CHM 421/621 Assignment 4

November 10, 2019

Due on 15th Nov., 2019.

1. Consider a system of N non-interacting particles, each with 3 quantum

levels of energy 0,  and 2, respectively ( > 0). The particles are
kept in an adiabatically insulated container of volume V and with rigid
walls. If the total energy of the system upon containment is U , then

(a) Find the most probable distribution of particles among energy

levels and the corresponding entropy.
(b) For small variations around the most probable distribution show
that the entropy can be written as a Gaussian. Find the standard
deviation of the Gaussian and show that the for N → ∞ the
entropy distribution resembles a Dirac delta function.
(c) For very large N calculate the thermal equation of state of the
system.

2. Consider a system of N non-interacting and indistinguishable particles,

each with 2 quantum levels of energy 0 and , respectively ( > 0). The
particles are kept in a container of volume V and with rigid walls and
in contact with a thermal reservoir at temperature T .

(a) Determine the canonical partition function for the system.

(b) Determine the average internal energy of the system and the specfic
heat at constant volume.
(c) Determine the entropy and the Helmholtz free energy per particle
as a function of the temperature.

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3. For a gas of non-interacting classical atoms possessing magnetic dipoles
at temperature T show that the isothermal magnetic susceptipbility χT
is related to the variance of the distribution of magnetic moment per
particle µz as ∆2 µz = kB T χT . (See Lecture 28).

4. For an ideal gas of N molecules of volume V and at temperature T

(a) Derive an expression for the distribution of velocities of the molecules

as well as the probable number of molecules with velocities in the
range d3 v = dvx dvy dvz of ~v .
(b) Determine a distribution function for speeds of the molecules.
(c) Calculate the maximum, average and root mean square speeds of
the molecules.
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5. For a canonical ensemble show that S = − P (Ek ) ln P (Ek ).
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6. A system consisting of N distinguishable, non-interacting, 2-dimensional

quantum simple-harmonic oscillators is kept at a temperature T . If the
fundamental frequencies of the oscillators for displacements in the x
and y directions are ωx and ωy , respectively, determnine the partition
function, average energy, entropy and specific heat at constant volume
of the system.