Chapter 3 3.4, For the first part, we use eqn. (3.2.31) with all w, = 1. We get kar sft ree, ynrak m {Se } sx, which is indeed equal to (A/T) + (U/T) = S. For the second part, we use eqn. (3.2.5), with the result that, Substituting for nZ from eqn. (3.2.10), we get Sis prams eae) 1 68, yin W {nz} = BBE.) +k mf De _ \. which is precisely the result obtained in the first part, 3.5, Since the function A(N,V,T) of a given thermodynamic system is an extensive quantity, we may write A(N,V,T) = Nf(v,T) (w= VIN). Tt follows that "(Sr)" +" (S), a] "rg Adding these expressions, we obtain the desired result. 3.6. Lot's go to part (c) right away. Our problem here is to marimize the expression S/k = —Y Praln Pa, subject to the constraints ° Poe =1 DEP of Lagrange’s undetermined multipliers, we are led to the condition and N-P,« =. Varying P's and using the method D-C +n Phe) — 7 — BBs - Ny} 6Pra = 0. In view of the arbitrariness of the 6P"s in this expression, we require that =(1+In Pps) = 7 = BEs— aNy = for all r and s. It follows that Prax oc exp(-BB. — aN). ‘The parameters a and 8 are to be determined by the given values of V and E. In the absence of the constraint imposed hy NV, the parameter a does not even figure in the calculation, and we obtain Pr x exp(—BEr), as desired in part (b). And if the constraint imposed by F is also absent, we obtain P, = const., ‘as desired in part (a). 3.7, From thermodynamics, Substituting (2) into (1), we obtain the desired result. For the ideal gas, Q « VN T#8/2 Therefore, (9 nQ/OV)r = N/V. We then get 3.8. For an ideal gas, jy (onmb D2 _ NAEP (mk P)*? Oe P weko iS 3.14, Tt follows that T(9 In Q,/AT)p side of the given equation then is V (2amkT)¥2) 5 In { Nm Sta 5/2; the expression on the right-hand which, by can. (3.5.13), is indeed equal to the quantity $/Nk We start with equ. (8.5.5), substitute H (q.p) = 32 (v3/2m) + U(a) and integrate over the pj's, to get 1 (2nmery's” “1 -U(ay/kP gan Sr) 2x(Wi0), where Zy(V,7) = fe 4 Tt follows that, for N > 1, a2 \3?2 asst nfov( ) } a] -ar iz, was wT) = Qamk! a2 S=M [> {i (2) beg] +k nzvur(2 ind Now Ar é In 4) RD feTW ET (U/kT?)BN wy SeTRT ENG kmnzakin{v’ eT} ome my 2. Dao Go . F> while ar Substituting these results into the above expression for $, we obtain the desired result for . In passing, we note that (H) = A+ TS = 3NkT+U. For the second part of the question, we write U(q) = 5 u(ry), so that BUC) = [peer TP + fu), i ot and follow Problems 33.23 and 1.4. ‘The quantity V then appears to be in the nature of a “free volume” for the molecules of the system. a) The Lagrangian is given by B= KV =D Ami, Dlr) Tl (Ma) + te (Mall where .N denotes the particle number, «= 2.4.2 denotes the cartesian directions, and r2, = 30, (vq —"yq)®. The canonical momenta ag |‘The Hamiltonian is given by H = Praia — = Dalry) +E le ir) +e (= rah 1 va ‘The canonical pressure can 3e written tat 31? aL 1 , 1 Gye Mell — Pa) = gps (Fe + Fy + Fe). ‘This is clearly the instantaneous force per unit area on the right, back, and top walls. b) The cartesian coordinates for the scaled position inside the box are Sia = Tia/L so the Lagrangian becomes f= SF md28, — Duly) — Te (Lia) + tea (EL) ‘er SG ia In this case the canonical momenta are. OL Bia ‘This lends to a Hamiltonian of the form #= fe, 5 + Do ulLsis) +> [uw (Leia) + tw (L Lia). iG ia P= ee with canonical pressure is 1 / ia A ype Dll) sia + ty (L— Leia) (A — Sia) Converting back to normal cartesian coordinates and momenta gives 2 Pe Patapon yy, a Ve'irsdry = AT belinda + uy(L— rear‘The first term is (2/3)(N/V) times the kinetic energy per particle 80 is O(N). ‘The second term is (1/3)(V/V) times the virial per particle so is also O(N). On the other hand, third term is proportional to the force on the walls divided by tke volume so is O(N) which is negligible in the thermodynamic limit. Comparing to equatio 5) for the averaye pressure we see that P aT 1 ‘ aN (5 wylris ris ia 3.15. Here, Qu (VT) = (1/N)QR(V,T), while Is unr) [ eon tape e which yields the desired result for Qyy. The thermodynamics of the system now follows straightforwardly. As regards the density of states, the expression auany= f *ateide = FF rs leads to anv. ae) =e for a single particle, while the expression