Solutions Manual for Introduction to Modern Statistical Mechanics David Wu and David Chandler New York Oxford OXFORD UNIVERSITY PRESS 1988Oxford University Press Oxford New York Toronto Delhi Bombay Calcutta Madras Karachi Petaling Jaya Singapore Hong Kong Tokyo Nairobi Dares Salaam Cape Town Melbourne Auckland and associated companies in Berlin Ibadan Copyright © 1988 by Oxford University Press, Inc, Published by Oxford University Press, Inc., 198 Madison Avenue, New York, New York 10016-4314 Oxford is a registered trademark of Oxford University Press All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior permission of Oxford University Press. Library of Congress Cataloging-in-Publication Data Wu, David. Solutions manual for “Introduction to modern statistical mechanics”. 1. Statistical mechanics—Problems, exercises. etc. 2. Statistical thermodynamics—Problems, exercises, etc. 3. Chemistry, Physical and theoretical—Problems, exercises, etc. I. Chandler, David, 1944- H. Chandler, David, 1944- Introduction to modern statistical mechanics. III. Title. QC174.844.W82 1988 530.1'3 88-27824 ISBN 0-19-505889-5 9876 Printed in the United States of America on acid-free paperPreface The following pages describe the solutions to many of the Exercises in pavid Chandler's text, Introduction to Modern Statistical Mechanics. That text is brief but demanding with the principles illustrated only through the numerous Exercises, Especially in light of this strategy, a solution manual can serve an important pedagogical role. While we do not present herein the solutions to all the Exercises, those we have skipped require no techniques that are not already illustrated by the solutions we have included. In some eases, we have pointed out additional references. While not absolutely necessary (the text is self contained), these additions may be especially useful for the topics not covered explicitly in the main body of the text. For instance, in Chapter 6 where at least one exercise leads one naturally to perform a finite size scaling calculation, we alert the reader to some introductory literature on this important technique. In the format we have adopted, the manual should look like neatly prepared problem sets. The prose is kept to a minimum, and the figures are generally hand drawn sketches, though a few graphs were plotted with the aid of a microcomputer. Concerning the preparation of the manuscript, we owe great thanks to Mary Hammond for her expert secretarial help.Chapter Chapter Chapter Chapter Chapter Chapter Chapter Chapter Solution Manual for Introduction to Modern Statistical Mechanics Contents Page 15 29 43 59 68 811. 1. Chapter 1, Thermodynamics, Fundamentals Entropy is postulated by the 2nd Law to be a monotonically increasing function of E (i.e., T > 0) and an extensive function. The first equation of state satisfies both criteria, while the second is not extensive since it grows exponentially with system size. So 1/2 S = LyY(@E/Lg) “* - is the correct choice. Indeed, you can convince yourself that SQE, AL, An) = AS(E,L,n) Further, (8) e 1 Woe n,L ie VE implying T > 0. For the tension, we have L -et = (38 re eee £/T = Ben micuba velo into bo 3 or f= TY(R/Ro)C1 - (2/2) 1, = Lyn. The principles we apply are conservation of total extensive energy and equality of temperature at thermal equilibrium. From the solution to Exercise 1.2, aus : 4 E=TY nh e/4 . Therefore, the total initial energy is cers? nO 6 cal)? ly agora = BOY « a? which is the same as the total final energy rin’). ni?)) a .or4 ‘ Hence1.5 1.12 (1) 92 pula (12) 2 (2) yp Assuming the system is surrounded by adiabatic walls, the change in energy AE is equal to the work fpdV due to changing the pressures pq and Pg + The final equilibrium state so obtained has new mole numbers ny and ny . Instead we can imagine arriving at this final equilibrium state in two steps. First we reversibly pump the particles to their final values. Then we do work by moving the pistons to their final pressures with the walls impermeable to any particles. We know the total change in energy of the system must again be AE since E is a function of state. Hence, the work done by changing nj and np can be associated with work done by changing the pressures. ep aa) 7 Brn 7 5 Pp eyn p,T,n natural variables => dG = -SdT + Vdp + udn 4 as. at Gp) tn)pin av © Pp npn = - 12 ay até Joan For a rubber band of length L, tension f, dE = TdS + fd + pdn . E is extensive. Therefore by Euler's theorem, E = TS + fL + un. Hence, dE = TdS + SdT + fdL + Ldf + udn + ndy implying0 = SdT + Ldf + ndy . oe gz 5 @ o & o w 1" S(T,L,n) by inverting T = T(S,L,n): 2, 20SL nT -=F > 80 8S aE n eet 2a(L7n) * The Gibbs-Duhem like equation is 0 = SdT + Ldf + ndy . We want to show this interdependence of these three differentials. We choose a representation, e.g., {S,L,n}, though we could also use {T,f} : as + (2 ar 3L)3,n ( dL + Sn)s,L anPlugging into 0 = SdT + Ldf + ndy _ est )1 ds a 20S 20s + (8(=3) + LCo) + nf- Sl dL n n 2 2 + Cs(- 4esL | u(- 288) 4 n (28 LY an no 3 nt =O. QED 1.14 The Gibbs-Duhem equation, 0 = -SdT + Vdp - ndy, implies du = -sdT + vdp , with s = S/n and v = W/n . Hence, Ope pOlyies (2), = 9), 1,16 From the definition of heat capacity a A -GDs), Further, since dE = TdS + fdl + udn, we have a(E-TS) = - SdT + fdb + udn and thus the Maxwell-type relation Hence2.9 Chapter 2. Conditions for Equilibrium and Stability ar (a) Stability criteria are generally (5 ) 2 O where X; and Ty are a conjugate. Therefore (i) is true, 0, since -p and V are conjugate. Also (iii) is true since ®), =+ v2), < 0 by the Gibbs-Duhem equation. None of the remainder are guaranteed false by stability. (b) From Part (a), we know to examine (ii) and (iv). Note aT _ (aT) (as Ges * > Gsby (ele =- (2) (2 = -Sdt - a Gly (Fy {dA = -SdT - pdv + pan} Since (aT/8s), is positive by stability, @) ap 5y)5 > 0 implies Gry <0. 3 But this implication contradicts (ii). Thus, (ii) and (iv) are inconsistent. 2.10 To derive the analog of the Clausius-Clapeyron equation in the u-T plane, note that the y-T coexistence line requires that p(y.) = p®(y,r) . But 0 = -SdT + Vdp - ndy implies dp + (S/V)4T + (n/V)dy . AS we creep infinitesimally along the u-T (@) . ap(8) coexistence line, dp when infinitesimally close on either side, i.e., Sars ay = Mar + HPHay or where2.19 2.20 bo = (B)6- (BYOB) a(S5)p Assume constant n . To prove (K./K,) = (cy/e,) we note that c face HE P re : icine (2%) = - (2%) (82 e second equality comes from realizing Ge = Ay Ges 7 and the third uses the chain rule. Since av 2 Je ynl St) pn] and since -(3p/av),, > 0 by stability, we have C, > ¢ Thus , ee Cy/Cy > 1, and since C/Cy = Ky/Ks » we have Kp > Ky « This inequality says that instead of working adiabatically, it is easier to compress something if you can leak energy out of the system into a constant temperature heat bath. (a) The rubber band heats up when stretched. Assume constant n. So, or equivalently (. Ore 3F)s,n Note, these two derivatives have the same sign since oT aL a0)sin Ge)s,n and the second derivative is positive by stability. aL To find the sign of GPein » we write2.21(a) a(E-fL) = TdS - Ldf + ... fea Ob _ (at tmpries Gs)en° ~ Gels.n given by stability Thus aL GPein 0 >o ae by stability GO), = Cer - c >o . Hence t > & In other words, the constant length rubber band Cae has the larger change in temperature. Since in general dE = TdS + f+dx , where f is the intensive field and x is the extensive parameter, the correct work term is HdM. (In other words, doubling the system doubles M, not H. This approximate extensivity neglects interactions such as mutual polarization which might occur if two magnetizable systems were placed adjacent to each other.) So de = TdS + HdM - pdV + udN , and dA = -SdT + HdM - pdV - ydN Stability then requires both > 0 and Jsyvyn2.23 oH BH)t,vyn > O° Using the representation {S,H,n,V} , the thermodynamic potential is 3(B-HM) E- HM. We then have M = M(S,Hsn,V) since M= (“= ). a(E-HM) = TdS - MdH + ... By the Maxwell relation 3M = (Ss)u « ar (Sy)y > 0 dy stability. ’ aM ar (b) Given (55), <0, we want to determine the sign of Gals? ar at) (as See eee e Gas = - Gala Ge d(B-HM-ST) = -SdT - MdH +... 