PHY 412: Statistical Physics
24-25 Semester II
Assignment – 2
Problems in black are for submission; Blue ones are for practice. Due date: February 19th in Class
1. Consider 𝑁 harmonic oscillators with coordinates and momenta {𝑞𝑖 , 𝑝𝑖 }, and subject to a Hamiltonian
𝑝2 𝑚𝜔 2𝑞2
ℋ ({𝑞𝑖 , 𝑝𝑖 }) = ∑∞ 𝑖
𝑁=1 [2𝑚 +
𝑖
].
2
(a) Calculate the entropy 𝑆, as a function of the total energy 𝐸.
(Hint. By appropriate change of scale, the surface of constant energy can be deformed into a sphere.
You may then ignore the difference between the surface area and volume for 𝑁 ≫ 1. A more elegant
method is to implement this deformation through a canonical transformation.)
(b) Calculate the energy 𝐸, and heat capacity 𝐶, as functions of temperature T, and N.
(c) Find the joint probability density 𝑃 (𝑞, 𝑝) for a single oscillator. Hence calculate the mean kinetic
energy and mean potential energy for each oscillator.
2. Consider a gas of 𝑁 hard spheres in a box. A single sphere excludes a volume 𝜔 around it, while its
center of mass can explore a volume 𝑉 (if the box is otherwise empty). There are no other interactions
between the spheres, except for the constraints of hard-core exclusion.
(a) Calculate the entropy 𝑆, as a function of the total energy 𝐸.
(Hint. (𝑉 − 𝑎𝜔)(𝑉 − (𝑁 − 𝑎)𝜔) ≈ (𝑉 − 𝑁𝜔/2)2 )
(b) Calculate the equation of state of this gas.
(c) Show that the isothermal compressibility, 𝜅 𝑇 = −𝑉 −1 𝜕𝑉/𝜕𝑃| 𝑇 , is always positive.
3. 𝑁 diatomic molecules are stuck on a metal surface of square symmetry. Each molecule can either lie
flat on the surface, in which case it must be aligned to one of two directions, x and y, or it can stand up
along the z direction. There is an energy cost of 𝜀 > 0 associated with a molecule standing up, and zero
energy for molecules lying flat along x or y directions.
(a) How many microstates have the smallest value of energy? What is the largest microstate energy?
(b) For microcanonical macrostates of energy 𝐸, calculate the number of states Ω(𝐸, 𝑁), and the entropy
S(𝐸, 𝑁).
(c) Calculate the heat capacity 𝐶(𝑇) and sketch it.
(d) What is the probability that a specific molecule is standing up?
(e) What is the largest possible value of the internal energy at any positive temperature?
4. Consider the statistical mechanics of a tiny object with only two discrete states: one of energy 𝐸1 and
the other of higher energy 𝐸2 > 𝐸1 .
(a) Find the ratio of the equilibrium probabilities 𝑝1 /𝑝2 to find our system in the two states, when
weakly coupled to a heat bath of temperature T. What is the limiting probability as 𝑇 → ∞? And as
𝑇 → 0?
(b) Use the normalization of the probability distribution (the system must be in one or the other state)
to find 𝑝1 and 𝑝2 separately. What is the average value of the energy E?
5. Consider a polymer formed by connecting N elliptical molecules into a one-dimensional chain. Each
molecule can align along either its long axis (of length 2a) or short axis (length a). The energy of the
monomer aligned along its shorter axis is higher by 𝜀, that is, the total energy is ℋ = 𝜀𝑈, where 𝑈 is
the number of monomers standing up.
(a) Calculate the partition function, 𝑍 (𝑇, 𝑁), of the polymer.
(b) Find the relative probabilities for a monomer to be aligned along its short or long axis.
(c) Calculate the average length, 〈𝐿(𝑇, 𝑁)〉, of the polymer.
(d) Obtain the variance, 〈𝐿(𝑇, 𝑁)2 〉𝑐 .
6. A surface with 𝑁0 adsorption centers has 𝑁 ≤ 𝑁0 gas molecules adsorbed on it. Show that the chemical
potential of the adsorbed molecules is given by 𝜇 = 𝑘B 𝑇 ln(𝑁/[(𝑁0 − 𝑁)𝑎(𝑇)]), where 𝑎(𝑇) is the
partition function of a single adsorbed molecule. Solve the problem by constructing the grand partition
function as well as the partition function of the system.
[Hint: Neglect the intermolecular interaction among the adsorbed molecules.]
7. Consider an ideal gas of noninteracting particles in the grand canonical ensemble. The macrostate is
given by 𝑀 ≡ (𝑇, 𝜇, 𝑉) and the corresponding microstates {𝑞⃗1 , 𝑝⃗1 , 𝑞⃗2 , 𝑝⃗2 , … } have indefinite number
of particles. Write down the grand partition function and grand potential. Then calculate 𝑃, 𝑁, and 𝜇
for this ideal gas.
8. Let us re-examine the generalized ideal gas introduced in the previous section, using statistical
mechanics rather than kinetic theory. Consider a gas of 𝑁 non-interacting atoms in a d-dimensional box
of “volume” 𝑉, with a kinetic energy ℋ = ∑𝑁 𝑠
𝑖=1 𝐴|𝑝⃗𝑖 | , where 𝑝⃗𝑖 is the momentum of the i-th particle.