for Qu(V,T) leads to N pay-1 Be) Tex for the N-particle system; ef. the expression for 3(B) derived in Prob- lem 28. Differentiate the stated result with respect to 8, to get ou 2) (poms ,) which amounts to the desired result: (£1?) ‘This means that — (H)? = -(0U/a8).BAS. Wo start with oan. (3.6.2), viz, ou = Be a See ae, +0, (a and differentiate it with respect to 8, keeping the E, fixed. We get PU Lipsy wns e, ar Substituting for (407/93) from eqn. (1), we get PU 4 ap (B°) — (EU +203, which is precisely equal to ((E-U)!). As for °U/88%, we note that, since (8), Gare (= : — er? {2 (-Kroy 2[, 2 (ON Bp AT’ al ‘RI v)], T’ [prey +1 (3), |: Hence the desired result. For the ideal classical gas, U = $NKT and Cy = $Nk, which readily yield the stated results, 3.19. Since G = Daivi. G =D (divi + aii). Averaging over a time interval 7, wwe get ‘ tr ter 3 [ Dean+anya=2 [ ea-S9 Oy 14 ‘ For a finite V and finite #, the quantity G is bounded; therefore, in the limit r — oo, the right-hand side of (1) vanishes. ‘The left-hand side then gives, (dom =) which leads to the desired result, 3.20. ‘The virial of the noninteracting system, by equ. (3.7.12), is -3PV. The contribution from interparticle interactions, by eqn. (3.7.15), is given by the “expectation value of the sum of the quantity —r(9u/dr) aver all pairs of particles in the system”. If u(r) is a homogencons fiinetion (of degree 1) of the particle coordinates, this contribution will be —nU, where U isthe mean potential energy (not the internal energy) of the system. The total virial is then given by ‘The relation K = —$Y still holds, and the rest of the results follow straightforwardly. Al systems considered here are localized. ‘The pressure term, therefore, drops out, and wo are loft with the result, 3 a Example (a) pertains ton = 2, while examples (b) and (@) pertain to n= 1. Inthe former ease, K =U = 32; in the latter, K = —}U = -E. ‘The next problem pertains to n = 4. K .. Note that a force proportional to q° implies a potential energy proportional 3.23. tog. Thus Ha ht aot (e>0). It follows that Fe Be /2m (2 2m} 1 iy £ ae yap 1 (Sat) = Te 82*/2m dp | for the values of these integrals, see equs. (13a) of Appendix B. Next, FP (cad “x a (ea*) = “Foe —— pp iB). where [(3) denotes the integral in the denominator. It to see that 1/3) is proportional to ~"/4, whence (eq) proves the desired result. straightforward 1/48, which ‘The key to this derivation is writing the partition ftmetion in terms of position integrals over scaled coordinates. Assnme a enbie box of size [ and volume V = L*. The scaled position for particle i is s; = rj/L. Thepartition function is Qn, =m/ oo(- aE wr) ae coal renfo(- aus 3) Os, coal Now the pressure is (eg NOx Vv “Ox ‘This can be simplified by going back to integrals over the normal positios ‘variables to give equation (3.7.15) Bin f (gro) oa oer) 8.24. By eqn. (3.7.5), we have, for a single particle, a) ‘The left-hand side of (1) i the expectation value of the quantity pow, Le ‘pn which, for a relativistic particle, is equal to mpu2(1—u2/c2)-¥/?. Phe Aosized result fol readily: In the non-relativistic limit (u-«), one obtains: (Jynou®) =: 3K7' in the extreme relativistic limit (u — ¢), one obtains: (me?) = 3kT. Note that, in the latter case, moe? is negligible in comparison with me?, so there is no significant difference between the kinetic energy and the total energy of the partite 15. For the first part of this problem, see Sec. 6.4 — especially the derivation of the formula (6.4.9). For the second part, equate the result obtained in the frst part with the one stated in eqn. (3.7.5) 8.26, The sli of ways i icity w(i){= Gj + ~ 1!/71(6 — 1!) arises from the variety isCalculation of the various thermodynamic quantities is wow straightfor- ward, ‘The results are found to be essentially the same as for a system of sN one-dimensional oscillators. However, since Q® (A) = ON (3) the chemical potential j1, will turn out to be s times ji. 3.28. (a) When one of the oscillators is in the quantum state n, the energy left for the remaining (N —1) oscillators is H — (n+ 4) fiw; the corre- sponding number of quanta to be distributed among these oscillators is R—n; see equ. (3.8.24). The relevant number of mmicrostates is then given by the expression (R—n+N —2)!