2. (8 aM -- Gay Gby - By the Maxwell relation porieycuicat a, - >0, by <0, T° ‘OTH * stability given (a) dA = -SdT + fdL + yam x= L/M k, fh, Xq and ¢ are independent of x, but not T. (0) 1 L 2 1 te 2. =3 nM = XQ) + cM = 3 hi Be 2Lxy + Mxg] + OM Since Xq is independent of L and of x, it's independent of M. 2 1 L 2. 1 2 2 uy gp hl- St xp] te = 5 A(x Xp) te M 1 2 (c) foes = bkx? = us1 2 fx = Zz h(x x (4) The phase transition occurs at u, = At up, f_ , the short phase has x = xs, and the long phase has X= xy, ; k 2 ho 2 12 Ug = uy implies - 5 x. = - 5 (x, a XQ) feces fo =f, implies kx, = h(x,- x9) . Thus 2 2 2 (kx,)° = hkxp = hkxg - 2ck , or hkxys vaK Arve + 20(k-h) aie nCh=K) : Since since k>h, ©>0 , we have, vnk Yoon + 2e(k-h) = Akxy fy cr ' h ; (e) xgaZ (x,- X9) implies Ax = or ax = YAK Yh + 2e(k-h) = hx, + x, O° 2.24 Near the liquid-solid phase coexistence AO. a n3 n (s) ee A ps Vv ve ale 18 Sir niawhich are functions in {n,v,T] . (a) (a) p™ and p{*) are the densities near the coexistence line. at coexistence, the temperature is the remaining free parameter, yO yO 9G) LW OL Ly, Explicitly, ey a) an V,T on Ae av n,T av n,T So Beco 2 a , 28 ay)" - acy" Substituting Br9(s)3° = p°) into the previous equation we get 3 [p34 Bara (8)? Tera ° Therefore the densities aré (s) . () _ 16 e © = 9 a g and wile ole and are constant functions of T. (b) (e) eee (d) Since weigge as _ 128 oF 1 Av 81 ge 12 Also, Ps 128 a 1 aT 1 iAs _ ap Therefore 4° = 2 , satisfying the Clausius-Clapeyron equation. Pp 2.25 Stability requires - (55), > 0 2 ap aisige Bad (2 or Sean = 7m een > © =a = 2ap (bp) Instability occurs when this function is negative. The boundary surrounding the region of instability, the spinodal, is where it's 0: ise., RT - 2ap(1-bp)® = 0. In the T-p plane, the spinodal is RT = 2ap(1-bp)* , i.e., the spinodal is a cubic polynomial with roots for T= 0 at p= 0, 1/b. Also note that the spinodal has extrema when Salta : Bp 7 07 BD - Mp +, that is when p= 1/b, 1/3d. Similarly, there is a point of inflection when ar ape = 0 = 3b3)- 2=0 , that is when p = 2/3b . Finally, 1 Ba Te = 35) = a7 5 ¢ These features are illustrated in the figure below. only p 1/2b. Van der Waals Spinodal 0.30 0.20 RT/a 0.10 0.00 0.0 0.2 0.4 0.6 08 1.0 pe The van der Waals equation of state for a given temperature To has only one interval in p, if at all, for which (2)_ <0, i.e., for which the fluid is unstable. This is reflected by the fact that the spinodal equation, p = ap@(1-2bp) , has only two distinct roots. In other words, the isotherm is shaped as illustrated in the figure on the next page. The Maxwell construction requires p(p,) = p(p,) which can only be satisfied within the height h. Any pair of points so picked will lead to a coexistence curve enveloping the spinodal region.Van der Waals Isotherms and Spinodal 0.075 0.045, oO ae 2 a 0.015 -0.015, 0.0 0.1 02 0.3 0.4 0.6 pb 2.26 phase a: pp = a * bBy phase B: pp =c + a(Bu)? At phase equilibrium, we = pp), ayo ay"®? , ana gi = p88. Thus a+ bg =c + (Bu)? » implying b+ rb* - Na(o-a) Bu = 3a The density can be obtained from the Gibbs-Duhem equation, dy = -sdT + vap , toe. (1/v) = 9 = (2), = ( ee wT ~ \a(Bu)’B so, p(%) =» 0B) = 2dBu yand we identify the positive root as the physical root to the quadratic equation. Hence (8). gf) . Jos na(ane) and db 2 8Peransition "2 * aq [b+ ¥ dD’ Md(are) J.Chapter 3. Statistical Mechanics 3.8 The probability in a canonical ensemble is -BE P(E) & Q(E)e = exp(2na(E)-BE] We assume that P(E) is so sharply peaked that occurs at the top (or very close to the top) of the peak. The following steepest descent calculation will validate our assumption: Expand gnP(E) = &n@(E) - BE about its maximum value 2nP() which occurs at , i.e., 2 ainP(E) 1 2 a°enP(E) gnP(E) = anP() + 6E SE | + 5 (SE) Fe fe | get uu Sees SSeS 0, because 2nP(E) negative has a maximum at a Pane = a (2n0-BE) i: a?an aren ae aE? © 5p2 |< - (2 @®) - 2 ano () BES OE 7 ~ B “BED SoHE ae gnats = 2 OEY © kg Hence 2 P(E) « expl- ESB) y 2kyT Cy ~6 ere For 6E = 10 ° , N= 10°), using = 3/2 NkyT , Cy = 3/2 Nk, , -109 P(E)/P() = e = 0.000 0001 anne) a billion zeros That's improbable! 3.9 W/N = implies3.10 So Nt S/kg = &na(E,N) = tn eater) where m = m(E) = E/e = Nan N - (N-m) £n (N-m) - m &n m N N-m N an ( ) + man Nan (e 8 +1) + Clearly, Lim S/k,=0 . Bro B Also, s/k,(E,N) = Nan (—S ) + me) an (AL, - 1) ee N-m(E. m(E) N = won (= &) + eve tn (EF - 1) a(S/ky) . ‘3 ora Ne _ So 1/kgT = sey = gin & 1) The last result is in agreement with the earlier formula, N/m - 1 = e®© . Notice, however, that 1/T can be negative when Ne : Eve 1 Bovis t, des, $$ implies 7<0. From p. 68, the canonical ensemble calculation gives -BA = N an(1 + e Fy = Ne(1 + eF&)7! Then = -B(A - = “Bey , _NBe__ S/ky = ~B(A ~ ) = N in(1 +e ieee , which is the same as in Exercise 3.9 from the microcanonical calculation, N= 0.01 moles is = 10°. an open, thermally equilibrated system is controlled by T, V and yu. Fluctuations in the energy and the density p = N/V are given by _ 2 2 <(O0> = - where £ is conjugate to xyor E and N varying, the grand canonical ensemble yields (2s82) 3 ore Cr) 2 ket Gr fr <(E)°> = > Vey” “B V,Bu we could calculate this last derivative precisely (see below), but for the purposes of an estimate, we only need to know that we'd only get e constant times Cy, the exact constant being irrelevant since it's som still O(N). So, as an estimate 2. 2 <(SE)°> = KyT Cy which is the canonical ensemble result. The RMS deviation ice Xecsey®> , *KpT 3KBN/2 1 “11 BkRIN72 Wi similarly, for an ideal gas, <(6N)@> = Yecsp)®> _ ve any2> 80 “Spy = ap Just for reference, let's evaluate the actual derivatives involved in <(6B)®> ¢ aN (59)v,6u aE (aE : Gv,on i aT v,n ( S = 1/T dE + p/T dV - u/T GN O = Edg + Vd(Bp) - Nd(By) - 33 => d(Bu) = E/N dg + W/W d(8p) zie zie and BBu E , V a(pp) SENG Gey, oR tho lyr Bp = 7 = Bp(N,V,T) ears rarele NOVON So, 3B 3 Gy, au = C, + (3/2 kgT)+(Sa)«N = (3/2 + O/M)NK = 15/4 Nky3.17 agx¢b. Show [¥g,f| = ] <=> p(x) = (xx) (a) b b b - = f e(xde(x)p(xdax - f g(x)p(x)ax + f f(y)p(y)ay a a a bob bb =f J wcorecyyp(x8(y-x)axay - ff ede (yypOop(y)axay aa aa Hence, if = , bob Jf eGor(yypootety-x) - p(y] dxdy = 0. aa This holds for all g and f if and only if p(x)[é(y-x) - p(y] = 0. The trivial solution, p(x) = 0, is discounted because it is not normalized, Thus, we must have p(y) = 6(y-Xq) , ~ where Xg is some point in the interval [a,b] . (ob) - = J J axay roag(yypGy) - fax £(x)B, 0) J ay eB, (y) « Hence, if = , J J axay rode y)Ep(x,y) - Px) Pw] = 0. This holds for all f and g if and only if p(x,y) = By (x) Poly) Note: The above proofs rely upon the fact that [f(x)n(x)dx = 0 for all f is equivalent to n(x) = 0 on the interval of integration. This is true because if n(x) # 0 we could pick f(x) = n(x) for which [f(x)n(x)dx > 0. For two dimensions, we can iterate theabove theorem on fax eGoLfay aly) n(x,y)] = 0 calling the term in the square brackets n(x) 3.18 For N spins in a field H, Bayan ae 2 CnyuH), npstl (a) 8,H, and N are constant in our ensemble: N -6 J (-n. pH) ist? Q- aang <= OCB) er8uH _ BuH = NuH Shit, oa = NuH tanh(-BuH) = - NpH tanh (ByH) s E (b) gng= 2 - > = - BA ke KT -A+E s-O4 = ka eng + Kk ,B = wk,fan (eM + MBM) — gut tanh (Bui) (c) Inthe limit T>0 or Br, tanh (ByH) > 1. So aig = > Nu3.19 3.20 (a) (b) (ce) i.e., the ground state has all spins + , or aligned with the fielg Lim NkgCen (eH + eSHH) - gy tanh(Bul)] = NkyCBuH - BUH] = 0 , pre hence, S39 =0 N N m= = <(Me)®> = a> - MS = gs - iG aay) a(BH)® Q 2 1 2% 12 a iauee CNy Q tanh(ByH)] Q (pH)? Q o(BH = Nu{eu-1)eanh@(euH) + 1} Hence, <(6M)?> = Nu@{1 - tann?(guH)} = Nu@sech@(auH) . Also, a im = pNu2{1 - tann?