x 10-! Jat = 589 am, 100 W corresponds to 100 J s~'; hence the rate of photon emission is (100 J s~)/ 3.37 x 10"? J)= 2.97 x 10 5°. (2.97 x 10 photons corresponds to 4.93 x 10~* instein, and so 1 einstein (I mol photons) willbe generated in about 34 minutes.) 0.11 2.3 eV corresponds to 2.3 x (1.602 x 10-! C) V = 3.7 x 10! J. Then use eqn 0.6 in the form (2/me)(hv —@)}" solongas hv > (a) hv = he/2. = 6.62 x 10-1 J when 4 = 300 nm: 12 {[2/09.10939 x 10-* kg)] x (2.9 « 10" ]!” = 8.0% 108 m 3.31 x 10-9 J < @; hence no electrons are emitted, Exercise: Examine the case where the ejection speed is so great that it must be treated, relativistically. Ww 0.12 Interpret the question = 0.13 tron differs by 10 perce Write x = hc/h- 08 For the relativistic ease Ee Therefore, a ” and so This difference occurs and hence at about 6 po Refer to Fig. 0.1. Energy Mm, ‘Momentun Energy conservation: h Momentum conservatit Parallel: h/2 = (h/2a) Perpendicular: 0 = (hjINTRODUCTION AND ORIENTATION 0.12 Interpret the question as asking for 2. such that the linear momentum of the photoelee- tron differs by 10 per cent. For the nonrelativistic case, T = p’ 2m = he/h— ©, with Write x = he/2 — ©; 80 par = (2mx)' For the relativistic case (etme? — meet mx)" = (1 +x/2me x/Ame? Pre = Ll when x © 04me® This difference occurs when he/ ~~ 0.4me2, and hence at he TmTS © Tame dnc? > and hence at about 6 pm. 3 Refer to Fig. 0.1 Energy My Momentum Af Energy hy, \\ Momentum Ay \ Fig. 0 Energy conservation: hu, + mec? = hv + (pe? + mic} Momentum conservation: Parallel: h/2; = (h/24) c080 + pcos Perpendicular: 0 = (h/A,) sin® + psind’6 0.14 From eqn 0.10, 1/3 INTRODUCTION AND ORIENTATION From (2) and (3): 1? cos?! + p? sin® 6! = [(h/&) — (hia) cos 8 + (Chi) sino? pP = hU(I/A? + (1/Aa)* cos? 0 — (2/2401) e080 + (1/24)? sin? A) 1 (C1)? + (LA0? — B/D C086) ” But from (1): Pie = (hy + mec? = hup? — mae = ((he/s) + mec? — (he/24)}? — mac* 6) ‘Therefore, combining (4) and (5): Ay? + A)? = Qa) cos = (1)? + (UPA? + 2lmee/ HLA Ps) — AO} = PAN, Consequently, Q/AAN(L = cos#) = Amee/ HY{(1/) ~ 1A} = Amce/ h(a — M)/hids Hence 5h = Ae —M = (h/mee}(1 — €088) = (2h/ mac) sin? 14 Exercise: Examine the non-relativistic formulation of the effect. Rul(1/22) — /n?)) Hence, plot 1/2 against I/n2, and find Ry from the intercept at n = oo (since then 1/4). The data extrapolate (linear regression) to [hoo = 2.743 x 108 mm 743 x 10* em™! hence Ruy = 4 x (2.743 x 108 em!) = 1,097 x 108 em ‘The ionization energy (J) is the energy required forthe transition ny = 00 +m, hence 1 = hcRy = 2.179 x 10" J, Because 1 eV = 1,602 x 10°? J, 1 = 13.6eV. 0.15 Use eqn 0.13. (a) 2 = (6.626 x 10-% 35) /(1.0 x 10"? kg) x (1.0 x 10° ms“) (©) p= mev/(1—v2/2)'?? = (0.95x10- kee (10.903)? = 9.1108 kg ms A= h/p=13x 10 m 6.6 x 10 @ dmv @V=aly in AT loa h/(3mkT)'; 1.43 x 10% vip. h/Qmeev" =IINTRODUCTION AND ORIENTATION -m(v?) = 3A (equiparition); p * m{v®)"”? = GmkT)"? hj GmkT)"” : 1.6736 x 10?" kg 1.45 x 10-1 m = eV; p= mv i= h/OmeeV)"? = (1.226 x 10° my Gi) V = ORV; GV HV; d= 1.23 om: 226 nmi(v/V)" 12.3 pmTHE FOU 1.4 Use the correspondence @ T= p/m 1 The foundations of quantum mechanics (6) 1/x —> bil | © w=Don— LA (a) ff + @dde =f fax + f 96 in : (b) (fF +9)! # f'? + g!; nonlinear. @) be =p, - ype (©) fe +a) + g(x +a) = fx +a) + gle +a); linear. @ fi Exercise: Repeat the ex (© ax? 2) + 8(-x) = f(x) + (—2); linear ¢ for (a) differentiation, (b) exponentiation. Exercise: Devise operat 12 [x pl=ih Therefore, we require x such that [x, A+ B](h/2m)"? = if. 5 Use the correspondence Write x = aA +bB, then because (a) T= p/m alA, B]+ 5B, Al =a~b 1 [aA +bB, A+B oi ae ©) w= Den =ih i@mny'? @u=y One solution is (@) b= xp, —yp, = ilmh/2)" i(mh/2) Exe Repeat the exercise for p = (H/2m)"/"(A — B) 13. (dst = ates an ieninctn geal (ajane* = Boxe” = 2 fs (jase = tx notanes (d/dx)x? = 2x; x? not an ef. (G/sovar+b) = aor baotanes (d/dx) sin 208 x; Sin.x not an e.f, Write E — in(@/3t), (b) (A? /dx?)e (@/dx?)e™" = 2aet” + 4a?x*e""; e4*” not an ef. (/dx?)x = 0 = Ox; x is an e.f.; ev. is 0. o* isan eigenfunction, eigenvalue a? Therefore, the relatvist (@/dx2)x? = 2; x? not anes (@/ax?)(ax +b) =0 = Olax +5); ax +b sane; ev. is 0. = (@/dx?) sinx = ~sin.x; sinx is an ef; ev. is ~1 a Exercise: Find the operator of which e*” is an eigenfunction. Find the eigenfunction the Klein-Gordon equ, ‘of the operator ‘multiplication by ‘conserved.THE FOUNDATIONS OF QUANTUM MECHANICS 1.4 Use the correspondence in Section 1.4 T= —(H2 /2m)( fax?) in one dimension ) {(2?/ax*) + (@2/ay2) + )V? in three dimensions. + multiplication by Yo «= (hfdlx@/ay (R/iN(0/88) for x = r cos 6, — multiplication by (x? > {1 (@/ax2) — (p)?) for 1/r, xp, and n 1 2m —> multiplication by p?/2m, p? = p? + p3 + p’ © w= Dan =i DeW. 9 =ie/op) +50 yx = ip, (@/Ap2) — pe(8/Apy)) 8? /ap?) — (@/aps)") — multiplication by Exercise: Devise operators for I/r, xp,, and e 1+ p'yme2y nc + i)(@/Ax), ete; ther ax?) + mt Therefore, the relativistic analogue of the Schridinger equation is Wea w/ax ty = Rew yar? the Klein-Gordon equation. Since W coset is a solution, the probability is not conserved,10 ‘THE FOUNDATIONS OF QUANTUM MECHANICS 17 @ [ver vnie = 082m [ye /00?y vas J orctaeyyas = f vgiaravavspanas Wy (yy/ax) — / (avg /ax)dvp/axyde [ [use =ao~ f eae] = Yeon vio + f basa? na teach limit y*y" and y*'y disappear; therefore fur But T* = Thence f ¥sTvydr = f(T Va)" yade, and so T is hermitian. ar = ram fevzpete= frye © J viens = evo ViBUo/90)d9 = {vim f n/9 [eygradrnae = [dota vad = 1) ik and sol is heii scone a)" Vode Exercise: Confirm that p, 2, and I} are hermitian. 18 (m|A-+iBin) = (mlAln) + ifm|B|n) in|Alm)* + i(n|[m)* [A, B hermitian, eqn 1.26} (n| Alm) — i(n|B\m)}* = (nl ~ iB |e)" Hence, A ~iB is the hermitian conjugate of A + iB (and A-+iB is not sef-conjugate, another term for hermitian), Exercise: Confirm that x + (d/dx) and x — (d/dx) are hermitian conjugates. a 1.9 (a) (pe) & (sin(xx/L)| (@) (ps x/L) | & (sin(x/L)| costerx/L)) = 0 2m{T) =2mE [V =0] {see eqn 2.32] sim(rx/L)) () (o? (_h 2 4E? =in(cln)in= n= ya Exereise: Evaluate (a) (p3), (b) (p$). THEFOU 1.10 Note that Qy ‘Therefore, the three fun Exercise: Are the funet 1. Use the relations (x, pr (a) Lx, y]=0 [basie ©) [Pe Py] =O [oa (©) Lx, pel =i bas @ 0, l= 2p "a (©) EY, Pe xe = YP + = nik Exerci Evaluate [x 1.12 (a) [1/, py}; use the Us, pal © Usp, - ype ye= = Lxpyypak =21py,y]ee-t xitp +P. x0) = F0/ay9yl = Fear‘THE FOUNDATIONS OF QUANTUM MECHANICS 1.10 Note that Therefore, the three functions are not linearly independent Exercise: Are the functions sin x, c0s.x, and tan.x linearly independent? Use the relations [x, px] = if [y, py] =i [2 all others zero, (@) [x,y] =0 [basic relation} (©) Eps. py] =0. (basic relation] if [basic relation] ¥ pg — pox? =x py — pox =x pe — xix tle, pelt VO) Exercise: Evaluate [ly +l), (lk + ysl +l) + ell ! LAS e*\a) = 7U/n!yA"la) {definition of 4] Since (ar-\/2x) = Laynyatta) [A"la) = a"|a) if Ala} =ella) [definition of e*] lence |a) is an eigenstate of e* with eigenvalue e* rence ipensiate of of with ele Exereise: Evaluate (J Exercise: Find expansions suitable for the definition of (1-+ A)! and (I+ A)!