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1. [Easy review question 1] Compare the free energy Ap of a system of volume V at T of a classical monatomic ideal gas consisting of 3N particles and that Am of a classical ideal gas mixture consisting of three diﬀerent monatomic chemical species of N particles each (at T occupying the same volume V ). (1) What is the diﬀerence between these free energies? First, guess your answer (with justiﬁcation). (2) Do your calculation of Ap and Am . Does the diﬀerence agree with your expectation? Solution Since this is an ideal gas, there cannot be any energetic diﬀerence. Therefore, the diﬀerence must be only the mixing entropy. Thus, Am is smaller than AP by 3N log 3. We can almost copy (2.2.3) in the text: enQ 3V Zp = 3N and enQ 3V Zm = N Therefore, Zm = Zp 33N . That is, Am = Ap − 3N kB T log 3. [ [ ]3N

]3N .

Since A = E − T S , this implies Sm − Sp = 3N kB log 3. 2. [Easy review question 2] A classical ideal gas consisting of N particles in a volume V has three low lying internal states (non-degenerate) equally separated by energy gap ϵ (i.e., 0, ϵ and 2ϵ). What is the chemical potential of this ideal gas? Solution The internal partition function is zi = (1 + e−βϵ + e−2βϵ )N . Therefore, A = Aideal −N kB T log(1+e−βϵ +e−2βϵ ) = N kB T log(n/nQ )−N kB T −N kB T log(1+e−βϵ +e−2βϵ ) Since N µ = G = A + P V , G = N kB T log(n/nQ ) − N kB T log(1 + e−βϵ + e−2βϵ ) or µ = log(n/nQ [1 + e−βϵ + e−2βϵ ])

What is the general implication? The chemical potential is less than that of the structureless ideal gas. The quantity in [ ] is the eﬀective number of diﬀerent chemical species, so 1

3. in the limit of long polymers). L)e dL ≤ Z (T. since you need not worry about inﬁnite integration rage.L∗ +1] min Z (T. Prove the equivalence of these two descriptions. L)eβLF + log 2 ≤ log Y ≤ log Z (T.1.6. so the hardest part of the mirocanonical-canonical equivalence proof is totally ignored.. so we are done. by a Legendre transformation: G = A − LF ) agree in the thermodynamic limit (i. 2. the eﬀective number of particles is reduced if there are internal states. Thus we are done.] Simply mimic what is illustrated in Fig. Suppose there are N noninteracting quantum spins with S = 1/2 in a lattice system which has an easy axis in the x-direction: H0 = −A 2 N ∑ i=1 σix . In any case. L∗ ) + βL∗ F + log(2N a)..L +1] L∗ −1 ∗ so taking the log log L∈[L∗ −1. Then. ∗ L∈[L −1. L)eβLF dL. The the rest is the same as the ideal chain case. because the integration range is FINITE. ∫ L∗ +1 ∫ Na ∗ βLF Z (T. Let L∗ be the L that maximizes ZeβF L . the (densities of) generalized Gibbs free energy G computed from Y (as G = −kB T log Y ) and that computed from the Helmholtz free energy A = −kB T log Z thermodynamically (i. In the general case.] Solution From the hint in [ ] I never expected most of you to compute an explicit example. L∗ −1 −N a You could replace the leftmost term with 2Z (T. ﬁrst we must demonstrate that log Z is extensive (for general monomer-monomer interactions). The second inequality is obviously OK. L)eβLF dL ≤ 2N aZ (T. L)eβLF dL. L) is the canonical partition function of the chain with a ﬁxed end-to-end length L. but this is much easier. [Statistical physics is not materials science. F ) = Z (T. −N a where Z (T. 4. If the polymer is ideal as discussed we know Z explicitly.e. we estimate ∫ L∗ +1 βLF 2 min ∗ Z (T.6) ∫ Na Y (T. That is. If you wish to be a bit more rigorous. we want a general relation that cannot be proved by the study of any concrete model.e. If the discrepancies are of order log N or less. so log Z is extensive. . F ) of a freely jointed polymer chain (The ideal rubber band problem in Section 2. obviously. we are happy. [Ensemble equivalence] We have discussed the constant force ensemble Y (T. and changing L∗ by 1 does not cause any extensive change.n/[· · ·] is the number of particles of each chemical species. L∗ )eβL F . L)e ≤ Z (T. L∗ )eβL F . That is. [You can mimic the proof in the notes.