(puH)} , BAN 2 acM> fang 2 () = Ja y 2 © SCBHY BIN” Cy? BAN As B>@, tanh(ByH) > 1. Therefore y,, = Nu, and <6) 04 = met) = 0. In other words, the ground state with all the spins aligned has no fluctuations. In an ensemble with constant M, all members have the same number ofspins up. For a given H, this ensemble is the microcanonical ensemble since E= - HM is also fixed. Note we can't generalize this ensemble to one with fluctuating extensive variables because there is only one: M, ynich we fix (assuming N is constant), i.e., we can't have E flowing independently of M from the system to an energy bath. So we want to use £, H, and N as our natural variables. tn this ensemble, N Meul ny = w(ny- n_) where n, = number of spins up act n_ = number of spins down = u(2nj-w) , and n, + n_ and B= - Hu(2n,-N) since a(E) = and S/ky = &nn(E) , g- 128), Binge) | agng ane ar (enta.10ien,)1) «2 kg SE NSH 3E an, 26 an, Vt Neny -2H so 1 2 BH = 5, in, ann! (N-n, )!] For N >> 0, sh= t2 tn ann, + (tien, )an(Nen,) ~ N i on, (Myen n, dan (Non, 3 1 1 ra = py Linn, - an(wen,)] = 3; tn ( 7 Thus, Bee ite eR. hence M= u(2n, - N) = Nu tanh(BuH)3.21 which agrees with Exercise 3,19 and (after a change in notation) with 3.9 as well. Substituting n, = M/2y + N/2 into the above equation for BH gives Nu + My 1 BH = 5, in (GE In the {A,B} basis, H Eb In Pauli spin matrices notation, H, = - do, and m= uo, Then H ® = a a 4 ‘ S ' c B & (a) B=0 v2 = w+ we (3) [i] -- 02 [i}--ete> ni-o swe? [i] --w@ fi} ear E= +h. 7 10 } basis is -a( | (b) H in the : 8A Since H is diagonal, ef = |@ © | , and o e 4 a Ba - Q= tre 8H. op fe a = e844 684 as expected. oe Doing the trace with | a> and | B> gives ef 9 e@ BA 4 0 e BA a= |B> = L[+> - [oI Bb), 4 teh + e8442 Ph BS 7 o1 qn the {A,B} basis H = -A ( ‘ 7 n=0 nt - Ff coat [: | 3 Gat ( ) n=O nt! o1 n=0 n! 10 even odd 1, ¢ ("2 cea fro} (4 2 cow § Car, for =gll +7 1 tall Sie J 2 n=0 nt n=0 nt! o1 2 n=0 nl n=0 nt 10 1 7,84, - BA, [1 0 1784 _ 784, [01 #3 le e (3 + gle e fy cosh 84 sinh BA sinh BA cosh pA * These matrix elements are the same as those arrived at by rewriting BA ( | in the {A,B} basis. Now performing the trace, oe tr e 8H - 2 cosnpa = ef + @ BA In the end, the route to the partition function is unimportant, since the trace is invariant to a change of basis. (c) Using the {+, -} basis, ( tr(me PH) = Ee = 5 (caleca]) |m| (fad+|B>) = 0 and similarly <-|m|-> = 0 , therefore = 0. (ii) similarly <+| |m[ [o> =e 84 ana <-| [mf [> = 84.So <|m|> = [ul - (ii) <(6m)%> = = cm? = y? a = - [THE -A we, fat) (i) The energies then satisfy the equation (dq) For Ee oOo, det(EI - H) = 0. So EF - (ug)? - 2 eM ub)** a? g-a/(uB)?+ 0° 0 or E and Q = Then A(B) = anl2 cosh(8/(uB)° + 4°) and the free energy of solvation is Te ente cosh( av uB)*+ 17) - anl2 cosh(ga)] } . A(E) ~ A(O) = leo, + do” nt Giy eo SH. 5 where c = BuE and d= a n=0 To evaluate the nt® term, note 2 Ceo,* do] = 0° + dr + ed(a,e, + 0,05) 2, 42 = (e+ d°)I since {o,,0,} =O. So [oo,+ doI” = (0% a®)"/? 1 for n even = (0% g@)int)/2 [co,+ do,} for n odd and eth Fk e+ a2) 1 a mE even fa Ke? PP Co ceo eee) n=0 a aaa aeaaet in A hs a es a n odd= cosh(/e*+ d°) «1+ sinn(¥ee+ a*) ( a e+ di’ Since TrI = 2, and Tro, = Tro, =0, 22, 42 ; Q = 2 cosh(By/uE + A*) in agreement with (i). (e) To evaluate . solving for |+> in the {A,B} basis, “hue, Jt>- 4 | 7 Ax? + (p-uE)? having energy - AyE)® + a® y ls A A ese ( qusies WE + E having energy AyE)* + a? = & ya ewe)? | ae a? + (Es ub)? Ef expt u2et+ a? 3 - expt-p/u7e*+ 477 Ja Therefore tanh(e/u*E* + 7) ae +(e = yp)? a2 + (Ee uB)? is true for any E since <|m|> = Te([ult e °F )/tr e BH Similarly < + » hence <|m]> = [uJ . This In other words, increases as the field increases. There is a competition between the field E which would make [A> and |B> the eigenstates, and the tunneling A which has |+> as eigenstates. Only as IE] > =, does pew 7 ¥ and , is in general no longer equal to - se unless m commutes with H. Systematic analysis of the fluctuation in that case is in fact equivalent to analyzing the quantum dynamics of the system, which is not the focus of this text. Bp = p/(1-bp) - gap” , pap) ve, (a) For constant v= 13 <(8p)2>!/27p = !/2ven> 2. a <(m®> = Geeaa,v ” “Gb a.v 7 VoGEp ev Bp)- (382). (1-bp)2 1 - 2Bap(1-bp) = <> or C(opep ecient THntiCa=bp) ° femaear ee wv h-2pap(1-bp)* which vanishes as the volume becomes infinite. (>) At the critical point G&),-—5 - 2pap = 0 and -—2 57 Mpa = 0 (1-bp) (1-bp) Do some algebra! bo 5 and 8 : -—2,- 2ap(1-bp,) 2a(2/3) ef IP Pe (c) Use the result of part (a) with V = 100d, » = q ana p= 121 | where x will be close to 1: x 8a <(5p)2917? | 1 7 5¥3C1 - 17x)Thus we have the table x <(5p)29 1/279 1 0.38 1.001 3.7 1.00001 37 (d) We're looking for "significant" density fluctuations in a volume 3, typical molecular volumes are ~ (5A)2 = b 6, V = ~ (10008) v = (200)3b = 8 x 10% . <(6p)291/2 ° index of refraction of distinguishable (by sight) fluids: To estimate significant » we checked the CRC for the H,0 = 1.33 n-Hexane = 1.37 or ABs 38, For small differences in p, we can consider n= p . So take <(69)°91/2 significant a = 0.03 . Solving for the difference in 1 B= B/x at p= p= ap» Me get: ATR = 109 A (SSO ee 6 aie Then xa 1410? (Soe) Seat OF oY = 10 In other words, critical fluctuations will be easily observed optically if you are within 0.1% of the critical temperature. 323 AB, NtNpaN. We can make an analogy with the ideal gas analysis of Sec. 3.6. 2 2. 2 <(Ng> )> = NED = N = J Cen,yn,,> - ] , naj= 1, if molecule i is in state A ij = 0, ctherwiseN 2 (xno > - ype] ne Cen, pny? > d eH? zero since different molecules are uncorrelated " eee ~” = Ncn,,>(1 - ), since each molecule is equivalent = Neng > = x ,xBN, 1 AB where Xq = SN/N , and xp et - xy.Chapter 4, Non-Interacting (Ideal) Systems 4.5 Begin with the equation at the top of page 94, BHu/2 _ .-BMw/2 BA = -anQ= f dw g(w) gn Ce 1 0 D-1 dw a! on Cebltw/2 _ 9 Blu/2, As long as Blw/2 >> 1, we can approximate this integral in the limit of pr= as lim pA = Bhw/2 TO (g+2) sua (DeT eee Hence 2 aang eo <> = aca) In,v 7 BAT) Similarly, 22a a2nQ s® ap Seay) Bhu/2 , -BMw/2 Senet : e igo” BC I du g(w) afa/E— = Bhale Hw/2 J » 2 Mo 2 ND Dt 2 2 2 => kgs () J du a! (hare) C- (aa arare) I - “0 e -e Change variables to x = Bmw and let kg O/T 20 ie ax Peer BD gM PT GR? 0,/T dx 0 In the limit T+ 0 , we encounter the integral © Dt x dx = 0 (8X1)?wT 4d = 0 + (D+1) P(D+1) c(D+1) = (D+1)! g(De1) . Seer er SCS Gamma Reimann Function Zeta Function For D = 3, we note ¢(i) = 1/90 , and cy ~ 12 a4 nk GP. Vv 5 B ® 2 Jee baet (2 ) ves = p> a> tJ, since ny and ny are uncorrelated => is ince = = + = N= const implies (2) Equations (1) and (2) imply dA a O ant /(N-N,)] + &n(q4/G3) applying Stirling's approximationor associating the solution to this equation with = .N- , we obtain «ND / = 44/4y - Ng a) BL ! Wi! = (ay + a3 /N as shown above Ny Ne i a) a My ng we : EAD CUNT LTO, we 7 aN aN (Ny + Ng = ND (Ny + Ng = ND = a, (2008 a 8a, Gg N a = 4, a Can (, ‘A 3a, Since A and B play symmetrical roles, = d3 7@—Y—) . B B (a, + Gy) Hence, / = 44/45 Similarly, ang? g2 _ Bees 201 2% %y Sa pag_y2 CMg- Myr)" = = KN” = Q : Na” Wot 3 ( Vg N a Ny Q ‘ap (N,+Ng= N) . 2 SE Q Bay STA Bay’ag.N ” “Q2 SBay’agN ~ 9a ay Fda, G2 Bay q a i a ta aay a “Sq Gap °T Bay “ag * Sa 3a, a,N Cas/(a, + a4,18 For an ideal gas of structureless particles we? (a) Then assuming a macroscopic volume, ek Voce (ue ¥K2/2m) ppV- tne =Janlit+e “~J= 3 J nk®ant1 + oH ™ Jak k (2m) 0 -4 3/2 fx? ent + ze) ax z= eft T 0 2 2 So wet hy x an(1 + ze™ ) ax a = (2aB 1/2 TX 9 = 4S t5)2(2) Substituting the series for gn(1+x) , o k ° 2 fepzl= st fF nk Ef xe ax va kel 0 eR ek aks 2 | k=1 To calculate the density, 2,2 7 112 72m wes Taps Tae - Vf um? 2 ak gee eee ee ereececae (2m)? “o 1s ge k 72m So pr = KH ok, 3/2 = f,,5(z) «4.19 2 2,2 (b) WK /2M) 5 gy (2m) -mav -" 3 ve pan 352) = g am 43 fs) i -3 = 3g (BPV) = 5 PV. (a) We want to invert y = pad = J (-1)8*) oh _3/? a1 Usingz= J e k in the method of undetermined coefficients, k=0 y= 3S CIET CS eyytyts 937? = k=0 Rel +1 (-1) 2 ct get = ast Le ely gel 3/2 0 Tae 0 it ° a+ ° ae ae 2-4 (-D L £-2 2 2 +CT Se te e,+ J [i © Cosy ae Q=1 33/2 0 2 Q=2 23/2 2 0 1 Equating terms, 0 = f3,9(eg) which implies cy = 0 and then - 1-0, and 2 O= Cy . 3 2 Therefore 2 = + (pa3) savB +. -ap*/am 2 (0) = ze “ = pride BP /2m for pre cK 1 1 + ze BP /2m V3 (ued gx? BP /am (ec) <|p[> = 3 i J ump? pr BP q (2m) 0 eee Seam anew? 6°For a single particle Vp = 1, so <[p|> = 2) WA 5 or = 8 n/< [p> (a) Bp/p £5 )2(2) 3/2. 5/2 J - (pr3)27 29/2 + = 4 {Cpr + (p3)?