/2, and iii. find their eigenvalues corresponding to the states ja) for which Ala) = ala). 1.18 AAAB > 116 ce” = (1+ A+LA2+.. 0+ B+ $B? +} U4 B+ Be) () A=sB=p5 14 (A$ B) + 4424248 + B+ Hence 2008 mA MP SLE (AF BE MAGB =14(A4 B+ SAP + ABS BAS BY) + Therefore, e*e* = e4+* only if AB = BA, which is so if [A, B] [B, [A, B]] = 0, then cf = 14 (A+B) + H(A? + AB + BA+ BY) + (1/3!)(A* + A?B + ABA + BAA + BBA + BAB + ABB + B) + 1 A+ B)+ J? + 248 + BY) — HA, BY + (/3D(AS + 3A°B + 3B? + BP) HA+ BLA, B+ 0.1f(4, (A, BI] Therefore,THE FOUNDATIONS OF QUANTUM MECHANICS Exercise: Find expressions for cos A cos B and cos Asin B, where A and B operators such that [A, (4, BY} = (8,14, BI] =0 (Use cos A = He" +e“), e LAT (H, pel = (p2/2m + VQ), pel = [Vs Pe = (hii) (VxN(@/Ax) — (8/82) VO} = (hifi) (V(8/Ax) — @V/9x) — V(x)(@/9x)) = [Hx] = [p2/2m + VG), x] = [p3. x1/2m = (2 /2myla/ae2, x] = (22m) ((#/dr?)x — x Jax?)} = (22m) {(d/dx){1 + x(d/de)] — x(C2/dx?)} am) {2¢d/ex) + x(d? /dx*) — x(d?/dx} ‘m)(d/ax) = (h/im) Ps (V(x) = V entails (H, pe] = 0, [H. x] = Cifimp, ) = Hex? entails [H, pe] = ix, Hx) = rreor entails UH, pe) = iR(@V 9x) = Ge? /4xep)(Or-!/22) Since (ar~' /ax) = (8/Ax)(x? + y? . x/r? we have (Hp = odxr?) LH, pel = (fim Exercise: Evaluate [H, T], where T= p2/2m, and calculate it for the three cases LIB AAAB > $((C)| with =[A, BI/i_ [eqn 1.34] a) A= x, B= pai[A, BI [x, pl =ih> C= Hence, AxApe > $h tc.) [pas Py] = Os hence Ap, Ap, > 0 (unrestricts Dp, B= V(x) 2m) {(9"/ax")V — V(2?/ax2)} 2m) {V" +2V"(a/ax) + VA ve@/ax)) 122m) {V" + 2V'@/ax)} = (2 /2m)V" = Gih/m\V’p, Therefore him)",“4 “THE FOUNDATIONS OF QUANTUM MECHANICS THE FOU and in general the rh. is nonzero 1.21 Construct the matices (6) Amex, B= pi/ [A, B] > ~elx, p3}/2m = (ieh/m)py {Problem 1.17] wi MAE > Heh/m)ipe) For systems described by real wavefunctions (p,) = Os hence then AWAE > 0, and AwAE is unrestricted : Poo Pa (©) A=x, B = p?/2m;[A, B] + [x, p?]/2m = (ih/m) px as above. , Pwo Pi ‘AxAT > (h/2m)(ps) = 0 for real wavefunction (non-degenerate states) Wel = | ps pa Exercise: Determine the restrictions on the simultaneous determination ofthe values of x? and (a) the momentum, (b) the kinetic energy. 1.19 (d/dt)(Q) = Gi/N)(LH, Q)) [eqn 1.35}. For a harmonic oscillator, H = p?/2m + $kx*, and, xp px== (Hx) = [p2/2m, x] UH, pol = [242 Pe (a/ds)(x) = sm) ih/m)ps [Problem 1.17] ikx [Problem 1.17] (d/a1)Xps) Therefore x) = (I/my(a/ar) (pe —(k/m)(x) ‘The solution of (42/d12){x) —ck/m)(x) is (x) = Acosat + Bsinat, o? = k/m (p) = m(d/at)(x) = —Amosin ot + Bmocoset which isthe classical trajectory Exercise: Find the equation of motion of the expectation values of x and p for a quartic oscillator (V oc x4), 1.20 Use egn 1.35.5 ince = (h/i)(8/24), V(#) = V,aconstant, and H = (1/2mr2)/2 (Le) = 1/2mr2y(2, 1) + Vk] =0 {LV tel « AV /09 = 0), Hence, (d/dt)(/,) = 0 Exereise: Find the equation of motion for the expectation value ofl; for a particle on a vertical ring in a uniform gravitational field. Examine the equations for small displace- ‘ments from the lowest point.THE FOUNDATIONS OF QUANTUM MECHANICS 1.21 Construct the matrices [xy] and ll pv 00 0 0316 ‘THE FOUNDATIONS OF QUANTUM MECHANICS f- 0v2 10 v2 J o-so] | oso wl ye o-s..|+zhl 20 s L J a THE FOU 100...) 030 rs) =3'| 00s iu © H=-@pAmy ravalues of Hare the (©) Since F = -4V/ fore (u+ $) hav et ple. ‘Therefore, ise: Evaluate the commutators {H, x] and [H, pl, and find the equations of mo- tion. What matrix represents the rate of change of the product xp,’ Exercise: Write downs 1.22 (vixp2xiv) = S(olxp2lv’y(velv) ae 24 (modes (ulxp2|u + 1)(v-+ Ix|v) + (vlxp2lv — 1)(v— I fxlv) 1h ae = (olxpilv + 1)(h/2may"™u + 1)"2 + (vlxp2lu — 1)(h/2me)" 20" © ty = h/2mw)!! Colpo N+)! + (wlxp2le (olspitv+ 1) = Solpslo'ipelv+1) (ulxpelv +2)(u + 2Ipalv + 1) + (vlxpelv)(vlpelv-+ 1) /2)' {(ulxpalv + 2\(u +2)"? — (ulspylv)(v+ 1)"?} Iw!) By the same argur = i(hme/2) hence (olepelv +2) = ool ('ipalv +2 = (olxlv+ 1)(u+ Apel +2) = ih Mw+ Dw +29)" ane wlepalv) = (ulxlv-+1)(v+ Hlpele) + (vbelv — )(v— Ipelo) =ih/2)( +) —v) = fin ) = (olxpslo)(ulpalv = 1) + (elxpelv —2)(0 v—1) se rea rere (b) Equation (1) has Equation (2) has Therefore, om abst vlxpelv—2) = (vixlv—1)(v = ipsle Then, combining all the elements: in(ueo — yy? (olxpzxlo) = G20? +2043) : Note that || Let Vit) = Exercise: Evaluate (v)x4[v) and (v + 2ixp2x}o 1.23 In each case HY = Ey with @H (12 /2me)V2 ~ (N8 2my)V2 ~ (2 /Areor) This can be expressed in terms of the motion of the centre of mass and of the relative motion of the electron and nucleus cos(t H = Hom + Hesave sim), the full ineTHE FOUNDATIONS OF QUANTUM MECHANICS Hex, = (02 /2my)V2, ne = —(12 /2n)V? — (€ with my = met mp. i (me + ms) (b) H = (12 /2my) VR — (UP /2me) V3, — (0? /2me)V2y Aor) — (2e*/4repra) + (e?/Ateor Hee (M2 /2m_)(V, + VA) + (e2/4mre0){(1/ri2) — (2/1), (©) Hescrosie = ~(02 /2me)(V3, + V3) + (€*/4zx60)—C/ra) — (nv) = (Ur) + fri) + (1/ ra) @ H=—(2/2mv (©) Since F = dV /dx, V = — f Fax = —Fx if F is uniform (independent of x) H = (2 2m) jax’) — F Exercise: Write down an expression for the Hamiltonian of a general Z-clectron atom, 124 (122m) (EW dx) + VOQW = ih /90) (a) Try ¥ = ¥2)0(0, then Crtpamy"e + Vine =ihwé (12 /amyy"W) + VO) — in /0 By the same argument as that in Section 1.12, (~N?/2m)(W"/W) = e, a constant hence ih(@ /8) — V(@) =e, the same constant; hence (a/atyind = (e+ VeOVin Equation (1) has the solution yr = Aes + Be, k = me?) Equation (2) has the solution In6(#) = In6(0) — (i/f) file + Var Therefore, on absorbing In0(0) into A and B Note that |W}? = |y/(x)[?, and so itis stationary. Let V(t) = Voosan. then ff Var = (V fa) sinc, 50 = W(x) expl—i(e/h)t —i(V/he) sinc) = WOx)(Cos } ising), @ =e1/h+ (V/he) sino The behaviour of the real and imaginary parts of W (essentially the functions cos(r + sin) and sin(r + sin z)) is shown in Fig. 1.1; the dotted line is cos(r + sin z) the full line is sin(x + sin)18 ‘THE FOUNDATIONS OF QUANTUM MECHANICS THE FO ‘The error functions and LA. Stegun, Dove on) cos (t+ sit Therefore, in the pest sin (r+ sina) Exercise: Evaluate P) 1.27 The most probable lor (or maxima) of [VPs Fig. 1 Exe vo ‘Consider the form of for an exponentially switched cosine potential energy, V(1~e~/7) cos, for various switching rates. (dani 1.25 Find a normalization constant N such that eqn (1.15) is satisfied. Hence, 1 — 3/1? = Exercise: Evaluate N [veicnw [6 f anos [7 Pee fine = Meanyta) [Pear = ev2(21/00)) 1.28 Base the answer ony Ninja? @ We pre ) We Consequently, y= (a?