/(R—n)(N —2)!. Combined with expressior (3.8.25), this gives (R-n4+N (R+N-1)! (Rw —2)! * RE Pn @ It follows that mgt R= pm RontN By iteration, ps = po{n/(n + 1)}". Going back to equ. (1), we note that RYN which completes the desired calculation. (b) The probability in question is proportional to gy—1(H — ¢), Le. to (BE —2)3-)-1_ For 1 < N, this is essentially proportional to (1 —2/E)34 and, for ¢ < —E, to e-8Ne/28, 3.29. The partition function of the anharmonic oscillator is given by a=4 f [oot { =F ‘The integration over p gives a factor of /2mm/B. For integration over q, we write, 2 alan? 4fe! 2 ee cnBed? glo 44a") = 9 Bed [1+ st00 + ie) + Plo + +s the integration then gives 74,9 lay SF Vn ays +t SlatIt follows that Bin sf, 15g? Qu) = a Mgr Gees” so that / Bf 15g? InQa() = const, — In -+ 5 + Seger whence UB=5 and CO) =k Next, the mean value of the displacement q is given by =f [i eotatna snags [ [sani In the dosired approximation, we get wate ferme af Jo Pee a = 00 ies Nf 6 3.30. The singleoscillator partition function is now given by SE ernterynvontoette Qi(8) For x <1, we may write * 2 Qua) = ents [ + Be iG + 5) fo + 4 c= a tame tel are S(0)= oer = [asa (Su) and bm oorIt follows that In Qy =In[Sy + ruSy +...] ~ In Sy + ru(S2/S4) ~-xfom(fo) edn fo (5) 3} ‘The frst part of this expression leads to the standard results (3.8.20 and 21). ‘The second part may, for simplification, be expressed as a power , (2+4+4- "\i pot) ‘The resulting contribution to the internal energy per oscillator turns out to be oo he (4 Bo and the corresponding contribution to the specific heat is given by 3.31, This problem is essentially the same as Problem 3.32, with g1 = a2 1, ¢) =O and 2g ==. 3.32. We use formula (3.3.13), with P, = p:/a: for each of the states in group Land po/qy for each of the states in group 2. We get hGeaoGes)) © (a) In thermal equilibrium, DS ger O- With 2 = (62-21), we have: pr = i/(ou + m2e*) and pz = 92] gx¢2 + 92). Substituting these results into (1), we obtain Sak “In (gs +9307") + —22— In (gxe" +) | n nt pe neta Writing the first log as Ing; +In{1 + (g2/a1)e-®} and the second log, as In gi + 2+ In{1 + (g2/g1)e-*}, we obtain the stated expression for S. (b) With Q = ge-#*" + ge82, it is straightforward to see that A= kT In{gre + gone} and 1 = {mere + mene 8) {e824 90%) ‘The formula $= (U ~ A)/T’ then leads to the desired result.(c) As T +0, 2 + ce and S indeed tends to the value kIn gy. ‘This corresponds to the fact that the probabilities p; and py in this limit tend to the values 1 and 0, respectively. 3.35, The partition function of the system is given by Ox = LOY, where @ = % Z being the factor that arises from the rotational orientational degrees of freedom of the molecule: v5 ; dnote dod 2 foo -0 {ib gen ons] Seog ant) /? (2nd sin? @ eos 9 2rd0 JAG ) St) ements IT 2 sinh(3yF) ie Bu ‘The study of the various thermodynamical quantities of the system is now straightforward. Concentrating on the electrical quantities alone, we obtain for the net dipole moment: of the system NowZ 3B aE M, =N(p cos 8) = =Np [ror (PF) 5 cf. eqns. (39-4 and 6). For Buk <1, Ms = Np- you. ‘The polarization P, per unit volume, of the system is then given by Pm /3kT (n=N/V), and the dielectric constant = by E+4nP deny? Rs ‘The numerical part of the problem is straightforward. 3.36. ‘Tho mean force (F) hetween the two dipoles is given by _ Se? (=a / AR) sin bd Ody -sin 6! do! dg odndg sin dO dig? a) (2)3.37. where Z denotes the integral in the denominator of (1). At high temper- atures, we may write a= | [i-oustou _ | sin 0 atten a a! ‘The linear term vanishes ou integration and we are left with / 14 Lyn? 09 eos 0 cos f — sin 8 sin 6 cosly — 9")? — Te ve sin d Ady -sin 0 db” dg! oe Ll’? ft 19,2 2.1, = 107 [158 za {84 t-o42.2 3} | Tt follows that 2 In Z = const. + 252M” and hence, at high temperatures, yg tt’? x28. wR By eqns. (39.17 and 18), we have, for a single dipole, S (anna) exo (Gayamit) L ,cx(Ban amit) At high temperatures, the exponential may be approximated hy (1 + Bon. nmdl) which vields, to the leading order in IT, fiz = Ba? pH. One readily obtains for the Curie constant (per unit volume) of the system Cy = No (0? why / Ke. Writing m = José, one obtains the desired result For the second part, we simply note that, for a given J, J ym _ HI QI 1 V/s _1 2s ~ 241 gi +).