/2 pA =e parse? a 3 correction is due to the negative correlation The finite pd between fermions (i.e., the Pauli exclusion principle implies that no two identical particles can simultaneously exist at the same point in space). However, as ph2+ 0, the effect of the exclusion principle diminishes as the particles become farther apart. 2 ax tz eX + 177! “1/2 (° 4.20 (a) fy ,.(2) = Hw J san? f ayy Cate + 77! 0 Since the derivative of the distribution [2 'e” + 1]! is sharply peaked at y = {nz , we integrate by parts to get fyjp(@) = fay v3? oY MMApevrine 7°? ee Wa 0 Expanding y3/2 around the peak at y = &nz gives t fyj(2) = fat 2, taney 3/24 3a¢anay!/?e + 3/8¢enay"/4? + 3vn -2nz (e“+1) - t = Gonz}? fat +s 30 “ganz (e"+ 1) : t -anz t =e ne? cf ae ee oy i m1) co eet The first integral is 1 and the second is of the order z!. So pad = (tnz)3/? 4/3¥mand z=e where eg = (H?/an)(6x7—)*/3 Be. (>) apd = f(z) = dx ¥ an(i +e 5/2 ale ff as" "ep dy 8 f3y2(2) To get the correction term in (Be,) we calculate f,,,(z) to order t?: i tet fa = 0 since the integrand is odd, and t 2 ° (eo + 1) ia a et Bees t ae tes (ev + 1) 4 3/2, wat “1/2 *~ cepte,3/? + EF (atep) J 30m 4 3/2, 2 & “1 = — (Be,) Ce (Be,) + (Be) 9 + 1 avn F 5 F y iF 2 50° Hence p= Zpe,ti + 2 (Be)? eee The pressure is not zero at T=0 because the exclusion principle requires all but one fermion to have non-zero momentum. 4.21 (a) Simply plug in the Fermi distribution given on page 96. -B(e-e,) (b) Since e 7 eee then 2 21-x 1+ Ef So, -B(e-e,) Blerep) a i Pyle -(1- p= 2p, - 2p,[1 J apli - (1-e 7 o~B(e-eR) = 20,0 Similarly, B(e,t eg) _ -(e,+ep) a i Peace eases iba tl |e loge Ker (2m) (21) ae 7 - 20 Furf ak exp(-BH?k?/2m,) (2m) 0 ~ Be, m we Fe (2a)? 2B ~Be we Fan. Therefore, pn = 94/1 he FF : ‘ — Fy vebé 422 Pag } any = eV = eM pve adsorbed degeneracy classical Limit _ Mad _ Bu, QBe Pad VO Pst t Also Bu = np A? for the classical gas, and y has the same value as in the above equation for e,4+ Hence, Bu 3 eFty3 , °s which implies 3,Be Pag/Pg = Pgh en 4 = 23 (a) B= BE, + B+ By then -B(E,+ Eyt Ep) A Gigs a= Je - % % % >2 2 Cy = ~kgB8/8B = kaa°L —>— J] (A) (B) (Cc) soy tc + cy Let E = Ey + Eg, Ey = zero point energy . which is independent of Eq. In other words, fluctuations produce Cy, and Eg has nothing to do with fluctuations, (b) Selec where energies e, and e, are relative to ¢, , our choice for the zero of energy. (elec) _ cy B 2 Yerec x a ~Be ~Be 1 emer) ac. leyeye + Boe58 1 “Be “Be 1 252 ~tEeee |+ eee “7 J elec (0) @= Grans“Serec”4nuc’ rot “Svin/Pan * 8° (trans) , ,(elec) | ,(nuc) , ,(rot) , , (vib) cv v Vv v WieitieeNow cletec) 2p 2 2 y = kB [ - “] % 9750,000/300 -100 e 7 < So cletec) 00 Y < wpe! at room temperature, which is negligible . Because of the high energies of excited electronic states, the contribution to Cy of excited states is negligible. Neglecting the excited states completely is equivalent to assuming clelec) V = 0, which is therefore a good approximation. Also, the above calculation shows that the ground state degeneracy doesn't enter into the heat capacity. 00 e Ignoring these terms doesn't affect dojec significantly and also won't affect either = d€nq/a(-B) or A = -2nq/B . On the other hand, gq will affect $ because even though the average energy doesn't care about the “Be, Be, a 0 0. degeneracy, = gee /e,e Eq + the free energy is affected. A sednta a Qn + ‘elec ~ ~ B *™ 8 * 9 + €q + Ky tng, Seiec * T = Kpingy -yan Thus the degeneracy accounts for an additive term to the entropy. N N Q= Merans Sint’! If we write “Be, 0 Vint = 80° (21,+ 1) (2Tg+ q rot Win Sot = Trot, : corto”? - Lee vib we are assuming: (1) The volume is large enough that qin, is independent of volume. This is important when distinguishing C) from Cy, since the difference will be that from Qinang: i-€+, the ideal gas value. (2) Excited electronic (or nuclear) states are sufficiently high in energy to be ignored in Q. (3) Internal nuclear motion is well approximated by a rigid rotor- harmonic oscillator, which neglects: - anharmonicity in the vibrations - centrifugal distortion - rotation-vibrational coupling. (4) The high temperature formula for grog assumes that Mog ST (ves, 12.1 K << 300 K) From the partition functions, we obtain Hw, = —82nQ/3B = Ney + NkAT + N = coth(Bhw,/2) + 3/2 NkKaT . 0 Therefore,Yu 10)2 2 2 Cy = 5/2 Nk, + n=) esch™ (Rhu /2)/ kT Ku, 2 2 7) esch®(BHu,/2) = 1/2 Nk + Nk,( Furthermore, Bhuy ‘0 = Nk, { 5/2 + 5— coth(Bituy/2) + ng, + En(T/O,.4) Bhw/2 Bw, /2 2n(m, + m, -ante 9 =e 9 y+ ent 4 (BB 3/2, no B -onn +i}. The necessary numerical input is: . . 3700 . 2Teng « T = 298 K Bling = “DoR Gop 7 121K b= 6.63 x 10°lerg «5 KOT eal 3 eee m3 Baue = (257% 1) (25+1) = 8 WT Tp 7 406 x 10 “em ” ~ a! pr®l, pp 79 yielding S = 51.7 cal/mol K , (Note: CRC value of 47.5 neglects the gn g contribution of 4.14 cal/mol kK) = "YC and Cy = 6.97 cal/mol K . N 4.26 Q(n,v,7) = 2 q 21m) 3/2 oN * BuyN Bu (a) a= J a efit {qe = ef) 2 2(b) = 2 p= 2/B agne auras OD = oR Vz implies z= op Hence, p= p/B , the ideal gas law. ( ¥«($9)*> sa ¥<(on)®> GJ eee pee fae e 2, _ adi az = SE = VE = Ve = aD We($p)2> 1 -10 . = Vio/pvy = 2.01x10'). ° a2 B (d) To second order in 6N a? anP(n) 2 anP(N) = anp() + 4 (Su)? ( on = a i.e., assuming a Gaussian distribution around with variance 2 <(dN)>~ , we get 7 -10712 a PIN) |g 10 "0D/2 | 10 nich is very unlikely . P()5.1 5.3 Chapter 5. Statistical Mechanical Theory of Phase Transitions Since the number of nearest neighbors in a D-dimensional cubic lattice is 2D, 1 E, wn (5+ 2p) =~ DN, where the ¥% corrects for double counting pairs. Note that for a two~ dimensional triangular lattice, each spin has 6 nearest neighbors, so that in that case where b, = 5,5 = 4 1 is the bond between spin i and iti. The b,'s iit i completely determine the sj's up to the value of s,. This degeneracy is related to the fact that only N-1 of the b;'s are independent: However, as N > @ , the contribution in energy due to the NER bond N-1 N-1 is small compared to the other bonds J So i= N N BJ 555541 BJ I by ist i 5 et New {o, = 41} FD). (8%, oP)". Cacosn(par I” . Note: With some patience, the reader can compute Q for finite N without neglecting edge effects. Also of interest is the transfer matrix method illustrated in the solution to Exercise 5.21.5.4 Note that the Ising model energy can be written as N - mH J (any-1) = 9 Y i=l id = ~ 2mH } ny + mii “4g [nya ist inj same as As a result, the answer is Qigtng (BeNeHidom) = explAN(mH with w= 2mH - 2Jz, © = 4J and sites to any given lattice site. e2( BH m= tanh (BpH + Bzdm) = Saal or me2(ShH * Bam) | 2(BuH + or 26(uH + zdm) = &n Now, an(t2B) = an(tem) = an(t-m) @-= cs vj z + Bzdm) _ (anj-1)(2ny-1) van TD ra eet Nz/2 92/2)) F) poegog (8s Neuse) GAS is the number of nearest neighbor B2Jm) 6zdm) -4 +1 which implies 8 = s——= m+ 2m/3 + ..., 1+m: am) about m= 0 . which is the Taylor expansion of &n\ see 3 So B= sym (2m + 2m/3 +...) or 12 3 gf = Jz(B 8.) Thus, for T+ T,, ne (t, - 1/2 = or p= 1/2. In reading this solution, try not to confuse the reciprocal temperature 8 with the critical exponent Bg. Finally, as T +0, 8+, it's easiest to analyze pzdm _ ,-B2dm m = tanh(p2Jm) = —-—————___ 823m, .-B2dm which clearly tends to -1 as B> © if m<0, and +i as Bre ifm>o. The complete mean field solution is plotted in the figure. Mean Field Magnetization 1.0 0.6 F 04+ m Magnetization 0.27 0.0 0.00 0.25 050 0.75 1.00 X,1/2DJ TemperatureIn this figure, only positive m are plotted since the curve is symmetric about the temperature axis, Note that k,T/2DJ is 1), where 7) is the mean field theory prediction of Tg. 5.8 In the mean field theory, different spins are uncorrelated. Thus a (B)up = ~HH YS (si)yap — 5 2 Tis 9:83) er i ij = -pH Dede = ; Yo Jaslsivee(saar » ij The desired result follows from the association (sj); =m. Al- ternatively, you may begin from the perspective of Sec.(5.5) where the partition function in this approximation is shown to be InQ = In Que — B(AE) yp where —B(AE) 4p is given . Eq.(d) of p. 138, and Quer = [2cosh(BuH + BzJm))|% : The desired result for the internal energy is obtained from differ- entiating this approximation for InQ with respect to —§. Here, in the differentiation, note that m is a function of ; in fact, from Eq.