/)terer [The values of @ and ¢ Exercis abilities are given by W depends on Z as e-2"”. Find N for general Z. because ||? is virtua Hence: (@) P= |yoparTHE FOUNDATIONS OF QUANTUM MECHANICS = ava) fe The error function is defined as (see Handbook of Mathematical Functions, M. Abramowitz, ind LA. Stegun, Dover (1965), §7.1.1; this book will be denoted by [A & S] from now fre, inthe present case PCr sx Exercise: Evaluate P(x > 0) and P(I 127 The most probable location is given by the value of x corresponding to the maximum (or maxima) of |y |; write this location x,. In the present case Exercise: Evaluate NV for the wavefunction, Consider then another excited state wave funetion (2(x/P)? = 1}e~*?”, and locate x. 1.28 Base the answer on |y/? = (a /)e-™”. The probability densities are (WO)? = 1/rra? = 1/(53 pm) = 2.1 x 10% pm? (b) WO = 1/4, 8, #)F = (faye? = 2.9 x 10? pm [The values of @ and ¢ do not matter because ¥ is spherically symmetrical.] The prob- abilities are given by use |? is virtually constant over the small volume of integration 8V = 1 pm? = IW(O)PSV = 2.1 x 10% (b) P = |¥4(1/a, 0, 6)°6V = 2.9 x 10.20 "THE FOUNDATIONS OF QUANTUM ME HANICS 1.29 (a) For the probability of being in a sphere of radius R centred on the nucleus, alow for the r-dependence of y ag [sino wf Par fe} @ nena fr ede a4 — [1420 + 2(aR)?} ™", Therefore, for R = I/a, P (14242)07 =1~Se (b) Find the 90 per cent boundary surface by solving 0.90 = 1—(1+20R + 2(aR)*} That is, solve {142aR +2(aR)*} e%* =0.10 Do this numerically (e.g, by successive approximation, graphically, or by soft ware). The outcome is aR = 2.66, so R = 141 pm. Exercise: ind the expression for the Z-dependence of the location of the boundary ital (Tables 3.1 and 3.2) surface. Repeat the calculation for a hydrogenic 2s 1.30 Refer to Fig. 1.2. From eqn 1.46, yt + ay? a enpn{d ml (21 + (24/2 The dependence of on d is sketched in Fig. 1.3, where we have written 1 = ai and d= piso ear(1 + (2/ar)*)"" Because 9/8 = }2ma)(8p/a°)/(1 + QB/a2))-"? = (SxB/a)/{I + (26/0 THEFOU we have dé /dp = Owb (y+ VY Py T Exercise: Consider cut 1.31 Refer to Fig. 14. Forsi path length when the re ‘The phase length foqn 6 The minimum of @09¢THE FOUNDATIONS OF QUANTUM MECHANICS wwe hat =0 when f = 0 (ie, when d = 0), as was to be shown, Fig. 12 Fig. 13 Exercise: Consider curving paths 1.31 Refer to Fig. 1.4. For simplicity consider a symmetrical location of P, and P,.'The true length when the ray passes through P’ is {a+ +07? + (b=? +a The phase length [eqn 1.46] is $= Qrv/oytni 212 4 malo — 2 + a2)" The minimum of $ occurs as d@/‘THE FOUNDATIONS OF QUANTUM MECHANICS (DMO +IP +02)" = sing, and (b= D/tb =)? +a}? = sing, the minimum phase length occurs when 0; and 6, are related by im sind = nasin®, which is Snell's law. Exereise: Consider an unsymmetrical disposition of Py and Py ‘Take HW = «(8W/812), Because H has the dimensions of energy, « must have the dimensions of energy x time?, or ML?. Try W = ¥, with Han operator on x, not f ‘The equation separates into Hy = Ey, = (E/x)8. The latter admits solutions of the form 8 ox cos(E /x)"?t. Then fires « f rar cosce i", which oscillates in time between 0 and 1; hence the total probability is not conserved 2 Linear mo 2.1 For the energy in(@ (a) k= meV) 0. va)=s 10k (b) Because p p/P feqn Exercise: What va equal to its Compta 2.2 In each case W(a)h 2.3 See Fig. 2. Exercise: Sketchth wells separated and Cooske +D ( a = HC ide Therefore, A =c2 Linear motion and the harmonic oscillator 21 For the energy in (a) use E = eV. ce NE)" = (5.123 x 10? m=!) x (V/W)"? LOV;k=5.1 x 10 mt = 5.1 om Ca) = Aexpl5.1iCx/nm)}, A = W/L", L on. i) V=TOKV;k=5.1 x 10" m-! = 0.51 pm (a) = Aexpl0.51 iGe/pm} (©) Because p = (1.0 g) (10 ms“) = 1.0 10° kg ms“ k= p/Neqn2.7] = 9.5 x 10" m=; hence (9.5 i 10" (x/m) Exercise: What value of V isn Jerate an electron so that its wavelength is equal to its Compton wavelength? 22 Ineach case |¥(x) a constant (A? = 1/3 L 23 See Exercise: Sketch the general form of the wavefunction fora potential with two parabolic wells separated and surrounded by regions of constant potential. 2d y= Coonke + Dsinks =c(=te*) = C - ie £1¢C Therefore, A = H(C ~iD), *)} Fee *) (cosge®* —singe*)} +c. sin?y 400s sing (e%* —e-™*)} + 0 sin? ¢) = AhASm LINEAR MOTION AND THE HARMONIC OSCILLATOR See Fig. 22. | Exercis Evaluate Jy for yy = Ao cost coskx + Ag sin sin kx Wavefunction (a) Potential Wavefunction + Teflections rr) Wavefunction | () + reflections Potential Fig. 2.1 = 19) & = | 10 0 ¥2 32 On Fig. 22 LINEARMOL 2.6 From eqns 2.12 and 2.13 4B} = (AB) Wx, 0) = (AB For normalization (oun [oreo Therefore, ¥(x,0) =@ ox (0,0) We seek the value of x which is satisfied by $ sity falls to one half its 9 From the uncertainty pi which i in accord with Exercise: Examine the 2.7 |W (x, 0)/*is plotedinFLINEAR MOTION AND THE HARMONIC OSCILLATOR 246 From eqns 2.12 and 2.13 wee.) = f edo. ndk = AB [ex fikx — Wham} ake 92,0) = 48 exptincyae Anjin eerie = (ABe™* ix) [e' e aur} 2AB(e* sin }Akx)/x W(x, O)? = 44787 (sin LAkx/ x)? For normalization (to unity), write AB = N; then 2N*Akm = 1; hence N = (2Akx)~! Therefore, (x Akrt)"/2(@* sin 4 kx) /x Op = 2/Akz)(sin $Akx/x) OP? = @/Ake) lim (sin } Akx/x)? = 2/ Mk \(LAkx/x)? We seek the value of x for which |"/(x, 0)/2/|W*(0, 0)|? = 45 that is (sin }akx/x)°/4 in $Akx) /(4Akx) = 1/V2 which is satisfied by 4 Akx = 41,392 [solve numerically]. Hence the probability den sity falls to one half its value at x = 0 when x = +2.784/ Ak From the uncertainty principle Ap,Ax > 4h, so AkAx > 4, and hence Ax > 0.5/Ak which is in accord with Ax ~ 2 x 2.784/Ak Exercise: Examine the properties of a Gaussian wavepacket in the same way. W(x, 0]? is plotted in Fig. 2.3. For ¢ > 0 wen = [eo fiex imam)6 LINEAR MOTION AND THE HARMONIC OSCILLATOR ~ 9.0m fro % W(x, 0) — i(ht/mN FONE" /x) with $00) = fronts [" Beltak = 0) +if"@) LF =f, f” sims] and £00) = (12+ fae — 3) sin faskr + (k/2) cos kr $"G) = 2k/x) sin } kx — ka cos bk os, Q § oat a 0 3 6 1a Wig 23 Then, to first order in ¢ wan? (¥0e, 0) —ivtr/myn fete /x)} x [VEO + (hrm NGC) W(x, 0)? + (ht /m)N (W(x, 0) f*xe U(x, F(a)e Vix [Wx OD? + lit /m)N? f(x) sin } Ake /x = 1 Cx, OF & k¢aRe/myN2 RG) /? z [week LINEAR MOT a) The function g(x)/(Akx ccated by the dotted line i 1/(AK), $0 v7 " 0.08} -ereise: Continue the d 2.8 Consider the zones set ot at each interface.LINEAR MOTION AND THE HARMONIC OSCILLATOR g(x) = 1 — cos Akx ~ bx Ak sin Akx The function g(x)/(Akx)? is plotted in Fig. 2.4 and its influence on |¥(x, 0)? is indi cated by the dotted line in Fig. 2.3, corresponding to atime ¢ for which 4khtN2/m = 1/(Ab)', so [WC DPF = WG, OF + (x(x) Exercise: Continue the development of the Gaussian wavepacket in the same way 28 Consider the zones set out in Fig, 2.5; impose the condition of continuity of y and y/28 LINEAR MOTION AND THE HARMONIC OSCILLATOR, vi = Ae + Be, i? Yun Aer Bets, W 2mE |? 2m(E — Vy/te y=k/k van ‘e'** [no particles incident from right) () At B=A4B {trom yu(0) 2) Ale L + Bre#L = Anette [from yu(L) @) kA-KkB=KA'-K'B', | {from ¥{(0) 4) KANCEE Be HE = RATRHE, [rom WyCL) From (1) and (3): a’ LE YA+ HU /)B; BP =kd-YAthaeye From (2) and (4) AreHE-DL 4 plese WobL plete HDL J+ para AeePE, Sa yar = plete ene i Ate [a4 pte — aye] maya Anya ye H {Dy cos kL —i(l + y?)sink'L} The transmission coefficient (or tunnelling probability) is P= |a"P/IAP = 1A"/Ar 4y?/4y? + 1 — y?)? sin? RL}, y? WE =V) Exercise: Find the transmission coefficient for a particle incident on a rectangular dip in the potential energy. 