(a) Calculate the classical partition function 𝑍(𝑁, 𝑇) at a temperature 𝑇. (You don’t have to keep track
of numerical constants in the integration.)
(b) Calculate the pressure and the internal energy of this gas. (Note how the usual equipartition theorem
is modified for non-quadratic degrees of freedom.)
(1) 𝑠 (2) 𝑠
(c) Now consider a diatomic gas of N molecules, each with energy ℋ𝑖 = 𝐴 (|𝑝⃗𝑖 | + |𝑝⃗𝑖 | ) +
(1) (2) 𝑡
𝐾 |𝑞⃗𝑖 − 𝑞⃗𝑖 | , where the superscripts refer to the two particles in the molecule. (Note that this
unrealistic potential allows the two atoms to occupy the same point.) Calculate the expectation value
𝑡
〈|𝑞⃗𝑖(1) − 𝑞⃗𝑖(2) | 〉, at temperature 𝑇.
(d) Calculate the heat capacity ratio 𝛾 = 𝐶𝑃 /𝐶𝑉 , for the above diatomic gas.
9. Consider rod-shaped molecules with moment of inertia I, and a dipole moment 𝜇. The contribution of
2
1 𝑝𝜙
the rotational degrees of freedom to the Hamiltonian is given by ℋrot = (𝑝𝜃2 + ) − 𝜇𝐸 cos 𝜃,
2𝐼 sin2 𝜃
where 𝐸 is an external electric field. 𝜙 ∈ [0, 2𝜋], 𝜃 ∈ [0, 𝜋] are the azimuthal and polar angles, and
𝑝𝜙 , 𝑝𝜃 are their conjugate momenta.
(a) Calculate the contribution of the rotational degrees of freedom of each dipole to the classical partition
function.
(b) Obtain the mean polarization 𝑃 = 〈𝜇 cos 𝜃〉 of each dipole.
𝜕𝑃
(c) Find the zero-field polarizability 𝜒 𝑇 = 𝜕𝐸 |𝐸=0
(d) Calculate the rotational energy per particle (at finite E), and comment on its high and low-
temperature limits.
(e) Sketch the rotational heat capacity per dipole.
10. Show that the Boltzmann entropy calculated using the condition of constant energy hypersurface and
using a small width ∆ about the hypersurface for a collection of noninteracting simple harmonic
oscillators are same for all practical purposes in the thermodynamic limit.
11. Consider that N one-dimensional, independent, (quantum) harmonic oscillators with the Hamiltonian,
1
ℋ = ∑𝑁 𝑖=1 ℏ𝜔 (𝑛𝑖 + ) (𝑛𝑖 ∈ 𝕎), are in thermodynamic equilibrium. (classical counting of states is
2
valid in this quantum system)
(a) Find out the entropy.
(b) Hence, making use of the microcanonical ensemble, find the heat capacity in terms of temperature,
and discuss its behavior for 𝑘B 𝑇 ≫ ℏ𝜔 and 𝑘B 𝑇 ≪ ℏ𝜔.
12. By letting two isolated systems exchange only volume (induced by, say, movable partition) to reach to
an equilibrium for the combined system, find using the Laplace’s method of evaluating relevant integral
that in the thermodynamic equilibrium pressures in both parts are same. Repeat the problem for a
hypothetical scenario where only number of particles are exchanged to show that at thermodynamic
equilibrium, the chemical potentials are same as well.
13. Note that one can write the grand canonical partition function, 𝑄, as ∑𝑁 𝓏 𝑁 𝑍(𝑁) where 𝓏 ≡
𝑒 𝛽𝜇 (called fugacity) and 𝑍(𝑁) is the canonical partition function with fixed N particles.
(a) Verify that for ideal gas, 𝑍 (𝑁) = (𝑍1 )𝑁 /𝑁!.
(b) Prove that for a grand canonical ensemble of ideal gas, the distribution of number of particles is
Poisson distribution.
14. Consider a collection of N magnetic moments (each of magnetic moment 𝜇0 ) which orients either
parallel or antiparallel to the applied external magnetic field B. The energy of a parallel configuration
is − 𝜇0 𝐵 and that of the antiparallel one is + 𝜇0 𝐵. Making use of the “constant magnetic field
ensemble", find the Gibbs free energy and thence the (zero field) magnetic susceptibility, 𝜒, when
𝑘B 𝑇 ≫ 𝜇0 𝐵.
15. Consider an ideal gas atmosphere in a uniform gravitational force. Naturally, there is a temperature
gradient but assume that each horizontal layer is in thermodynamic equilibrium.
(a) Find the chemical potential of the gas as a function of height z from the ground. Take acceleration
due to gravity as − 𝑔𝑧̂ .
(b) If there is no diffusion happening (i.e., the gravity balances the diffusion tendency due to the upward
density decrease), then using the result of part (a), find how 𝑛(𝑧)/𝑛(0) (𝑛 being number density) varies
with height. Assume temperature to be constant with height for the sake of analytical tractability of the
calculation.
(c) Using the solution to part (b), find at which height the pressure of the gas reduces to 1/e-th of its
value at the ground (z = 0)?
