Solution

ID: past-exam-of-the-thermal-and-statistical-physics-course-of-the-university-of-cambridge/2018/section-b/b3/solution

Classical translational statistics. Write the number density as and the thermal de Broglie wavelength as . Quantum exchange is negligible when wave packets rarely overlap:
The equivalent state-counting statement is that the mean occupation of each thermally relevant one-particle state is much smaller than one. The equations in this question count one internal species; with equally populated spin states the relevant density per species is .
Let be the dimensionless quantum gas fugacity, with the lowest one-particle energy chosen as zero. Both quantum distributions can be written
If , then for all , recovering Maxwell–Boltzmann statistics. Conversely, low occupation even at the spectrum's bottom requires for bosons or for fermions; either condition implies
A single high-energy state can be sparsely occupied even in a degenerate gas, so the condition must hold across the relevant spectrum, not just for one arbitrarily chosen energy. Also, classical translational statistics does not imply that all internal excitation energies or other quantum effects can be ignored.
Grand partition function, density and pressure. Noninteracting particles have independent occupations of each one-particle state. Put . Summing the allowed occupations gives
Therefore
The grand potential is for this homogeneous gas. Replacing the sum by and using gives
The mean number is , giving
For bosons, the grand sum requires when the ground energy is zero. A macroscopic condensate at the limiting must be separated from the continuum integral in the condensed phase. The following small- calculation is in the normal, nondegenerate regime, so that complication does not enter.
Density expansion and inversion. Expand the occupation as a geometric series:
The Gaussian wavevector integral for its th term is
It follows that
For the inverse series, put and try . Substitution gives , hence
The leading equality directly connects the density and occupancy criteria for classical behavior.
Pressure and its first quantum correction. Expanding the logarithm in the pressure expression gives one extra factor compared with the density series:
Insert the inverse series. To second order in ,
Thus
The first quantum correction at fixed density and temperature is
It is negative for bosons and positive for fermions, and vanishes in the classical density limit.
Virial coefficient. Define the number-density virial expansion by
The coefficient has units in this convention. Comparing terms gives
This is the exchange contribution to the second virial coefficient. It arises without a pair-interaction potential; the underlying gas is noninteracting. A molar-density convention would multiply this by the Avogadro constant. For equally populated internal species, exchange occurs within each species and the coefficient in terms of total density is smaller by a factor .
Why the two signs differ. Bosonic exchange symmetry enhances the probability of nearby identical bosons, whereas fermionic exchange symmetry suppresses nearby identical fermions in the same internal state. In the dilute regime, the normalized equal-time pair detection correlation is
The exchange part follows by squaring the Gaussian one-particle coherence factor . At zero separation this gives for bosons and for one-component fermions. Integrating the exchange pair weight provides a direct coefficient check:
Bunching therefore acts like an effective statistical attraction in the dilute equation of state, lowering the pressure needed at fixed density. Exclusion acts like an effective statistical repulsion, raising it. Neither description asserts an actual interparticle force. Different internal fermion species do not exclude each other from a common spatial location in the same way, explaining the importance of the species convention.

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