2.9 Consider the zones atthe single interface. tout in Fig. 2.6, Impose the conditions of continuity of y and Ae + Be’ 2mE te 2m(E ~ V), uM Vu = Are () AtB=A Q)ik(A {from y(0) = yu(0)] B) =ik'A’ [from y{(O) = YO] Note that LINEAR @ E VK q| ie | a —_ 3 3 } 7 ‘Therefore the second (2a) ik(A- B)= Hence B/A=— (@b) (AB) =k He B/A=--y)} R=(1-y e-) Ey Note that R is indepe tion R is ple The fu Exercise: Considerp is the reflection coeft 2.10 Use the normalized ¥LINEAR MOTION AND THE HARMONIC OSCILLATOR Fig. 2.6 Fig. 27 Therefore the second condition becomes: (Qa) ik(A = B) = A", or -i4(A = B) = A with 3 = k/x Hence B/A = (1+ id)/(1 = id), so that R= |B/AP? = 1 for E 2b) k(A ~ B) = KA, or y(A ~ B) = A’ with y = k/K Hence W +b? = [On ON ith a = vie and E> V T+ Va-a) Note that R is independent of m. If E *~ 10.1 eV and V * 10.0V, we have R A: 0.67, The function is plotted in Fig. Exercise: Consider particles incident from the other side of the step with E > V. What isthe reflection coefficient? 210 Use the normalized wavefunctions in eqn 2.33: = Q/L)"? sin(nzx/L); also use30 LINEAR MOTION AND THE HARMONIC OSCILLATOR (1/4a) sin ax forall n @P, = [vise wr=f P, = H(1 = @/n))} = 0.08085 yt) f° sins /Lyax = § {1 2/0) sint}nm)) OP, fae = 1 [0 sans Lyd Q/L){8x — (L/2xn) cos(nz) sin(2 x/L)) (£1)"L/2n) sin2nxdx/L)} (Q/L)(8x + (L/2z) sin(Qardx/L)) © 48x /L when 8x/L <1 p, Note that Jim Py = (a) $, (b) 4, (©) 28x/L the last corresponding to a uniform distribution (the classical limit) Exercise: Find P, (and P;) for the particle being in a short region of length 8x centred ‘on the general point x 211 The zero-point energy is E = L = (h/mc)/V8 = Hence L = 0.86 pm. /8meL? {eqn 2.33]; hence, for Ey = mec? we require @, where ie is the Compton wavelength (4c = 2.43 pm) Exercise: At what length does the first excitation energy of a proton in a box equal its rest mass? 22 Since Ey = n?h?/8mL? [eqn 2.33], F = ~(4E, (AL) = 2'h?-/AmL? For an electron (m = me) with n = 1, F =f? /4mgL*, hence L = (8 /4m.F)"? = 0.4939 pm/(F/N) hence, when F = 1.0N, L 49 pm, Exercise: Consider the case of N particles in a cubic box. Find an expression for the product pV (p: pressure, V: volume). Discuss the relation of this result with the perfect, as equation of state LINEAR Mt 2.13 Use the wavefunction} The result is also obvio Exercise: Evaluate (t) asin B. Account forit Classically ?)=( an = {fb Classically, Exercise: Evaluate (x? 15 Intuitive solution: (py Elegant solution ) = (nipln) Therefore since (pLINEAR MOTION AND THE HARMONIC OSCILLATOR 213 Use the wavefunction Yr, = (2/L)"* sin(nmx/L) and the integral (1/4a2) {a®x? — ax sin@ax) ~ }cos(2ax)} ayjds = (2/L) fxsinenns/Lyde 'n) {n?x® — nw sinQnx) — Mfeos@nx) ~ 1} = £ he result is also obvious, by symmetry Exercise: Evaluate (x) when the particle is in the normalized mixed sta Account for its dependence on the parameter B. {Jsin@ax) — ax cos(2ax) ~ ax? sin(2ax)} =e | x? sin? (mx /L)dx = $1? {1 — 3/2n?x)} = {12°{1- 2x} =0.2831" (LVI {1 6/n?x?)} = fim Ax, = L/2V3 Exercise: Evaluate (x*) and Ax for the mixed state yi cos B + ya sin. 215 Inwitive solution: (p), = 0 because the wavefunction isa standing wave, Elegant solution: p) = (nlpin) = (n|pln)*{hermiticity] = (n|p*\n) = —(nlpin)Lp* Therefore since (p) = ~(p), (p) = 0.LINEAR MOTION AND THE HARMONIC OSCILLATOR Straightforward solution: (Pe = 2mEy = HE /AL pe = [(Pe— (0 (pW? = nh Using the value of 4. from Problem 2.14 AxnAPa = (L/2V3) {1 — (6/n?x?)}" (nh/2L) = (n/4V3) {1 — 6 /n?x)}!? h = (ax (V9) [1 6/n?x?)}"” (8/2) AxiApr = (4/3) {1 — 6/22)}"” (1/2) = 1.1357(0/2) > h/2 as required, Exercise: Repeat the calculation for the mixed state Yi cos f+ Yo sin B. What value of 6 minimizes the uncertainty product? 2.16 Refer to Fig. 2.8. Consider the case E < V, LINEARM Because ¥ < 00 eve respectively). Atthe i Vi) = ¥iy(0)/Vu) = wy(L)/vu(l) = WinL)/Yan(L) = Because y’/¥ is cont This pair of equations tinal It follows that ‘Then, since tank Consequ ‘Therefore, But arccos: = + Solve this equation for and finding the values MA? /2m for each valLINEAR MOTION AND THE HARMONIC OSCILLATOR ’ VW = Ae“ + Bes Vu = A’e + Bre Yin = Ave + Blet* Because y < 00 everywhere, A = 0, B respectively]. AC the interfaces of the zones: Yi(O)/Yr(0) = ~K(A — B)/(A + B) Viy(O/ uO) = iK(A’ — BY /(A' +B) Wi(L) uC y/(A'e* + Brethy Win(L)/ Yuu) = —K(A Brey (Ate* + Bie) =e [B -ause ¥/¥/ is continuous at each boundary, (A= BY’ + BD =e (a’ee — Bie**) / (ae This pair of equations solves to (-iyya'e +iy)A' = (1p) It follows that (1—y%)sinkL ~2y cosk =0, or tankL = 2y/(1 = y’ Then, since tankL = 2tan($kL)/1 — tank), tan(4RL) = y Consequently. (JRL) = 1/(1 + 72)? = hk (mV) Therefore KL = 2arecos {hk/QmV)'?} + nx, n= 0,1 But arceosz = fr ~ aresinz, so kL+2 amv)!") = Solve this equation fork by plouing y = kL and 2 arcsin(h?R2/2mV)!"2 for m= 1,2 inding the values of K at which the owo lines coincide, and then form Ey = rn. This procedure is illustrated in Fig. 2.9 for the 5 so, with kL = z, y = z and y = nx — 2arcsin2/I5,247 LINEAR MOTION AND THE HARMONIC OSCILLATOR, use E < V,z < 15.) We 84, 35,77, 137 h2 /2mL2) with zq the intersection value oft. (Be 2.9, 5.9, 88, 11.7 for m = 1,2, 3,4; hence E (A? /2m. ‘When V is large in the sense 2mV > NA2, are sin(R2k2/2mV)!”? ~ 0, Hence the ‘equation to solve is KL * nt. Consequently E, ~ n°h?/8mL? in accord with the infinitely deep square-wall solutions. Exercise: First consider the special case V = 6h*/2mL?, and find the allowed so. lutions. Then repeat the calculation for an unsymmetrical well in which the potential ‘energy rises to V on the left and to 4V on the right. (@) P=IA"?, Solve the four simultaneous equations +B=A'+B Ale*t 4 Best = Areltt 4 pleritt ikA —ikB = KA’ + «BY Ale 4K Ble! = kare — ik Bre Ht for A” in terms of A, and substitute into the expression for P. For E > V, the four conditions are A+B=A'4B! ASHES Ble = Arctl 4 prerit ikA —ikB = ik’ —ik'B WASH! — WB = ike —ikBre# Solve these equations for A” in terms of A, and also substitute into P (b) Write e = £/V @EVviP=|1+ were [iit (mV L?/P\(e = [a mv a= 1) 0, the two limits are the same. Exercise: Evalute P for E > V. LINEA 218 v4 = 0/L)'4sin three are nodes. Exercise: Repeat t 219 Ey = nh? /SmgL! Taking Roc 140 Exercise: The colo which the rings has to conjugate. What 2.20 H = —(2/2m\@ Each term must be¢ with ‘ ‘The solutions, with, 5, For orthonormality,LINEAR MOTION AND THE HARMONIC OSCILLATOR LAB Ys = (2/L)!? sin(dex/L) = 0 when x = 31, L, of which the central three are nodes. TS Exercise: Repeat the question for n = 6 By = n2(h? /8meL?) [eqn 2.33, m = me} Engi Ex = Qn + 107 /8meL3);he/A = Ents ~ Ex Hence, 2 = 8mecL?/(2n+ Ih Because n = 1N and L = (N ~ 1)Roc [Wis even] A= BmceREc/ WYN — NF/(N +1) A fnm = 3.297 x 10->(Ree/pm)?(N — 1)?