Physics 7230 – Statistical Mechanics 1 – Spring 2018

Problem Set #2
Due Wednesday, February 7 at 3pm

Problem 2.1: Rigid rotator in phase space. (20 points)

A rigid rotator is a model for a diatomic molecule whose intermolecular separation can be
regarded as fixed.

a) Consider a rigid rotator in two dimensions, which can be taken to be a particle of mass m
constrained to a distance ρ from the origin, but allowed to move in the azimuthal angle ϕ.
Find the conjugate momentum, and determine the Hamiltonian as a function of coordinates
on phase space.
Describe how to divide the two-dimensional phase space into “cells” of volume h with
lines of constant energy, starting with the line of zero energy. Calculate the energies of the
states associated with the cells and compare to the energy eigenvalues of the corresponding
quantum mechanical rotator.

b) Now consider a rigid rotator in three dimensions, which we take as a mass m fixed at a
distance r from the origin but free to move in θ and ϕ. Define the conjugate momenta, and
write the Hamiltonian in terms of the phase space coordinates, as well as writing it in terms
of the angular momentum squared M 2 and the moment of inertia I, which you should define
in terms of other quantities.
By evaluating the volume of the relevant region in 4D phase space, show that the number of
microstates available to the rigid rotator with angular momentum ≤ M is (M/h̄)2 . Estimate
the number
q of microstates that can be associated with the quantized angular momentum
Mj ≡ h̄ j(j + 1), where j = 0, 1, 2, . . . or j = 1/2, 3/2, 5/2. . . . and compare to the result of
the corresponding quantum mechanical rotator.

Problem 2.2: Microcanonical ensemble for ultrarelativistic gas. (20 points)

Consider an ultrarelativistic gas, with one-particle energies ε = pc. In this problem we will
find the thermodynamics of this system using the microcanonical ensemble.

a) First start with the integral

Z ∞
I= dr e−ar . (1)
0

Evaluate it and take derivatives of both sides (both the expression for the integral, and its
result) with respect to a to prove that
Z ∞
dr r2 e−r = 2 . (2)
0

1
Now use this result to help prove that the following 3N -dimensional integral evaluates to
N
Z 0Y
(8πR3 )N
V3N ≡ (4πri2 dri ) = , (3)
i=1 (3N )!

where the prime indicates the integral is to be over the region 0 ≤ N i=1 ri ≤ R. To do this,
P

let R ≡ r1 + r2 + . . . where the ri are magnitudesR of three-vectors, and define the volume
enclosed out to R as V3N = AR3N . Then integrate dV3N e−R over all 3N -dimensional space
two ways: in terms of one 3N -dimensional radial integral, and in terms of N 3-dimensional
radial integrals, and solve for A.

b) Use the result of the last part to derive the total volume in phase space for a gas of N
ultrarelativistic particles with energy between 0 and E in volume V , and from this obtain
the number of microstates Σ(N, V, E). From this obtain the thermodynamics of the system
to derive the results (all different from the nonrelativistic case),
E CP 4
E = 3N kT , PV = , γ≡ = . (4)
3 CV 3
Does the ideal gas law still hold for this system? Is this what you expect?

Problem 2.3: Canonical ensemble for ultrarelativistic gas. (20 points)

a) In the canonical ensemble, show that the partition function of the same ultrarelativistic
gas (N particles, ε = pc) is
 !3 N
1  kT
QN (V, T ) = 8πV  . (5)
N! hc

From this, reproduce the same thermodynamic relations as in the last problem, now with U
as the energy:
U CP 4
U = 3N kT , PV = , γ≡ = . (6)
3 CV 3

b) Using the inverse Laplace transform, derive an expression for the density of states g(E).
Compare the result to the number of microstates Σ(N, V, E) found in the previous problem.

Problem 2.4: Fluctuations in the canonical ensemble. (20 points)

a) Show that for a system in the canonical ensemble

" ! #
∂CV
h(∆E)3 i = k 2 T 4 + 2T 3 CV . (7)
∂T V

2
b) Verify that for an ideal gas we have the two results,
* 2 + * 3 +
∆E 2 ∆E 8
= , = . (8)
U 3N U 9N 2

Problem 2.5: Classical anharmonic oscillator. (20 points)

a) Consider a single one-dimensional classical anharmonic oscillator, where the potential is

V (q) = cq 2 − gq 3 − f q 4 , (9)

with c, g and f some positive constants. Assume g and f are small. Show that the leading
contribution of the anharmonic terms to the heat capacity is

5 g2
!
3 2 f
k + T. (10)
2 c2 4 c3

b) In the same system and to the same order, show that the mean value of the position
coordinate q is
3 gkT
hqi = . (11)
4 c2
Explain why this depends on g and f the way that it does.

Problem 2.6: Quantum anharmonic oscillator. (20 points)

Now consider a one-dimensional quantum mechanical anharmonic oscillator. Instead of work-

ing with the Hamiltonian we will work directly with the energy levels, which may be taken
approximately to be,
2
1 1
  
εn = n + h̄ω − x n + h̄ω , (12)
2 2
for n = 0, 1, 2, . . .; here x is a dimensionless number related to the anharmonicity, which we
will take to be small. Show that to first order in x and fourth order in u ≡ h̄ω/kT , the
specific heat of a system of N such oscillators is given by
1 1 4 1 1
   
C = Nk 1 − u2 + u + 4x + u3 . (13)
12 240 u 80
Notice that the anharmonic term has a piece that grows with temperature.