so √ √ z1 = T r cosh(β A2 + B 2 ) = 2 cosh(β A2 + B 2 ). 3 . These partition functions come close when the temperature is suﬃciently high. [Hint: for example. βB ).where A is a positive constant. Is there any macroscopically meaningful diﬀerence? Solution The formula we need is eα·σ = cosh α + (n · σ ) sinh α. Therefore. where · · · denotes the traceless terms (notice σx σz = −iσy ). i=1 (1) Compute Z1 = T r e−β (H0 +Hi ) . the unit direction vector.] (2) Compare this with { } Z2 = T r e−βH0 e−βHi .13 of my Introductory QM notes.e. the spin operator is ( /2)σ ). Notice that the trace of the second term vanishes. and σ denotes the Pauli operator (i. We can compute eβAσx eβBσz = (cosh(βA) + σx sinh(βA)) (cosh(βB ) + σz sinh(βB )) = cosh(βA) cosh(βB ) + · · · . 0. so in the above formula α = β A2 + B 2 . see 27. [ ]N √ 2 2 Z1 = 2 cosh(β A + B ) . but at low temperatures they are quite diﬀerent. Thus. we cannot easily study a quantum system with external ﬁeld based on the study of the system without it. so the interaction Hamiltonian reads N ∑ Hi = −B σiz . where n = α/α. N Z2 = z 2 . where To compute Z2 ﬁrst we note where z2 = T r eβAσx eβBσz . Z2 = [2 cosh(βA) cosh(βB )]N . and n = C /α. That is. We apply an external magnetic ﬁeld B in the z -direction. z1 = T r eβ (Aσx +Bσz ) = T r eC ·σ √ with C = (βA.. N Z1 = z 1 .

±. where ∑ Sz = i σzi is the z -component of the total spin angular momentum (I ignore /2). · · ·|e−βH0 |· · · . B ) = ∑ M 〈±|eβAσx |±〉 = cosh(βA). where |· · · . we get only the ‘classical version. ±. M ) = Now. M )e+βBM M identical to the Z ’s above? What is the lesson you learn? Solution [To outline the idea. I wish you taste how grave the mismatch is. The (N ) dimension of this subspace is just N+ . · · ·〉 = 〈+|eβAσx |+〉 〈−|eβAσx |−〉 . M )e +βBM = ∑( N ) N+ N+ coshN (βA)e+βBN+ e+βBN− = coshN (βA) 2N coshN (βB ) As expected. · · ·|e−βH0 |· · · . etc. 4 . Z (T. ±. Therefore. ±. M ) = T rM e−βH0 = 〈· · · . where N± = (N ± M )/2 (as the classical case). (3) What is the partition function Z (T. ∑ Z (T. I identity σ and the magnetic moment vector.’ [Legendre-Laplace correspondence fails in QSM] I said the Legendre-Laplace correspondence so useful in classical statistical mechanics is not always allowed1 . That is [ ]N+ [ ]N− 〈· · · . ±. M ) for this system under the condition that the z -component of the magnetization is M (without the B ﬁeld)? (4) Is ∑ Y (T. M ) should be the trace of e over the subspace speciﬁed by Sz = M . · · ·〉 is the ket with N+ +1/2 states.) P βA i σxi Z (T. so they are extra questions. ignoring /2.The following questions can be tricky. B ) = Z (T. We know Therefore. Y (T. This space may be understood to be spanned by |±〉 · · · |±〉 (where |±〉 = |1/2. 1 I emphasize that this is ﬁne for microcanonical. · · ·〉. canonical and grand canonical ensembles. ( ) N coshN (βA) N+ Z (T. ±1/2〉).

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