1 Homework Set 2: PH321, EQUILIBRIUM STATISTICAL MECHANICS, SPRING 2012 Instructor: Arindam Kundagrami TOTAL MARKS: 5, DUE: Thursday,

April 05, 2012 (In class).

I REPEAT ONCE MORE THAT SOLVING SINCERELY (AND ON YOUR OWN) THE HOMEWORK PROBLEMS WILL COMPLETELY PREPARE YOU FOR THE EXAMS. DISCUSS BUT DO NOT COPY. PROVIDE ALL DETAILS OF YOUR CALCULATION (DO NOT JUMP STEPS). ONE MARK WILL BE DEDUCTED FOR EACH DAY OF DELAY AFTER DUE DATE.

1. a) Calculate the grand partition function as a function of T, , V for the classical ideal gas. Writing the single particle partion function Q1 (V, T ) as V f (T ), show that the ideal gas law holds for the classical gas. b) Calculate the grand partition function for a set of simple harmonic oscillators. Find the average values for particle number N , energy E, Helmholtz free energy F , and entropy S for the system. Show that these values (E, F, S) match with those you had gotten from the canonical ensemble (for the single particle partition function you may choose either the classical or the quantum expression). c) Suppose there is a at surface of a solid in contact with its vapour. The vapour atoms stick to the solid surface at most one atom per site. Energy per site on the solid is if a vapour molecule is stuck to it, is 0 otherwise. If there are M available lattice sites, calculate the grand partition function of the system as a function of M, , and T . Then determine the chemical potential of the vapour-solid equilibrium as function of the number of adsorbed molecules (N ), T , and the total number of lattice sites (M ). [1.5 marks]

2. Consider the the ideal gas in quantum-mechanical ensembles. Unlike for the classical gas, all the calculations for this gas start with the assumption that the gas molecules are 1) indistinguishable and 2) of two types - bosons and fermions.

2 a) Reproduce (done in class) the expression for P V for both types of particles in a microcanonical ensemble (write all steps including those which are omitted in the notes/book). b) Reproduce the grand potential (A = P V ) for both types of particles in a grandcanonical ensemble, and hence nd average N, E, and the mean occupation number ni (i ) . c) Find the entropy for both types as a function of ni (i ), and show that these results are consistent with the general formula: S = kB
i [ n

pi (n) ln pi (n)], where pi (n) is the

probability that there are n particles in the energy state i . d) Now consider one more type of particles called mohions. If the occupation number ni (i ) of an energy level i for mohions is restricted to the values 0, 1, ..., k (0 and 1 for fermions, in comparison), then show that the mean occupation number of that level is given by ni (i ) = 1 e(i ) 1 k+1 (e(i ) )k+1 1 .

Check k = 1, k = lead to fermionic and bosonic results respectively. [1.5 marks]

3. Consider the ideal Bose gas (non-relativistic, 3 dimensions) in the grand canonical ensemble. Always start from the expressions for P = P (, V, T ) and N = N (, V, T ) in a grand canonical ensemble. a) Find an expression (as function of P, V, N, T, z) for the equation of state for all values of T > Tc , where Tc is the condensation temperature. What happens when n3 0? b) Prove that E = (3/2)P V holds good for this non-relativistic gas. c) Find an expression for Tc as function of the mass and density of the gas molecules. d) Show that the pressure in the mixed (T < Tc ) phase does not depend on volume. e) Which value of n3 corresponds to Tc ? f) Write = (N, V, T ) for T Tc . g) Show that Cv 1.925N kB at T = Tc . Further show that Cv vanishes near absolute zero. h) For the reversible adiabatic process, S and N remain xed. From this show that P V 5/3 =const. just like a classical ideal gas. i) Show that in the mixed phase the entropy is extensive only in Ne , where Ne is the num-

3 ber of molecules in the excited single-particle states. This is why the condensed molecules in the ground-state are called entropy-less. [2 marks]