Advanced Thermodynamics and Molecular Simulation (22/23)

Homework Set 1
to be handed in by Moodle individually by 3/10/221

1. Read Exercise 1.2 from the book by Widom for the energy distribution
Q(E) and reproduce the plot given as a function of δE/Ē. Plot also values
of dE / E = 1/50 and 1/100 (use a suitable plotting program).

2. The probability of observing a closed, thermally equilibrated system with

a given energy E is Q( E ) µ W ( E ) exp(- E / kT ) = exp[ln W ( E ) - E / kT ]. Both
ln W ( E ) and E / kT are of the order of magnitude of the number of
particles in the system, N, which suggests that Q(E ) is a very narrow
distribution centred on the most probable value of E. Verify this
suggestion by performing a steepest descent calculation with Q(E ) , that
is, expand ln Q( E ) in powers of dE = E - E and truncate the expansion
after the quadratic term. The term E is the average value of E, which
usually corresponds to the most likely or thermodynamic value (U). Use
this expansion to estimate for 0.001 moles of an ideal monatomic gas the
probability of observing a spontaneous fluctuation in E of the size
of dE = 10 -6 E .

Data: Boltzmann’s constant, k=1.38x10-23J/K

3 3
For ideal monoatomic gases Cv = Nk and E = NkT
2 2

1
This exercise forms part of the continuous evaluation and each student is responsible for
handing in their individual contribution which should not be a copy of other people’s work.