(b) on p. 136 with AH = zJm/y, we find ae H + 2JM)(1— m? J(1-m? or (a + IM) —m")/h— Bed(t—m?) for T < T,. For T > T, and H = 0, mean field theory gives m = 0, and thus predicts zero internal energy in that case. This prediction is incorrect since (although the average coupling to the field is zero — i.e., there is no broken symmetry and long ranged order) there are still correlations between nearest neighbor spins.5.18 @(K') = 2¢(K) - h(K) where h(K) is analytic at K = K,, K' = K'(K) = 3/8 &n cosh(4K) KK) = Ks and h(Kg) = B(Ke) Assume Ca |K- KI near K=K, that is, C= { a less singular part } + a|K - x I* . The second term with a > 0 dominates as K+K, . @ Then since c=— 3 g(K) , dk’ we can write g(K) = { a less singular part } + b|K - K,|?% where b is a constant. Plugging this into the first equations above, we get {a less singular part} + b|K'- Ko|°% ~ a{a 1ess singular part} +b] = KP - nc) As K> K, » the dominant contributions are ifs bIK'= Ko [2% = ab]k - Kol? . Taylor expanding K'(K) about K = K, gives Keke Be w= x) © Hence, [Bee OO nD IPE ae nee or | Bi |?% = 2, which implies (2-a) en alk, Ssaateetor OK a= 2- gn 2/ gn =| aK 'K ce Note that the actual value of h(k) is irrelevant. (e) N (s ee yh/2 + 8,8. ,K mq’) = J eae ceaeetea S541 8) SyeerSyett Jet N exp{ J (hs, + Ks.s,.,)] = Q 1Syztl gar vst N N a, 0 ALO mf ew f* gp = ats 3 3 2 0 Oa Thus, a, = ecosnin) « /e™sinn®(n) + eK = &Xteosn(n) + /sinn2(h) +e]. Further, Hence, 492 . gn(a,) = K + taLeosn(n) + Yeinn@(n) + oN],5.22 sinh(h)cosh(h) sinh(h) + @ 2 Ysinh®(h) + eK cosn(h) + Ysinn2(n) + eK Don®tn) 9 ek Lim = lim sinh(n) + ( 1+ cosh(h)/¥sinh”(h) +e) ee nee cosh(h) + Ysinh@(h) + eX =0 (a) Q(K,h,N) = sete) tei aeaeeneaiseg! i qOee)Eejregttue teediasia fee {odd s, i : oft sya" sy]+h+K[sy_5+8] 2 oN y-g* yt ERK Cy-2*8y)}) = CecK ny 7? QcK' sh" N72) Thus, (n/2)(s, +83) th+K(s, #55) (n/2)(s,+8,) - [h+K(s,+8,)] ‘ He 1783 1783 h'/2)(s,+8,) + K' = rKnyte” 1"83) #91937 For all the possible states of s, and s3: hie Kk" 2(heK) , 2k s,= 5351 f(K,h) e a) 51 = "53 £(K,hye* fet (2) spesge nts fiKynjen* K 2 eek, gens ok, @) By multiplying Eqs (1),(3) with Eq(2) twice quickly yields f(K,n) = 2Lcosh@(h) cosn(2K+n)oosh(-2Ken)]'/4Division of Eq(1) by Eq(3) quickly gives ' 1 cosh (2K+h) 3 nC cosntqaKeny J Division of Eq(1) times Eq(3) by Eq(2) twice easily leads to K' = anfcosh(2k+h)cosh(~2k+h)/cosh@(h)] / 4 (b) For K,h >0: [2K +h| > |-2K + Al, so that ork ea) >1, implying h! > h. Farther, ak 8 cosh(2K + h) cosh(—2K +h) cosh?(h) = axle + eWtK-hy(endK th + ew) | 1 aang | eet <> a 38) 0, 208E 4 This problem illustrates how phase transitions can arise due to competition between entropic and energetic effects. P © P Q= Bim (ea? 5 cnet Te uty yf a expl-BE/20 + (en J 9980 a} as i The integral can be evaluated to be P 7 Pp ° -8/2oLE-o/B(eu J u,)} exp{a/2eC@ (ey J u,)]*} f age ist! ist -° - P = expt BH ¢ J uy) Jui - 78 ova 2P' ist Jat So, i sey | «uu, uu 7 ditt eee Q= fe ne {ceayP/? z is 2P i,j=1 } ' {u,} From the text, we know = 2 cosh pya® + y°R?] Hence,. 0 ap eBEC/20 3Q(e) =f dee! ateEy / 2 = 2 wf ae cP 29 asin (ava® + yPR?) -wE//a® + eRe j ae oo /20 zeosh(Ya* + y"E*) As 8 >=, cosh8x, sinhgx + e®* , so wf dE expl-se*/20 + ava + yPEPI(ye//a® + vB?) <> = —2 J de expl-88°/20 + pa? + yPE?] wf ae cP) (yea? + y?e?) f ag e ONCE) where the last equality defines W(E) and the weighting function e BW(E) as gee , the weighting function becomes a delta function « 6(B~ E,,,) where Eqi, is the E that minimizes W(E). Exploiting this idea is a method of "steepest descent." Note 2 - HE nich impties Engin” © oF ote Ms? + ye In the latter case, oe = oy" - a°/y2 which has the real solutions E, = + ule - 4)? e x when gy°/a > 1. When this condition is met, we have broken symmetry. In other words, E, starts contributing to W(B) at oue/o = 1. For ou?/A <1, = 0, while for ou“/A>1, as in *5.27 (a) so where For 1 (b) sr= , * 0. This emergence of broken symmetry will cause <(sm)*> to diverge at 9 = 0 = A/y2. More is said about this broken symmetry in the isomorphic problem, Exercise 5.27. Doing the sum over spins with the transfer matrix method (Exercise 5.21): } ene e bY expl ) ahs, + 8Js,5,.4] g- -phepa) inl i Piet e BY | gBhtBd the eigenvalues of M te(q') = tr eee Nae A, > A_ are the eigenvalues of g , and = “ - 1/8 2nQ(h;8,N) = - 1/8 CN gna, + gn(1 + = nh?/20] arge N, therefore, 2 i aoe Nh A(ns8,M) =~ 5 andy + 5 2 SciESEEneeeeeanee =n 5 -u- i an (cosh(gh) + Ysinh@(gh) + e4)3 At this point, notice that A(h;8,N) is even inh, i.e., if h minimizes A , so does -h . Further, ; 2 lim ra h Infor A NU 55-4 - [hl].Thus, we're looking for bistability in A like this: A A B B crit Since f is even and { +=, A will have a bistability in h when hoe gain’ < 2 for h'> O near zero; i.e., A is concave downward at h = © when d4/ah' < 0 for h' near zero. Hence, 3A/dh = 0 can be used to determine the critical temperature. Alternatively, note that taking the p>= limit gives tim cosnigh) = e®!*! | aim sinn(gh) = sign(n)e®l*!, ana hence pee pee = 2 Cn ere ance lly 2 =u CB -o- [nj and does show bistability. However, we don't get an equation for 8 from this analysis. crit (ce) Near h=0 for h > 0, we find hee 283 th faire = NE i sinh(gh) e“P"] peBd =n i- oe since sinh(gh) = gh .This derivative changes in sign as a function of 8 when 2Bomity 1 e Pe crit o 8 which is an invertible function in g since it's montonically increasing. Another way to view the analysis of this Exercise is to solve for # = 0 to find the stable minima in A(h) . This equation can be written A'(hmin.B) = 0 , an implicit function for g = Bh) 8 is then the limiting value of g = p(h.-), ash, 20, erit min min Ey and so we look for th hae = 0 and solve for. Berit’Chapter 6. Monte Carlo Methods in Statistical Mechanics To perform Exercises 6.10, 6.11 and 6,146.16, you will collect statistics from long Monte Carlo runs, These exercises help illustrate what must be done to obtain reliable information from such calculations. In this regard, efficient and fast computer codes are important, and as emphasized in the text, much can be done to improve the programs listed in the text. at the very least, one should use a compiled version of the codes. As a standard of excellence, however, you might want to view Jeffrey Fox's Monte Carlo of the Ising magnet.* It utilizes binary arithmetic only and machine language, and it runs from 10° to 103 times faster on a PC than the Ising model program listed in the text. As well as providing rapid access to good statistics, the greater speed permits one to view rather large systems in real time. The views are both instructive and pleasing to the eye. Some new books on Monte Carlo methods in particular and computer simula- tions in general are worthy additions to the bibliography of this chapter: M. H. Kalos and P. A. Whitlock, Monte Carlo Methods Vol. I: Basics, (Wiley Interscience, New York, 1986); H. Gould and J. Tobochnik, An Introduction to Computer Simulation Methods, Parts 1 and 2, (Addison-Wesley, Reading, 1988); M. P. Allen and D. J. Tildesley, Computer Simulation of Liquids, (Oxford U. Press, Oxford, 1987). The last of these is especially pertinent to the material covered in Chapters T and 8. See eee eee eee eee eeeseeee een eeate ‘ + Fox, "Fox's Ising Model Simulation for PC Compatibles," placed in the Public domain on 3/25/88.6.10 Above Tg, we find 0, decays more or less exponentially as i gets farther from j, and random thermal fluctuations destroy long-ranged correlations. In fact ,; + 0 for i far from j until T > T, from above, at which point Sy #0. Below T,, we have broken symmetry, and as T > 0, we find || is significantly greater than zero, This is an indication that we are frozen into either the up state or the down state. One result of this broken symmetry is that as our runs apparently show «s,>? oe and hence + 1 as well, we will observe c,, + 0 as T+ 0. J 1.00 ~ aan Spontaneous magnetization 0.60 l| 0.40 0.20 0.00 0.0 08 1.6 24 32 40 kat 0.60 Correlations in the 0.48 Ising Magnet 0.36 0.24 <8} Sj >- <8) > 012 0.00 00 08 16 24 32 4.0 