‘Treating m as a continuous variable, the partition function of a magnetic ipole assumes the form J Q(B) = f ; ea diy = sinh (8qu_JH); 2 Boal cf. ean. (3.9.5). It is clear that this approximation will lead essentially to the same results as the ones following from the Langevin theory — except for the fact that the role of j will he played by gitz.t, which skould be contrasted with the expression (3.9.16) of the quantum theory, 3.40. (a) By definition, Cy = T(A8/AT)y and Cy = T(3S/IT)as. Now G),- GBD. © OT) \OE) 4° \OM yp NOT)" aU — TéS ~ Sd = HaM — SAT, with the resalt that (JH/A) yy = —(8S/2M). Equation (1) then becomes OS\ _ (0S) _ (aH) (aM ® AW) \OT) yy OT) yy VAT) yy Multiplying (2) by T, we obtain the desived result for Cu — Cur (b) The Curie law implies that M = CH/T, This means that (OH/0T)x¢ = H/T, while (AM/AT)q = —CH/T?. It follows that Cir ~ Car = Ch? /T?, at che same time, dA 8.42. Let Ni(N2) be the nmber of dipoles aligned parallel (opposite) to the field. Then Ny +N2=N, while -—Nye+ Noe = —Efz), No (N +E /s). The number of microstates associated with this macrostate is given by MM THN — E/Y TRON + EVE) ‘The entropy of the system is then given by the expression QU, B) = . 1 k inn 3( Joa which is essentially the same as ean. (3.10.9).For the temperature of the system, we get which agrees with ean. (3.10.8). ‘The partition function of this system is given by the usual expression (3.5.5), except for the fact that the Hamiltonian of the system is now a function of the quantities p, +(e; / )A(rs), and not of the py as such, However, on integration aver any component of pj, from —oo to +50, we obtain the same standard factor VZnmkT — regardless of the value of ‘the corresponding component of A. The partition function is, therefore, independent of -he applied field and hence the net magnetization of the system is zero. ‘The Shannon information for a single message is given by J = —>, P-In P, where P, is the a priori probability of message r from among all © pos- sible messages. The maximum information is obtained from varying the probabilities, usng a Lagrange multiplier to maintain the normalization, DP. = 1, and demanding the solution is stationary, Ty — ps (© ») =~ OP [npr — 1 pe ‘This implies the P= coust, i.e. all messages are equally likely. Therefore P, = 1/O, which gives I) = InQ. Any other set af probabilities gives smaller information per message. o= Kooping to the general eases in which probabilities of individual mes- sages messages do not need to be equal, consider a sequence of two mes- sages. The @ priori probability of message r followed by message 1 is Port = PyPrsGros. The quantity G,, is the correlation between the two messages. A value of Gry greater than unit implies that the first message r increases the probability of finding the second message 1” above P,». The have the following properties: Yo, Prw = Pp Pie, S,P.Grys = 1 and Sy, PGyy = 1. The infor o messages is given by Ty =D Prot lt Pore = SO PpPesGirr! Wu (Pp Pee Gre)- Expanding the logarithm and using the above summati properties gives B= 2h DPPC lnG = 2 +L PPG oon (ZH ) a a =Now, using Ing <2 —1 for all x > 0, we get BS 2+ PPG, = ‘The information contained in two correlated messages is reduced compared to sum of the information contained in two uncorrelated messages. Anal- of the first 65536 digits of = results in an information per character %2.3=In 10. That makes sense hecanse the characters 0,--- ,9 are ‘uted in the digital representation of = Furthermore, since the digits of m are uncorrelated, the information per pair of characters is Jz = 46 = 2h. Analysis of the first 15,000 characters of A Chrismas Carol by Charles Dickers gives 1, ~ 3.08 ~ In21.75. ‘This value is rea- sonable since most of the characters are lower case letters of the alphabet and blanks. The nonuniformity of the disteibution of letters reduces the information below In27. When analyzed two charactors at a tine, the information is I2 © 5.4 © 2In 15.25. The strong correlations between characters in Kglish text reduces the information well below 2/;.