PH 304: Assignment 6 (Quantum Statistical Mechanics)

1. The Hamiltonian matrix for a quantum system can be written as

0 1 0

H = g
1 0 1 g>0
2

0 1 0

Compute the canonical partition function and the average energy as a function of the
temperature.
2. Hydrogen molecules can exist in ortho and para states. The two electrons of H2 in
para-hydrogen form a singlet (antisymmetric) state. The orbital angular momentum
can thus only take even values, i.e.
h
2
Hp =
l(l + 1)
2
where l = 0, 2, 4, .... Calculate the rotational partition function of para-hydrogen,
and evaluate its low and high temperature limits. Also calculate the low and hightemperature limits of the average internal energy (ignoring vibrational degree of freedom). (Hint: Remember there are 2l + 1 states for each l).
3. Consider the one dimensional quantum harmonic oscillator with mass m and frequency
in the canonical ensemble. The partition function is given by
Z(T ) =
where, n = (n +

1
)h
2

Z X

knT
B

n2 (x)dx

n=0

and n (x) are the eigenfunctions in the coordinate basis. The

probability density function P (x) is then

P (x) = A

knT
B

n2 (x)

n=0

where A is the normalization factor. Write doen the expression for

dP
.
dx

Now write the

position and momentum operators in terms of the creation and annihilation operators
and evaluate

dP
.
dx

Similarly, evaluate the term xP (x). Compute the ratios

1 dP
.
xP (x) dx

Integrate this equation to find the expression for the probability density P (x). The
probability density should be properly normalised. Verify that the answer matches
with the diagonal elements of the density matrix derived in class.