kal Fig. Representative results for exercise 6.10. The lattice was equilibrated for 100 passes, and then statistics were compiled for 5,000 passes. Spin-spin correlations were measured up to the fifth nearest neighbor+Fig. The effect of the interface is to introduce long-ranged correlations between spins along the interface, even while T << Ty and the correlations in the bulk are only short~ranged. However, as defined in the code given in the book, the ground state of the 20 x 20 lattice, even with the biasing field on, has all the spins aligned the same way (with the exception of the biased spins). Simply setting the initial configuration to be an interface would sample a metastable well. To observe the interface fluctuations we can increase the bulk of the lattice relative to the interface by changing the dimensions to be 4o x 20. Note that in implementing the calculation, there are four columns of spins each that can be considered bulk or interface. In our calculations the dependence of and on the distance from the biasing field is averaged over. Correlations shown in the graph are Ksysp> > <8p> 08 Correlations with spins in the interface A 06 e Vv A > vo 04 A io $ Vo 0.2 0.0 1 2 3 4 5 Neighbor distance These representative results were obtained on a 40 x 20 lattice at k,T/d = 1.2 using 100 passes to equilibrate and 10,000 passes to mfasure correlations. The biasing field keeps spins 1-20 up and 21-40 down in the top row. Spins in columns 1, 20, 21 and 40 are considered to be in the interface, and columns 10, 11, 30 and 31 were taken for bulk measurements. The upper line shows correlations along the interface, and the lower line shows the correlation of a spin at thg interface into the bulk. Correlations between bulk spins are ~ 10 1074 and are not discernible on this graph. or6.12 A straightforward algorithm is to choose a large enough, or equivalently, to scale the range of the uniform random numbers [0,1] to (-%nax? Xmax] SO that most of the Gaussian will fit in this range. Then trial x's will be accepted with a probability « p(x) , normalized so that for all x, prob(x) <1. The trouble is that the fraction of accepted trial x's tends to be small. This fraction is just that of the area under the curve to the rectangle: 1.0 0.0 - max In other words, if we pick x uniformly from the interval, we will then reject most choices. This inefficient method does not exploit any form of importance sampling. There are a couple of possibilities for improvement. Ea ‘ox is due One is to imagine that the distribution p(x) = Ya/7 e to an energy E(x), where BE(x) = ax? » and to employ the usual Metropolis algorithm with diffusive motion. Then trial samples will tend to come from the regions of lower E(x) and higher probability. The drawback is that one random number x;,, is correlated with the previous one x, from which it made its move to x,,, = x, + 6x , with 6x small. Nonetheless, the calculated moments should be correct. Another method, equivalent to the "force bias" Monte Carlo of problem 6.13, is to change 1 , to reflect the more likely regions of vw p(x), thereby increasing the A ,'s . wy 62The first algorithm described above corresponds to m , = constant xXx 12 and A, «e7ax'” | as we said, that scheme is not very efficient. If xx, instead we make a change of variables, such as x = f(y), with y picked uniformly from [0,1] then the probability of picking x in [xg,xg + dx] is | XXq X=X where y = f'(x), So if we want to achieve 100% acceptance A, = 1, then our trials must be chosen with , = Yan e ™ xx xx and thus x 2 0 2 = awe which implies f Vg) = Vai fo MW ax = erf(x,) oO i.e., f is the inverse of the error function, Note this scheme only generates positive x; the sign should be assigned randomly. In some problems, such a perfect solution is not possible. But as long as A, 1 increases and begins to approach unity, we have made good progress. In the present context, any change of variables favoring sampling smaller x is better. For example, let bday eB where ye [0,1] is uniformly picked. This implies yer faoe ae x =(1-y)/cy x . . n = 0.0 05 1.0So the x are picked with probability 1, © —*— , and so we must accept with probability (1+ ox) 2 2 Ae (_+ ox) Via oo x @ to preserve wy . The proportionalities are chosen so that 1, ¢ 1 and A. 1. Again only positive x are generated and the signs should be x £ randomly chosen. Note only one index is retained because any given choice is completely independent of previous choices. (a) The condition of detailed balance, w ,/w, = exp(-BAE ,) , wi v'y w with AB, = -E , gives w v mA = wy. 7 = exp(-BAE ,), or A, = Pte ' vw vw viv viv Since A, is a probability, A ,¢ 1 vw w BE Tr, BME, e w <1, we let a e YY and vw ea vw = 1; otherwise, we can switch indices, v#v', i.e., ~BAE , e YY andA ,=1 vw (>) To make a transition every move, we let A ,=A, = 1. So then w v'y DP, vos vit eee eee ae w w { I-p, vo= vel This form, which is independent of v, is possible because of the symmetry of the problem — each pair of adjacent levels is6.14 6.16 equivalent to any other pair. With detailed balance, designating E,>E , v' = v#l , we therefore have, Seseeadtareiaseuaten ar ase ee or pre - 1+x 1+ ebltw Note: inthe limits tw+0O, priv/2, and twee, pro 7 “B(Hy” ME + BL) pptye (a) Q=f agltre le ° 2 fF ape 8? /2%pp mo egugee eee erage veer eC ceaeaeeee 3T6E,,5) ” G BCBE, SY q Evaluating the trace gives aire, ia! 2 -BE /20 cs 2 = dE ie n(pl a” + E+E a-f e coshla( u'(E + Ba) © 2 = 2(a/u) J dE e FE /2E cosn(Be) , and so 2Q -BE°/20 TE.) Ge) 8 sinh(BE) ¢ 2f ape = 2(a/u) [aE BE et. sinh(BE) u (E+ EL)/é from which the desired formula follows directly. The modification to include windows is simple. Since we are basically adding a potential that is infinite outside the window (i.e., not under the umbrella) and zero otherwise, we need only check if we've steppedoutside the window. This is done at the time we also check e BAE » rnd . Moves outside the window are rejected. We can scan through each window for the minimum in A(M). Once one is found for a given T, we can assume for T' near T , that M')., is near Main» 80 we need only scan a few neighboring windows. However, as T+T, , it will be hard to find the minimum since a wide range of M are equally probable. We find that the barrier drops faster than the minimum moves in as illustrated in the schematic figure. Notice that the criteria of a vanishing bistability can be used unambiguously to define a critical temperature for finite systems, of course, such a definition leads to system size dependent T, which becomes the true critical temperature only as N= Lx L+**. So, our min 2 several values of L. The L > @ behavior of Mgin/L° is the exact M(T), results for the "phase diagram," ( vs T is shown in the figure for and we've plotted M(T) on the same graph for comparison. 1.0 N a £ os Magnetization for iS = Different Lattice Sizes L=0o 0.6 4 4 2.0 22 24 26 kpl/d These results were obtained with 5000 passes/window, and each window had the width L°/20 except for the L = 40 case where we used L@/40 window widths.As described above, we determined T, for each value of L by extrapolating to Maj, = 0. The results of those extrapolations are given in the table. We then extrapolated T, to the L + © by using a procedure known as finite size scaling. In particular, we assumed tr, - Ty]? «1 7 Te where T, = T,(*) . We determined the exponent b from the slope of [T, - T,(L)] vs. gn L . This procedure gave b= 1.0 0. Then a plot of T,(L) vs. 1/L gave Ty = 2.26 + 0.02 as the 1/L + 0 intercept. This estimate can be compared with Onsager's Ty = 2.269. L Tg(L) 10 2.60 20 2.43 30 2.38 ho 2.34 A discussion of the finite size scaling method is given in Sec. 1.2 of Binder and Stauffer's Chapter in Applications of the Monte Carlo Method in Statistical Physics, ed. K. Binder (Springer-Verlag, N.Y., 1984). Also see Part 2 of Gould and Tobochnik's Computer Simulation Methods referred to at the beginning of this manual chapter.Chapter 7. Classical Fluids 1.10 The kinetic energy and pair potential parts of will be the same as 7 "1 discussed in the text. For the three-body term, we write . 