/(N + 1) sc = 140 pm and N = 240 nm, The colour of tomatoes is due to a molecule resembling f-carotene, but in which the rings have undergone scission, This enables the two terminal double bands to conjugate. What colour are tomatoes if carrots are orange? H = ~(12 /2m){(0*/0x2) + (07/ay?) + (87/024)}; HW = Ey. Write ¥ = XYZ, then (UP [2m)|X"VZ + XY"Z + XYZ") = EXYZ, 2 fam) [(X"/X) + (PY) + (2"/2)} Each term must be equal to a constant; therefore '/2m)Q"/Q = E2, or — (WP /2m)Q” = E20 with Q=X,¥, and Z, and E=E* +8" +87 The solutions, with Ly. are therefore Ynsayne = C/L)? sin(ngrex/L)sin(nyrey/L) sin(n_m2/L) Enynyne = (12 +n + nV For orthonormality Vamaste = @/1) sins sinnrx/Eoe x J sincary/t)singa,y/ pay xf sinenire/t) sinen_nz/t de6 LINEAR MOTION AND THE HARMONIC OSCILLATOR Oifn, éng, ni én, orn, xn, 5 = | Litn, =nz, ni) = my, and n The degeneracy of E = 14(h?/8mL2) is equal to the number of ways of sat 2 ni + n2 = 14 with my, positive integers greater than zero, In this case the states (1,23)(1,3,2),3,1.2)(3.2,1),2,1,3), and (2,31) are all degenerate; hence the degeneracy is sx. Exercise: Show that a leaky rectangular bor, in which the potential energy rises to V ouside the box i also separable. Find the energy levels when V as the value employed in Problem 2.16 am a +B) = sar Ly/L>. Therefor Ey where A states (ny, ma) and (Aya, /2) are dey enerate (b) The states related by the relation in (a) are doubly dé Write yer, 9) poe) =) oa ay 2 ; ny =F [opr soles Lar] =5p0 It follows that Division by p@ gives wey mate and multiplication through by 1? gives Ppt rl, ImEr? pp eae Hence, if ©"/@ = Pp" rol, 2mEr? > P corresponding to Pp" + 1p! + QmEr i? — m})p =0 and the equation is separable. 4 (2m), my = 0,1, ‘The solutions of ”/@ = —m? are @ = 2.23 LINEA} where J isa Bessel everywhere, includ Therefore, because R), we requite and the permitted y tions. For instance, and find and the correspond E Exercise Determine The Schrdinger eq Substitute y = (mo andy" = &y/dy? ‘Substitute eqn 2.43 Use a ThenLINEAR MOTION AND THE HARMONIC OSCILLATOR Equation (2.1) is a form of Bessel’s equation and its general solutions are (0) = Adimi (kr) + BYjmi(kr) k= QmE)"?/h where J is a Bessel function and ¥ isa Weber function, The requirement that p be finite everywhere, including at r = O, implies that B= 0, Therefore, alr) = Adjm(kr)—|oms| = 0.1.2, Therefore, because the radial wavefunction must vanish on the circumference (at R), we require Jimj(R) = 0 and the permitted values of k may be determined from tables of zeros of Bessel func- tions. For instance, if my = 0, we solve JER) =0 and find 2.405, 5.520, 8.654, ete — = 5.78, 30.47, 74.89, ete Exercise Determine the energy levels with Jn] = 1 The Schrdinger equation is (1? /2m)(dy/ds*) + Sexy = EW Substitute y = (ma/h)'x with o? = k/m:; then ye" —y2¥r = —Ay, with = B/ Yao and y" = d?y/dy? Substitute eqn 2.43: y= Ny Hye @fay\(Hee"”) — Pye? = AHP? by?)(He) = (HY — 2yH, = Hy + Hye = QyH, —2vHy —2yH,— Hy + He (given) Hy — Qv+ DH er Qu+ DM) —y Mle"? = aH"? 20+ Iho = (v+ Lhe, as required,38 LINEAR MOTION AND THE HARMONIC OSCILLATOR, 2.24 The harmonic oscillator wavefunction for v 6 is proportional to f(y) = 64y® — 48094 + 20y* — 120 JS (2) = 642) — 4802? +7202 — 120 = 0 at the nodes This function has the following roots: 5.525, 1.784, 0.1902 [use, e.g. MathCad’s root operation| and therefore there are nodes at y = 22.351, 41.336, 20.436 Exercise: ind the nodes for v = Therefore as in equation 2.44 2.26 (a) (v+ Ilxlv) = Mea? [Hendy HeQne*dy bx =ayl [Hos (toes + ote ‘dy (Table 2.1) ly [orthogonality Mot D! Pn 221(y + DI Tea PE w+ DPE Sw+y (b)(v+ ON eeaNe [Hay (Ploer + vll-a} dy at Luly + Loy + 07H, =e NeW Heald LINEAR Exercis + Evalute ( 2.27 (k/m)}, By ‘The separation of e: ‘The wavelength req 2.28 P, = vite 16.1 pm. y Use Table 2.1 for tt (@) Po= (Hi ©) P= (HELLINEAR MOTION AND THE HARMONIC OSCILLATOR [orthogonality] aNyx!22**2(y 42)! [Table 2.1] OAD pattev 4 900+ DIM Exercise: Evalute (v + 3]x*|v) inthe sa 227 w= (k/m)}, Sho [eqn 2.42} ‘my = 1.008 w = 1.674 x 10 kg; v = 2/20 {@13.8.N m7}/(1.674 x 10” kg)) 4.33 x 10" 5“! (or 6.89 x 10"? Hz) ‘The separation of energy levels is eo = 457 x 10 Exercise: Consider the effect of deuteration on 2. 228 P, = y2(x = 16.1 pm)/¥2(0) [x is the displacement from equilibrium]. When x = 6.1 pm, y = (me/h)'/2x = 1.33 0, m in Problem 2.27]. Use the wavefunctions Yo = MoH(y)e", so that v2 = NBHE Py = HE)” HO) with y= 1.33 Use Table 2.1 for the Hermite polynomials: (®) Po = {30)/HBO)e” =e (b) Pa = {H2(y)/H3(0)} e-™ = (1/144) {16y* — 48? + 12% = 0.617 Exercise: Repeat the calculation for the deuterated species and v 229 (x) =O by symmetry, (ps) = O by reality (Problem 2.15]. AlternativelyLINEAR MOTION AND THE HARMONIC OSCILLATOR, 0 ”) -f VED /ax ode = (tk joy"? (V3 Ap. Which is in accord with AxAp, > $f. A Gaussian function is a minimum uncertainty function, Exercise: Deduce that Ax Ap, = (v + $)f fora general value of v has V(x) = —V and all solutions are oscillatory for positive ener: 2.30 Zone IL in eqn 2.17 Zone I: y= A’e*s + Bio R= 2m(E + VI? Hence $ can be constructed from eqn 2.53 and T = QM in eqn 2.50 by replacing « in eqns 2.48 and 2.49 by —ik 3 Rotation 3 E =mi(t/2 E =mi(2/2n my = 1674 x1 Hence E = (130% = he/AE Exercise: Caleu Write x = ros Similarly Therefore, Thats,3 Rotational motion and the hydrogen atom 2 kg, R= 160 pm; M?/2myR? = 1.30 x 10-2 J 30 x 10° Jym? and AE = (1.30 x 107 (1 = 0) = 1.30 x 10-5 10° m= 153mm Exercise: Calculate the effect of deuteration on E and (1 <0). 32 Write x = rcosg, y= rsing, r= (x? uf afar, af ap Similarly, Therefore as) (mea is) 22 (anod)hs P36 sing cos aROTATIONAL MOTION AND THE HYDROGEN ATOM fe Similarly, @ rsing cose wt arg Fag costs 8 _ 2singcosd 9 r 3 7 8 It then follows that as in eqn 3.2 Exercise: Derive an expression for V? in cylindrical polar coordinates, x = r cos ¢, sing, r= 02 +97)? a, 6 9 ‘ar * 3x06 ) te ice) =0 if mem "= 1, nan integer] (Note that when m= m, the integral has the value 27.) the wavefunction e cos 6 + e-¥ sin B, and find an orthogonal Exercise: Normali linear combination of & ande ROT The moment ofit Then “The rotation rate is To = O16 Kg Since the dise re my = 15x10 Exercis state? Hown 3.6 See Fig 3.1. Wet @ superposition & 37 (@) v=") = Nexp For normal cROTATIONAL MOTION AND THE HYDROGEN ATOM 35 The moment of inertia of a solid uniform disc of mass M and radius R is 1 = 3MR; hence [= 2.5 x 10 kg m’ B =m} (R221) = 22x 10-* Ym ‘The rotation rate is 100 Hz. Hence @ = 2nv = 628 s~!. The angular momentum is fo = 0.16 kg m? 5“! If this is set equal to |m,|h we require mj] = 1.5 x 10" Since the dise rotates anticlockwise when seen from below, m, is negative. Hence my = 15 x10" Exercise: How much more energy is required to raise the disc into its next rotational state? 