1 - a a) By) > = g MINI) (N-2) jet J B fanl 7 N 7 -o- far%non-1)expt-8 ur, j)Itdutr, 5)/dry ry 5 /{ arNexpl-8 u(r] ipjet jet du(r,,) N N eece pcs 12 a n-2 .-au(r’) nq-eu(e™) =e ay [80 Jorg Pip Met) fa? © 1 f arte au(r Hee BI 1 (2/N) 0 & fan, Jorg cope (Ey fp) Therefore, for a uniform system & = 1 - (8/6) f dr g(r)r du(r)/ar . Q.B.D. aia f ante BO)~ 4) = an far r2pe PRO) 4] 0 Yar? .-eutr) f * pF -pu(r);_, du = le "| ooul re (-8 ) ar AS ro, u(r) +0, and 3 3 fate apu (re) eteeiet ed : zp fe 1 zp {-pu(r)] + 0 for quickly enough decaying u(r), i.e., faster than r73, Therefore, theboundary term in the integration by parts gives zero. As a result, ~pul 2 .Bulr) |, du = Ff arte PM 1g 2 3 (- 4) Jo Une 2 = = 6/6 f dr oP) p OB , Q.E.D. For hard spheres ° 3 aa a 2, _ ang ane B(T) = - anf fara Fo zby - For a square well o 3 BA(T) = - 20 [ - I arr? + if ar r@te8- 13 } At the Boyle temperature, 3. Bee, 38 [g'3 - © Bo" o)] = 0, therefore, e/kpTy =n or The figure shows a graph of the square well By with o' adjusted such that ar r@u (r) =e far 2 LJ 3 ° which implies o' = 9'/3, . with this choice of o', the square well Byshould be a reasonable estimate of B{'), However, unlike the square well By, B{') vanishes at very large temperatures since eM) 159 aspeo. well is Square we 1/7 7.28 The velocity or momentum averages are isotropic and factorable from the coordinates. Therefore, only one average is necessary to answer all parts to this Exercise. 2 2 2 2 -sp°/am -p°/2m (a) > = f apve /fape » 2 ~6p2/2m J ap, (p/m)? e = z J ape Bp,/am since the p, degree of freedom is statistically uncorrelated from the others. Performing the integral gives 2. 1 “O° Alternatively, aln 2 2. 24 wet ft ateie ve ZR O = G3

= ev2rcv2y (L x ‘y My? = em ear) a ee evs a evi t vet vo = aev> = = 0 x 2 2. 2 eye: (vy t Bvy)D = KvI> + adevodvy> + DTEWY> aoe. (1p) vy rar? in Classically, these averages won't be affected by isothermal volume/pressure changes (i.e. through the potential) since the momentum distribution is dependent only on the temperature. When the classical assumption”breaks down at extremely high pressures, one would then need to consider the quantum dispersion of particles since the dispersion (i.e., the uncertainty principle) leads to statistical correlations between positions and momenta. Since the Hamiltonian is separable, one can factor the partition function as discussed in Chapter 4. This gives -Bhu/2 3N -3N = (eblu/2 _ -BMu/2) where we have used the fact that & +n) Mw with w = vk/m is the nth energy level for a one-dimensional harmonic oscillator. In the classical world, the partition function still factors, NON 1 N N -BH(r’, p) Q awe Jap’ e . 727.31 (ce) (a) ( rc ~Bk(x = xg)°/2 ° ~8p2/2m =a l dx e hi © = 1 [2 [2m 43N «it x el = (Blu) 3" Since e*hhw/2 ~ 1 + Blw/2 for small g , Og, ~ C0 + BE) - (1 - Bey mM 2 y3N = (Bhw: Q classical For p * pop (but p < pg.) we approach the g(x) for a close packed system, 1.e., delta functions spaced % apart. The lower the density, p, the broader the peaks, and the more rapid the decay to unity at large x. g(x) at high Pp x/l(b) Since u(x) is © for |x| < % and zero otherwise, g(x) is therefore a step function at low p. As p +0, g(x) =e 6ulx) g(x) at low p 2 gt 0 0 1 2 3 4 5 ~ x/I Notice for a hard potential system, gu(x) is either infinite or zero, So Bu(x) is independent of temperature. Thus g(x) is independent of temperature. The configurational properties of hard core potential systems have no temperature. (d) Since the integral of pg(x) determines the number of neighbors, and since there will be one neighbor between 0 and (3/2)2, we have (372) ax Bop (x) = ee 2 0 cP =t (e) Note that the momenta are uncoupled from the positions, and that the momentum distribution is proportional to exp(-Bp°/2m) . Thus, (i) = ay = 5 ket Finally, (iv) = + pe 1 N+ <> = ZN kGT where we have noted that = 0 since the "potential energy" is zero for all acceptable configurations. (f) Since gp = p + bp* + ... , we can identify b as the second virial coefficient. Hence 2 ~ Bu (x) 1 MOOG) == 5 fo dx-1)- 2. b=-4 f axle I Note that b is independent of temperature. (g) The partition function for the system can be calculated exactly. The easiest way is to think of the excluded volume due to the rods (N2) as being subtracted out of the possible position space of each rod (L), Secondly, configurations which are identical except for the switching of rods are counted as the same state, i.e., we need to divide by a factor of NI. So, a fe a ou a-iL dx, due d WoW fy i 2 : " 1 1 N . ow (Lh - NR). This value for Q can also be arrived at from scaling and changes of7.32 coordinates of the configuration integral: First, adopting one particular ordering of the rods, Qiro Wl 1 L 74 if axy A ee which becomes after a change in variables to xj = xj - ig, L-Ne L-Ne 1 1 a-4 f ax} fo dxs AsO x 1 He aeceead — yey = yop 6b > NR) N Then aenQ pps ipiee [antec TAN Thus, b = 2, as already noted. (a) Neglecting the internal structure in the low density limit, the gaseous Ar is an ideal structureless gas. Thus, for M atoms (id) (ia) | _ aang ‘i 2nm 3/2 Pus eteeoM z) 2 = an ( SL 3”? + gnp = f(g) + imp , with p= M/V. (>) Let u,(RN) stand for the total potential energy for all N water molecules with RN denoting all the coordinates necessary to describe the configurations of all N water molecules. In the low density limit, different argon molecules do not interact with eachother, but they do interact with the water molecules. Therefore, quite generally, we can view the total potential energy of the solution as M vcr) + Yu (ny: RN) W i isl Where rn, is the position of the if argon atom and there are M such atoms. The partition function is then N 7 N far... dry exp{-scu,,(R") + Lue sR") J} 11 Q = expl-Nf,(8)-ME(8)] iy py far N -MP (8) ~Bu, (RY) So fave where Q, and <.. denote the partition function and ensemble average for the pure liquid water solvent. Now, since the argon is dilute, different argon atoms are uncorrelated. Thus, the average of the product can be replaced with the product of the average. Hence, due to indistinguishability, me(B) oy “U(r RY) M a-9, So Wee > -MEe(s) + Baul -su(r,, BY) wsqveé Bau _ ty QV epee Meo where e , , it is obvious that du = 0 when U(r,5 RN) is zero.(d) At phase equilibrium, the chemical potentials are equal. Hence, £(B) + tnpg = £(8) + anp, + Bau , smplying pg = peau and since for an ideal gas, 8p = pg + Bp = oan : Q.E.D. We can simply plug into the result for dy derived in Part b. Alternatively, we can follow the suggestion noting Au = change in Helmholtz free energy due to introducing one argon atom into pure liquid water. = ~ kgT £n[Q(1 argon, N waters)/Q,] from which the desired result for exp(-BAu) follows immediately. Next, define Au, according to a -BAu Bau, ([r - re |) e = c, indicates the ensemble average weighted by that A-potential energy. Thus, from the definition of radial distribution functions,day, A 7 My Soe egy (PHA) Ugylr) « Integration from 4 = 0 to A = 1 gives the final desired result. 7.33 To prove the virial theorem in two dimensions, use the same proof as given for Exercise 7.11, except that now, x, = Mae differentiation, this brings down a factor of 1/2 rather than 1/3. One on therefore finds Bp/p = 1 - (Bp/4) f dr g(r)r aut) = 1 - (Bpn/2) J, arr? g(r) Sued 1+ (n/a) J dr ®ty(r) $e BMT) 0 where we have introduced y(r) defined so that g(r) = exp[-pu(r)]y(r) . For hard disks, oP) Lg nee =1, r20. Thus, eB). g(r-g) ae dr As a result, a 2 Bp/p = 1+ pr/2f dr réy(r) 8(r-o) 0 2 = 1 + (po"/2) y(o) Recall that y(r) is the distribution function for cavities. It should be continuous at r = g . However for r > g, g(r) = y(r) so y(o) = lim, g(r) . Hence, roo Bp/p = 1 + (p0°n/2) go")7.35 (a) Let U, = 2 Cug(rs,) + du,(ry5)] . Then from BU. un farye * den a 1 1 da/an = - ay aa one finds using arguments similar to those in Exercise 7.32 that 2 da/dd = (p°v/2) f ar a (r)uy(r) Integration over A from 0 to 1 yields the desired result. + U,) -8y (o) aay = farNe 9 Ny farNe © ~BU)>5 Further, w> ,=< J uj(r,,)> deOiritasj coatd = (p?wa) f ar By(r)uy(r) « Therefore, since A - A) = - k,T £n(Q/Q,) 4 A-Ay £0 far gyirduy(r) «8.7 Chapter 8. Statistical Mechanics of Non-Equilibrium Systems Since H[z] = 1 z> qt 0 2 e20* ee where @ is the Heaviside step function. We can then write e - gD kpa(O) = x, <élq(o) = a*]> <éla(0) - q"}> - * The first term is a conditional probability given q(0) = q . However, since q(0) is statistically independent of v(0) in the ensemble, we can drop the condition. Note that the original expression can't be factored in this way since v(t) = v[t;q(0),v(0)] . So then kpa(0) = <6lq(o) - a*)> , and since the distribution for v(0) is even and the time origin is a1arbitrary, * Kp q(O) = <|v[> <é(a-q )>72x, Recognizing HTT gc (t)] = @Lv(0)] gives the transition state theory expression for ky. (TST) t/t = ar’(t) t t 2 2 J at'cv(oyev(t')> = 2f at’ e 0 0 2ev'> att - eT], Integration and enforcing the initial condition of AR@(0) = 0 gives t) = 2cvoat + 2ev>2fe8/t = 1, For t << 1, to 2nd order int, 2 erie ce aR?