36 See Fig 3.1, We have plotted (1/2m)"e0s3¢ for m =3 10 Om = (12m) 008d = 1 72)Zcos4p — for ms = 4 Fig. 31 Exercise: Superimpose the imaginary parts of on the diagrams. Draw re ¢ for the superposition e' cos B + e~¥ sin 8 = Locum =v So avrmi = Nexp(e*) = N exp(cos + ising) For normalization, W°W = N29%'¢ I [wPag = I [required]44 ROTATIONAL MOTION AND THE HYDROGEN ATOM Therefore, N= 1//{2x 19(2)) = 02642 {Uo(2) = 2.280, given}. The form of jwris 2—2H% = 0,06980 which is plotted in Fig. 3.2. os we EX ‘same integration range but differently expressed =0 — [podd under @ > —$, cos@ even und o> -9) sing)? f * singe Fay =0 [same argument as for} are f exemtananenenta npsiingay f e818 sing + icos @)ee™Or*taD cai 2 [ * cos be 2nhN7h 2) may 1,(2)/1o(2)} h = 0.698% (l,) < hibecause itis the weighted average value, and m = 0 contributes signifi cantly to the sum. Exercise: Re omission of my = 0. v=N Dem Newooevining) [ Expectation value =a(hin =anni | Therefore, when ait Exercise: The uncer (A1,(A sing)? > ‘examine the limita The Schrédinger eat Aty = —QIE/h Write y = 09; the (sine ro Write 0”/0 a Because (4/dé)sintROTATIONAL MOTION AND THE HYDROGEN ATOM Exercise: Repeat the calculation for a wavepacket found in the same way but with the omission of my = 0. 38 V= NS SCa™ /miyem? = NY (1/m(ae*™ = Nertonortang) Normalization: Expectation value rion? [ ston ajape $98) (— sing + icos pet reritne day = ecu? | sean? (2a) = ah (2a) /To(2e ‘Therefore, when o is large, lim_1y(2a)/Io(2a) = 1, and so (le) © ah Exercise: The uncertainty relation for cyclic variables was quoted on p. 75 of the text (AL)*(A\sing)? > 412(cos $)?, Investigate it for the wavepacket of this Problem, and examine the limit «> co. 39 The Schrédinger equation is given in eqn 3.2 Aty = -QUE/W)y ) + (1/ sin )(@/26) sin (0/00) Write y = 4; then with @ = d@/d9 and = d/d¢, ete (1/sin? 880" + (1/ sin8)0(d/d0) sin 96! = —QIE/H)OO ©"/ + (1/@) sino(d/d6) sin6@' = —Q21E/H?) sin? Write ©”/ = —m?, a constant; then (1/@)sin (4/48) sin 00’ = m3 — QLE/R) sin? @ Because (d/d) sin8@! = @' cos + ©" sind, this rearranges into 0" sin? + @' sin cos 0 = (m} — Q1E/!2) sin? 0)3.10 aul ROTATIONAL MOTION AND THE HYDROGEN ATOM Exercise: Identify this equation in M. Abramowitz and I. A. Stegun, Handbook of math- ratical functions, and write down its solutions. The expression for the Laplacian in cylindrical polar coordinates (Problem 3.2) is Now substitute 1 pap whence ce 1a (ales eae Pe pa rar However, from Problem 3.2, ‘Therefore, ed 2a 1 # coo a vi bap P36 “fa (ee) Now we let p -> r, and obtain with La a 1 oS (snot) + Sind 98 (: 7) Sint 0 36° The Schrisdinger equation is E)y tomaan 312 ROTAT Write y = 06) 21 E/Re = 6; then Divide through by Write 129 our and hence that and the equation is Ts the eg Itis sufficient to sh @ Hu =-40P A? sine? Hence, A*%y Yoo = 4S/m) ME Hence, Ay & furROTATIONAL MOTION AND THE HYDROGEN ATOM , 1 La ofmath Write ¥ = @(@)0(), a? = sinéo 06% * Sino 30°" QUE 2 = 6; then 1 oo o* sin?6 dd? * Sind Divide through by ©4 and multiply through by sin? 6 1@@ | sindd do = sino +62 sin?@ = 0 eae te wwe and hence that 0 sing in sin and the equation is separable. Exercise: Is the equation separable if V(0, #) = af (0) + bg($)? 42 Itis sufficient to show thatthe ¥ig, Satisfy A7Yjqy = —I(0-+ 1) Ym [eqn 3.2 (@) Yu = —3G/2n)"? sine ‘A? sinde* = (1/ sin? 6)(07/aG) sine! + (1/ sin8)(3/00) sin (0/28) sin Be" (1/ sino + (1/ sin 8)e!8(d/d8) sin @ cos = ~(1/sin )e! + (1/ sind)e(cos? 6 — sin? a) = —(1/sin )e + (1/ sind)e*(1 — 2sin?@) = —2 singe" Hence, A?¥;1 = ~2¥41, in accord with 1 = 1 Yay = 1(5/x)"cos? 0 — 1) A°Gcost6 1/sin)(4/d9) sin9(4/d0)(3 cos? 6 — 1) 6(1/ sin8)(4/a8) sin® 6 cos. -6(1/ sin 6)(2 sin 8 cos? 6 ~ sin?) .6(2cos? @ — sin®@) = —6(3 cos? — 1) Hence, A?Y:9 = —6Ya9, in accord with = 248 ROTATIONAL MOTION AND THE HYDROGEN ATOM =i (1=22)de bx = cos] = 1 aon [ i [ioe - 00 J Wire f " Hag =0 Geoste — 1?sineae fae Exercise: Repeat the calculation for Yay and Ys. 3.13. (a) The moment of inertia of a sphere is = 3M R? (Problem 10.1}; therefore, on writing this value as Mr?, we see that r = (2/5)"?R. (b) Consider rotation perpendicular to the axis. The mass ofa disk of thickness dx, radius Ris pdx where p isthe mass density ofthe disk. Therefore a pR'l; therefore 1 = MP 14012) npRixtdx = hrpR'l ‘The mass ofthe cylinder is M Setting this value equal to Mr? gives Exercise: Evaluate the radius of gyration for rotation of the cylinder about its axis. 3,14 From eqn 3.34, E = JU + (02/21) = (1.30 x 10“ JCS + 1) [Problem 3.1) Draw up the following Table, using degeneracy gi = 21+ 1 J| E/Q0" gs ° o 1 1| 260 > 2% AE(1 ~0) = 2.60 x 10-75 ACL — 0) = he/AE( = 0) = 7.64 x 10“ m = 0.764 mm alculate the same quantities for the deuterated species. ROTATIO 3S Refer to Fig. cos =) The minimum angle up the followinROTATIONAL MOTION AND THE HYDROGEN ATOM. BUS Refer to Fig. 3.3 Fig. 33 D}, hence @ = arccos(n The minimum angle is obtained when m; takes its maximum value (my = 1) nin = arccos(l/ JUTE arceos{ Y1/1-+ 1/0} Jim @nin = arecos 1 = 0 Draw up the fol {angles in degi 6 = arceos(mi/V/ 45.0 90 135.0 @ =arcos(m/V8)| 35.3 65.9 90 114.1 144.7 arcos(m /VTB)| 30 $8.7 73290 1068 125.3 150 Exercise: The chlorine nucleus has a spin J = 3. What values of @ arso ROTATIONAL MOTION AND THE HYDROGEN ATOM. | 3.16 See Fig. 34 Exercise: Repeat th 3.18 Use the equation pr at es (rye jae | s0° ure with (@) Roin=hh ayn Then, because —_— @ Fig. 34 Exercise: Draw the corresponding diagrams for! = 4 But 2/a = py aquired BAT us = RioYoo = (1/a)*? (20°"!*} (1/2V} = (Ifa)! ©) Rox Q-—) . @ Jaye) 1) = f vr anv'yeae VP = (Ura C/O fae? yrer [A Gia = (/ma’)! {—@/ar) + (1a?) e " auntt/na’y [ap f° sinodo x |—(2/ar) + (1/a®)} e"*r2dr [21m 010 a =er ua? f {-@r/a) + (P/a)) ear a Hence, ~2uE} L stertde = nie" ae | a —2nE/P =1 = - 28? /ua®\(-a/4) v) = [ vie = /na'y(-e aren) [46 [ sinado [ (/rje-*!*rar Exercise: Confirm */Azeor Wade 3.19 The radial nodes are (2/4 cpa) (22M 4a?) = —E [A600 = 2E ry Hence, (7) + (V) = 2Ey — Bis According to the virial theorem, for Vo 1/r, (T V), as here,ROTATIONAL MOTION AND THE HYDROGEN ATOM Exercise: Repeat the calculation for a 2s-orbital 4B Use the equation preceding eqn 3.40 in the form. (/ry@ fare R+ { ue? meg) — UL+ D/P} R= —QnE /P)R with E = —(uet 320 %e22\(1/n?) [eqn 3.44) (@) Ryo sn = 1,1 = 0; E = —(uet (327 (C/N /de? yr Ryo + (He? 2 eOHE L/P) Rio = —¢ LE 2) Rio ‘Then, because Rio oe" (@/dr?\r Ryo = 2 = -Q/a)Rio + (7/a?)Rig Qyary (ue? 2zxegh?\(1/7) = —Q But 2/a = s1e?/2meoh; hence 1/a® = —2uB/M, so E quired. (b) Rap ox (2 rae - 40? /2ua) (€/8r?)r Ray = 2Ryy +r Rg & (—(4/a) + (5x20?) (Afar) + (5/242) — (r/4a° = (1/24*) = (r/4a) = (1/44?) r/a) Hence, ~2uE/h? = 1/4a?, as required. © Ru x 4 pipe”, p = 2r/3a\1 proceed as above, obtaining [12 = 1/902 Exercise: Confirm that Ry; and Ryo satisfy the wave equation, 319 The radial nodes are atthe zeros of Ry; denote them ro. (@) Yar: Roy =O when 2p =0;p =r/a Hence, ro/a = 2 or ro = 2a = 105.8 pm (©) Yar: Riy = 0 when 6 — 6p + p® = 0, p = 2r/3a. The solutions are po = 34 V3, of ry = 3+ VIGa/2) = 1.902, 7.102 oF 101 pm, 376 pm32 ROTATIONAL MOTION AND THE HYDROGEN ATOM ROTAT Find (a) the Z-dependence of these node locations, (b) the location of the radial nodes of (i) 2p-orbitals, ii) 4s-orbitals. [A general point in this connection is that A & S lists the locations of zeros of many functions. use [tera = nya (on = Aja? [Petr = AZo? BAZ sinosvae Rear P Rar "LY normalized] rian Weta) [a zroiret Ther . (outen = [zo [ee 420 4 BP LHe = H(z /ay {24a*/Z* — 9604/24 + 120042") = 6(a/2, asowbitl (r)ss = (1/243(Z/ay> J Zr/a + 4Z*r?/9a") B2ri3e gy = das = yraay(zyay [“(6— 42rfa +42 > pel = @21/2ya/2) (@) R= (Z/a) “The general expression is Therefore, wit 1-1 + D)/n*}\@/Z) A For simplicity sp (1/243)(Z/ay (b) R= (Z/ay® Therefore, wit 207(a/Zy ‘The general expression is (Pam = 8 (1 BLL = LC D/n? + 1/30?) (a/ZP (©) The most probable radius, r, is where (@/dr)r?R? = 0, or, equivalently, where (a/dp)p?R? = 0. Select the principal maximum (the outermost in each ase) 2, cx pte? (d/dp)pR? x (2p ~ p*)e? = Oat p = pas therefore Exercise: Use asym 2, implying r= a/Z Z, and determine the be Gi) pRB, ox pt pyreROTATIONAL MOTION AND THE HYDROGEN ATOM. (4/dp)9R? 0c {202 - 0)? - 29% p) ~ p= p)*}e* =0ap=p Therefore, solve ps(p. ~2)(p2 — 6p. +4) =O, finding p, = 0 (atnucteu), p. = 3 ~ V5 (ist antinode), ps = 2 (first node), p. = 3+ V3 (second antinode, principal). Hence p, = 3 + V5 = 5.23607, so rs = 5.24a/Z (iit) p?R3, p46 — 6p + pe (ido)? R3, cc p(p — Wot + 108p? ~ 2649+ 252, Therefore, solve pa(p’ — 18p + 1083 ~ 264p2 + 252p, - 72) = 0, finding ps (outermost) = 8.7160. Henc 4/22 = 13.01 aZ. Exercise: Evalute (r°)q, and (r) Find the most probable radius for an electron in a 4s-orbital gai p= [” perar = (Section 3.12) = "Rar tegn 3.46) (8) R= (Z/ap)*(1/9V3(6 — 6p + pe? (22 /3aq)r (Table 3.2} Therefore, with r = 3o/2Z)p wf He —oo errr For simplicity, set Z = 1; then (b) R= (Z/ag)*(1/9V6)(4 — p) pe {Table 3.2] 5) [4 wreraten (32) Pdp = 1.259 10-9 Use a symbolic integration program to evalute the probabilities for general Z, and determine the values of Z for which Ps, = 05.s4 ROTATIONAL MOTION AND THE HYDROGEN ATOM Roam aaa y= [ree a n= [or ‘Pod As in Problem 3.21, Pd tn Bs ce = [0A Z/a) Jf Riese Foon 3.46 ‘The general express 3ay)\* ® 2) ye Zz Exercise: Ee 6 a 5ee Decora) ; 8 . © m=( ie 326 1 = hcR Ge! 1/1 2 1(H) i asa) We ave used the integrals (un = nom me = 9.10939 x I [oo nreeta = m4 Gin — o)/m = I, Consequently, as obtained using symbolic integration in MathCad. 1-10 Exercise: Evaluate (1/) foreach orbital vase cc [~ RagRyr20r cc [2 — Zrfayer®Per*l ar The experime ce 7) [ar = ar aye ar = 8a" (822) — Pa" /382') =0 Confirm that Yor and Ys, are orthogonal Exercise: Evalatet | energy of". 3:24 Evaluate |Yar!® = [Yol?Riy = Rlp/47- BO 3.27 Fora given valu of WO) = 4(Z a} A 15x 10% pm forhydrogen |. Hence, the degeet \(Z/a)/an = (1/8 2.69 x 10°" pm=> (6/9V3"(Z la)? /Ax jay 7.96 x 10° pm Exercise: Calculate) tum number equal toROTATIONAL MOTION AND THE HYDROGEN ATOM. as aini= [ame [owner = Z/apapvorziay [ aynre dr = RH~/ay The general expression is 1/P )nim = (Z/ay?/wUl + C+D Exerese: Evalute (a) (1/r2) for a 2p.-orbital, and (b) ((1 — 360s? 6)/r°) for(i) a 2s-otital, (i) a 2p,-orbital T=heRiie. 1 = Es) I(H) = 1D) = he(Rus — Rp) = hel — Hode"/Bh ec = (stn ~ to)hCRao/me smart + mg), shy = memg/(me +m) (un — H0)/ Mme = Um img) — [mang + ma) meliy ~ mg)/(Ome + mg)( re + mg) = mele — mp)/mume ime = 9.10939 x 10-7" kg, mu = 1.6735 x g, mp = 3.3443 x 1077 k (i, Hp)/me = —2.7195 x 10+ Consequently 1(B) = 1(D) = = 2.7195 x 10-4) « (2.1799 x 10") 5.9282 x 10-8 J = =0.357 kl mol~"(—3.70 meV) ‘The experimental values are 109678.758 cm~ and 109708.596 em", s (GH) = 1(D)) fem™! = —29.838 em“! (~0.357 KI mot Exercise: Evaluate the ionization energy of positronium on the basis of the ionization energy of 'H. Fora given value of there are 21 + 1 values of my, For a given n there are n values of I. Hence, the degeneracy g is = Salen =nn—p+nan Exercise: Calculate the average value of mj for » alom in a state with principal quan tum number equal ton but with J, my unspecified.56 ROTATIONAL MOTION AND THE HYDROGEN ATOM 28 Refer to Fig, 3.5. The rotation (a)-»(b) corresponds to 3p becoming 3d, the rotation (b)-+(c) corresponds to 3d becoming 3s 4 Angular m 41 @) 1) = Ova inj = ir a/dzh ((a/az | Therefore, ©) Therefore Exercise: Evaluate4 Angular momentum 41 (@) lesb) = PEy@/92) — = (hy (Ly @/22), = (hi? (1/22), (09/82), 2] = @/a2d — 20 Therefore, Therefore -(A)ona Exercise: Evaluate (ly, /.] in the position representation.38 ANGULAR MOMENTUM Bly = Ue? = byl — LE Ilely + ly (lye — bel) = WE Uy hly + lly bad — 2 = -ihlely ~ ily, = —iMlly + ble) 42@) Be © eae -2e 45) 5 Ledylyls + Uys bellybe + &yUlys belle — EE ladglady + alll tel Uys lelyte + Uys = 2 ladalyly + ally lly + bly be] lly belle + bly, belle = EE = iN [lelely + lalyle + bebe + llyle} (b) ss2e ye ©) sts? =( ©) es leet] il, fe = iti : (©) Wes llas I) = ides tel = ih(—inyh, series ex Exercise: Evaluate (2, /)] and (2, (2) fee, 46 (a) Note thats,a (ye — lly) — Hale — fee) + Rldaly — he) because ool inl = Gl.) +jG,) + KCAL) powers j Hence, equating both sides term by term reproduces the commutation rules, eqn 46, (©) Note that srs Exercise: Show that if ly x ly = il, and Ip x ly = if, then 1 > 1 = iAl, where but only if [lig ay] = 0 or all 4. 4 (©) Note that sa (10) (0) - (4-9) (10) i -0|G5)-Ca Em nd fcy-Cy-G) ee ~ ane {(52)°(02) (3) hence, identifying these with s(s + IDR? iden lal Then, following the¢ “The eigenvalues of s? are therefore 4 tified lm tation of an angular Oe cence the following matrices constitute a represe Exercise: Confirm t ‘momentum with 1m ANGULAR MOMENTUM 010] 101 o10 =1 foreach g] Exercise: Express 5, 5,5, a8.a single spin operator and e!* inthe form a-+bs.. Evaluate 46 (@) Note that ssa = $f, 8 = cos(})a + isin) 8 because cos x consists only of even powers of x and sin.x consists only of odd powers. (6) Note thats, —tiha €05(sy/R)ee + isin(sy/ = cos(}a —sin(yp (6) Note that se = Exercise: Evaluate the effect of!" on (a) an estate, (b) a B state 447 Suppose [!, 5] +b = ly ily; then +h) = hl, and (0,17) = 2h Then, following the development that led to eqn 4.15, alam) = Ulyde + Ue LD) = (bg de — Fa Em mh — hy IL, m) = (mm — 1) yl, m) ntly, Fl, m) oc |f,m~T1) and {_|l, m) o¢ l, m-+1); therefore, isa lowering operator and f_ isa raising operatorCa ANGULAR MOMENTUM Exercise: Find a matrix representation of these /, and 1, ‘angular momenta’ corte 1 (draw on the matrices in the Exercise to Problem 4.4, sponding to L 48 (a) (0,01l|0,0) =0 [eqn 4.2 (b) (2, 1lfy12,0) = v6 [eqn 4.29} (©) Q.2 12.0) = (2,212, WavB = (2,212, 90mV(HVB) eqn 4.29) 2V6r? 12, Oll412.—1)(2, —IIf-[2,0) insert complete set] (JB )(h/6) = 61? feqn 4.29, 4.30} (©) 2, 01-1412,0) = (2, 01st + Ul. 44112,0) = (2, 01,1212, 0) ~ 2402, O12, 0 = (2, 0l,1-[2,0) = 6h (£) (2, OU 1212.0) = (2, O12, 1)(2, NL-12,2)(2, 22,2) (2, 21125 1)(2, Ny [2,0 (JB) AM ANDAR) = 48H @) 2.01451-12. Exercise: Evaluate (3, 11.13, 1) and (3, 31 fyle3. 1 49 Gi ip) «Gi he) = hi Sn tbe bh Xba x = inj, +iha — ji x jat5 Xho feqnd.8 ax b= . iM +42) (As Gy — 52) * Gi — a) # iMGr — jn), jn — dois not an angular momentum.) Exercise Find £, such that jy cos + joing is an angular momentum, (p-pa)/V3, py = (p+ Ps) VD). Then py, [Lo 11,0) in the notation l,m). The J label will be omited 4.10 Ineach case! = 1 and py p- > |I,—1) and pe henceforth, (2) (Pellekpy) = (/2{(—11 — (Nel = 1) 10) = G/2)U(—Mlel ~ 1) (Ale) = G/2)(-A— ==ih (b) {sll tpy)= W/2)U(-H = (MN = 1) +1) =0 (©) (Pallylpa) = 1/2 V/V) Ol, = LIL B= 1) (1/212) {(01L.