(t) = 2¢v>ct + 2cv°>22E1 - be - 1) 1 32 ev? ot? = cdvgt)®> 0 i.e., inertial (non-diffusive) behavior. For t >> 1, an@(t) + 2cvort - 2ev®on? = 2cv'oa(t-1) which represents the long time diffusive behavior, The function is plotted for all time in the figure. AR Wt) 828.20 Vee 1a 4.2 1 2 d= 3 J at cylorey(ey> = gS ar“(t) = vor o toe then v= DAD. pm. <% mv“> For Ar, MW = 40 g/mole, so at T = 80K 1 = 60 fsec , The primary variable x(t) drives the bath, and the driven bath affects the primary variable through the force f(t) = y(t) + fae Xp(trt!) x(t") t ' da ' ' = fy(t) - 8 J at! So] Cyltet')) x(t") d(t-t = f(t) + BC,(0) x(t) - ac, (t) x(0) £ : - 6 J, at’ cy (t-t") x(t") (a) where the second equality uses the connection between x,(t-t') and Cy(t-t") , and the third arises from integration by parts and the fact (essentially a notational convention) that f(0) = f = J ey, = £,(0) fy(t) difrers from f(t) only as time evolves from the initial phase space point at t = 0. Now consider the average of fy(t), averaged with the initial conditions x and x held fixed: ee b Ua BxF.

=< fy(tixk ty, 5,b eb > b : b ivvi x,x fixed at t-0 This equation follows from the fact that the distribution of initial bath variables differs by the factor (gxf) from that when the bath is8.22 uncoupled from the primary variable. Let us employ the y;'s that are the normal modes of the bath, where mode y; has the frequency w,. Then we have 5 : BxC AY, 7 ] | = 1 ¢,, Geo b ee ee i 4 b~ Bxery. » = Bx J 0 cos ut = BxC,(t) () fattest 4 > where the second to last equality follows from the fact that each y; is an independent harmonic oscillator variable and therefore obeys a Gaussian distribution. The last equality is true since for normal modes 2 yyy = DP 845 » hence ate 2, Cyeyyyy > cos(w st) = } ersyp> cosu,t By combining Eqs. (a) and (b) with mx(t) = folx(t)] + f(t) and averaging over initial conditions of the bath variables, the generalized Langevin equation follows directly. (a) Argon Gas t The very slow decay has a time scale of t , the mean collision time in the gas.(b) (ec) <*> Argon Solid The oscillations persist for long times because for small displacements the atoms effectively sit in a harmonic well with period T . The slow decay is due to collisions with other atoms and also anharmonicities in the well which cause dephasing between different trajectories. Argon Solid The decay in the oscillations is due to the processes described above. Note that even if the lattice were one-dimensional, the minima of would not drop to zero because the ensemble average is over various initial conditions, so the turning point times are averaged over. In three dimensions, we have orbits withno turning points. This is reflected in the three separate phases that are averaged over: 2 2 2 i 2 2 2 2 ew (Owe (t)> = <(¥ECO) + VCO) + VECO) (VEC) + vy Ct) + VE (E))> = 3 in the case of an isotropic lattice. (a) CO in Solid The small oscillations are due to the vibrations in the lattice. The long time decay is due to the infrequent process of a CO molecule flipping over completely in the lattice, 8.23 For a small perturbation from the equilibrium zero-field distribution, the fluctuation-dissipation theorem tells us the rate of relaxation to equilibrium is the same as that of a spontaneous fluctuation to that non-equilibrium distribution, At time t = 0, the field is shut off but the flow ¥(0) + 0 . Since the flow will dissipate with time, V(t) = AV(t) « <6y(0)-6y(t)> « 8.26 The relaxation time is then = Substituting e,(t) eee oe, (t) + p(t) into the rate equations gives Gy (t) = = (kay kyg) ey (bt) - ky gent) + ky 30 65(t) = - Kg 0, (6) = (Kgot Kyg) Op (t) + Kye or, in matrix notation, a ]% ae kit Kg 3 ce ky3 ‘ a Jog kag Kgat Kaat [ea Keg The homogeneous part can be solved by expressing a in terms of the 2 eigenvectors of the above matrix, while the inhomogeneous part just adds a constant to d; and dy: written in the basis that diagonalizes the above matrix, 2 ¢ " » o 8 8 2 a o ey v e 4 o 8 8 5 a o where f, and f5 are constants determined by the initial conditions. Thus the concentrations c, and cp can be written as the sum of two decaying exponentials, mat wage o,(t) = Ae + Bye + vast hat 1 2 en (t) = Ase + Boe + a 5, where |,'| and |,'| are eigenvectors of the above matrix. 2 2 (a) So, At “Ant 1 2 de, (t) = Aye + Bye mAyt mAb bon(t) = Ale + Boe where M2 = C(k3¢ ky3) He (k 35% ky) 1/2 2 + tv {E(k + ky3 (got Ky3)1/2 } Ky gko3 -8Q (b) For e << 1, then Ki3 7 ko3 »> kay K30 . We can write 1,2 31 3 £7 ALK 3y# ky 3) + (got Kog)1/2]° = (kay kay + Kaikog + Ky 3ka9) = [kg kyp)/2 + (Ky 3% Kog)/21 wtraSi~t kay + Kaikog + Ky akg, )/L(kat Kya # Kaot kg)/2l « : 3132 * Kaikag * Ky 3gq)/E(K3y* Ky3 * K3a% Kog A, 5 18 now conveniently written in terms of the small parameters 1,2 i k31k39» So that we can expand the root Yi-e = 1-35: Ayia = Elkgyt kyy)/2 + (ky 3 + ky3)/2] a . ' ‘ é x {rer 3 (31k 35 k3)kog Ky 3k 30)/( (kay Kg t Kot k33)/2) qeSo the + root is [(k 4+ kp3)/2 + O(e)] (2 - O(€)] = kyy + kag = TE 13° 13 * Ko3 * "transient and the - root is (K3yk 3p + Kay kog t Ky gk3p)/(Kay* Ky gt Kgot kp g) = (kak ky 3* Ky3) = Ty 3ike3 * Ki3k32 23 rx * From the above, k k -1 23 13 “1 1 . (SO) + hole) i > rm * “31 Kg * Rag 32\ky * key transient and so the relaxation is dominated by 1, . When k,. =k. , pxn 23 * 13 -1 Thxn * (Kg) * K39)/2 (c) As shown above, the faster transient decay occurs on a time scale of pote (kia + Koz if ko 13 2 yg (d) The two decay rates are analogous to the two rates in the reactive flux description: 1,0) = trnansient “< Trym * The connection can be made by imagining preparing the system at the transition state, i.e., in state 3. Then the decay into states 1 and 2, c;(t) and eo(t), follow the two decay rates, one much faster than the other. But o,(t) « <én,(0)én,(t)> by the regression hypothesis, and the time derivative of <én,(0)én,(t)> is just the flux in the reactive flux picture. In particular, a is on the order of ky or k39, and is the plateau value for the reaction rate.(e) This is similar to the transition state theory idea where e 82 is the probability of getting to the transition state 3, and D = 1/n is the rate to cross the barrier (3) once there. As we showed previously « TST) cly|> « a 8.28 T= 300K n = 0.01 poise D,. = 1x 10 °cm*/see Ar m= 40 amu 1,0 = 18 amu ar (a) and (b): The velocity distribution is just the Maxwell-Boltzmann distribution and is independent of the potential. So we = om = 1.87 x 10? om?/sec® or eve ol? «4.3 x 10" em/sec for Ar atoms in the vapour and in solution. (ce) Assuming inertial motion in the vapour, the time to move 10A is t= sonsev >'/2 = 2.3 psec . (d) Since an@(t) = 6Dt , the time to diffuse 10A in solution is t = 170 psec, We are justified in assuming diffusive motion since 170 psec is long compared to the velocity relaxation time calculated in part (e).(e) The relaxation of the non-equilibrium distribution will follow the same rate as that of spontaneous fluctuations, such as in , The decay time for is given by Trelax 7 BmD = 16 fsec . (f) From 8.24 p= = a 1 2or 3 wee 7 an@(t) So if n doubles, D halves, and the diffusion time t = Sf doubles to 340 psec. In contrast, since the temperature is still 300K , '/? = 4.3 x 10" om/seo remains the same. 1