| — 1) + (OD) = (1/2iV2){hv2 + hv?) = —ih (@ (pallets) = (1/206 /V DUO + LIU = 1) + 10) = (i/2V2){(Oll4| — 1) + (OlL|1)) = G/2VB(hd2-+ b= ih © (pallelpa) = C/21/V2) 010, + LU — 1) = 1) = (1/2V3( (01 1) ~ WLI) =O aluate (py|l-lpe) (Pslly|peds (Pellst-lps)s and (daylbeldse) Gin + AIP = FUR Ja? + ited + BHT EH ed det (@) GJgmy + UAL. my) = Mjvmy + MAGE + ede + Lim) xi Exercise: Evalue 4.12 {l,l} = Ming = Rs + foots + [sing [sin (0/28), os sin (8/2), (cot 8 cos (@fi cot) = ond [cot 0 cos 6, cotANGULAR MOMENTUM = PMG +1) — mlm; + DEUG += my + DUM +UU +) — mm) + DP? i G {eqn 4.22) ae eqn 4.29} 429] UG +) —mj(m; = 91 1) = mm, + 1))!") $1 — mlm; + DUG +0) (m; + Im) +2) +50 +1) = mj(my +1) iG +1) —mj(m, —) im (my + D735 + 1) = 3m} — 3m a jomj + 31f31i.m)) = 313m) ERLIG +1) = mm + 1) UG + DCm + Dim) + 2)"7G, Exercise: Evaluate (2) (j,mj+2j31j,m,) and (b) (j,mj — 11j31J.m) 412 {1,,1,] = Rfsin # (9/08) + cot8 cos (8/3), cos (8/30) cot sin (8 /20)] A?{—[sin 6 (9/98), cotd sin @(3/29)) + [ot cos $ (8/39), cos #(8/80)] + [sin 9 (8/80), cos 6(/00))} {sing (8/28), cos (2/20)] = 0 [cot 8 cos (8/89), cotd sin #(3/04)] > Il De sin (0/28), cot8 sin (0/96) ibe omitted ae e eo = sin (8/28) cotd sin $(8/84) — cotd sin g(a, ag) + sin? p cor6(3*/3008) cotd sin $(@ sing /9)(8/30 sing (9/00) = sin?® 6(9.co18/20)(8, ) — cot sin? (8/0006) sin? $ cosec"6(3/34) — cotd sin cos (0/00) [cot cos 6(@/8¢), cos $(0/00)] 19 cos 9(0/89) cos (3/30) £08 6(8/80) = cot8 cos p(0 cos 4/29)(8/30 8.608 6(0/04) ) + e018 cos? 6 02/8990) — cos" #(8 cot /80)(3/80) — cos? # cot 0(a#/3996) cot cos $ sin (3/08) + cos? cosec*9(A/ag) [cot# cos #(0/89), coté sin @(9/a9)) [cos # (2/34), sin (3/84)] = cot? {cos #(9/A9) sin (3/24) — sin 6(8/94) cos 0(8/99)}a ANGULAR MOMENTUM = cot? Afcos? 6 (8/3) + sin? $(8/88)} = cot 03/84) ve {les th] = fPfsin® @ cosec?#(a/04) + c0t8 sin pcos 4(0/20) cosec?9(3/38) — cot 8 cos¢ sin (3/20) — cot 0(3/30)} aed 2 ((sin? 6 + cos? p)cosec"6 (9/2) — cot? 6(0/3)) = F2{cosec?0(3/3) — cot? (3/86)) = R2(0/08) = ile as required. i (1/P01My Because Exercise: Find 414 30 36 36 jixh cote 2 » = osee@ — cot =n 2 6 = 2h ia ixd Exercise: Evalute [1] inthis representation 4.13 1 Yam, = AA6— mtn — 1D) Wanti_ Wes = W si Oo Yat =(1/2RVaai Yao = (/hV)I_¥: Exerc: Uni Vani = (1/RV6)Va; Yo.-2 = (1/2AE V1 eqn 48 1. = —he™((9/90) —icot0(3/3)} [eqn 4.32]9/00) ANGULAR MOMENTUM £-¥((9/00) —icot9(0/29)N sin —Ne~*{2sin0 cos de — ii sind cos6e™) —AN sin8 cose; hence Yas = —2N sind cos be =e ((0/28) — ico10(@/89)\(~2N sino cose = 2N (cos? 0 — sin? + cos*6} NGBc0s?# ~ 1); hence Yo = (2/3)"2NGBeos*9 — 1) ~(2/3)" Ne (0/08) — icot4(8/89))(3.cos?6 — 1) = (6)Ne-#2¢080 sind; hence Va sind cose i) — ict (3/29)} sind cos Be“ = ~2Ne-™ (cos? 4 ~ sin? @ cos? o}e-# = 2Nsin? Ge"; hence y22 = N sin? ae 1/28)|51/4}"? = (15/32)"/2, we have Find expressions for the f-orbital wavefunctions, | diz = Git) x Gi+ Hi xithXb+hxbth xi xhth xb = itis + Nin = Exereise: Under what circumstances do j, and jz satisfy the veetor relations set out in eqn 4.8o ANGULAR MOMENTUM feqn (4.411 lusing je = jx £ifs) ‘Therefor ~ upheld abd) y= 0 = ladda fusliddin-t because jis jij) = 0. Similarly, jullie is = Mili is diagonal in the coupled representation; the magnetic intera off:diagonal components, Use the vector coupling coefficients in Appendix 2. Hl Hoag!» 1) = (in /R)B(RiSte + 252.) (H9/P)B(a13h-+ grbf)laa) = yep BCs + 82)I1, 1) = (un Beis + 8 lap) + 1pa)) = (un/h)(B/V2)(FM){(g1 — g2)laB} “81 + g2)|Baa)} = (/2VInB(e) ~ e2llap) ~ Ifa Hexag| = (48/A)B(gis12 + 82522)8B) = Hog0,0) = (4n/AYB 51+ 6052 1/¥ = unBOei — 211.0) fore, on writing g = $(g1 + g2) and Ag = 4(g) ~ g2), the matrix is 5’, Mi\HIS, Ms 10,0) 1 fiat gn98 0 cus 0 Agua’ —3ny 0 0 0 0 $n —gunB Inthe uncoupled representation, Hyg has only diagonal element Hagglae) = $119B(@) + g3)\a) = gpp Blac JupB(gi — g2)e6) = AgusBlap) = }anB(—a1 + 22)/Ba) = —AgunBipa = ~}0B(e1 + 22)16B) = —eunBi66) On the other hand, Js) -s2 has off-diagonal elements. To calculate these, use 5422 ANGULAR MOMENTUM (hJ /2)8, « splat) = (hd /PE)siesclaee) = FJ eer) (hJ /N2)s1 - Sala) = (hd /PP){s,252cleB) + $51482-laB) + 581524 laB)} = th Jap) + $hJ\pa) (hJ/N)s1 -sa\fax) = —}hJ \Bar) + $ht\o) (hJ [128 -82\6B) = {hI BB) The overall matrix is therefore (om, ym mama) (a 0 o o (ap Sid + AgusB o (au tng o (561 0 0 dhJ - gusB When AJ >> junB, the off-diagonal elements are negligible inthe coupled represen tation, so that is then a ‘good? description and the eigenvalues are +A and ~3hJ When iB 3 hJ the off-diagonal elements are negligible in the uncoupled represen tation, so that is then a ‘good’ description and the eigenvalues are ++gu4pB, +AgupB. Exercise: Consider a system of two spin —} nuclei, one in a local field (1 ~ 04)B, the other in a local field (1-¢2)B, and coupled together by the spin-spin term (hJ /A?)T, 1 Set up the matrices ofthe hamiltonian and find the eigenvalues in the cases J large and J small 1G,4) = [2,2) [Seetion 4.12] 16.3) = (/V2{H1,2) +210) L-1G,3) = h/N4IG,2) + lo-)(0/VIIN,2) + 12, D) (h/V2/610, 2) + 211, 1) + 212, 1) + ¥6/2,0)) (h/V2)(V60, 2) +4I1, 1) + 612, 0)) therefore G,2) = 1/2V7){VG0,2) + 4)1, 1) + V6I2,0)) L.\G,2) = GVDNG, 1) y+ )(1/2V7)(V6)0,2) + 411, 1) + B12, 0)) = (ty/2V7)16\ — 1,2) + 2V810, 1) + 4VEI0, 1) + 4611.0 +2¥6I1,0) +612, -1)) G/N 7pm ~ 1,2) + VEO, 1) + VBL, 0) +12, —1) therefore 1G, 1) = (1/VT4){\ = 1, 2) + V610, 1) + V6I1, 0) + 12, -1)) L1G therefore 6.0) = Now evaluate ( G, 4IhlG 6, 31haI6, 6.06, By symmety That is, in genera Because (G, Mel Exercise: Calcul 4.23 (jini =>ANGULAR MOMENTUM. LAG, 1) = QV5)HIG, 0) (h- + Le-)(1/V14){| — 1, 2) + ¥610, 1) + VII, 0) + = (h/-¥14){2\ — 2, 2 = 1,1) +61= 1,1) +610,0) +6|0,0) + 611, 1) +211, —1) +212, -2)} 2h/V/14){| — 2,2) +4| — 1, 1) + 610, 0) +4], -1 therefore 1G, 0} = (1/-¥70){I — 2,2) +41 — 1,1) +610, 0) +41, Now evaluate (G, MzlieIG, Mc) for each Mr (GAllelG,4) = (2,212.2) = 28 3leIG.3) = (1/2){(1. 21+ Q, eth 2) + Ls suet = ONAN 2+ AN 2 +22.) = HR = ihe G, 2) = (6/28)(V6,21 + 4(1, 11 + V6.0) x{V610, 2) +411, 1) +612, 0}) p/28)|6-+ 16-+ 6) = (h/14){(—1, 2| + ¥6(0, 1] + ¥6(1, 0] + (2, 11} = 1,2) +0+ Véil,0) +212, —1) h— 01)B, the (h/4y(-1-404642) = th hd /1)1y Tp, G, Olf.|G, 0) = (h/70){(—2, 2| + 4(—1, 1| + 6(0, 0 + 4(1, —1), J large andy x{-2| — 2,2) — 4] — 1,1) +0+4]1, -1) + 212, h/70)\-2 — 16 +0 + 1642) =0 ed represen- and —3hJ. ed represen By symmetry (G,—1hIG, — G,—31hG. Thats, in general, (G, MillaclG, Mu) = Mi Exercise: Calculate (F, Mzliel@, Mz) for the same configuration, 2S (jj; jms im e 2h)ANGULAR MOMENTUM Cmymal? |. which completes the proof jmljreljs.jm)) and evaluate it for 5 Group t) Bout (ju jas jm Linas im, Exercise: Find a general expression for (ji G, Mrlli|G, Mz); see Problem 4.22. SL (a) H:0: £,C; (b) COs: EG, (©) Gye EC (@) cis-CIHC=t (e) trans-CIHC (®) Benzene: E Napihalen h) CHCIFBr (i) BOHy: E Exercise: Clas « 52 w= J y'wydr ‘symmetric repre : requirement. Bat ranslation trans Hence only HO ments. For addit Phillips, Tables Exercise: Which electri dipole m Write f = (ils D(E) = 1,the6