Past exam of the thermal and statistical physics course of the University of Cambridge / 2019 / Section A

Use the Gibbs-Duhem equation for a homogeneous, extensive, single-component thermodynamic phase:At fixed temperature, this becomes $dp=nd\mu$, with number density $n=N/V$. Separately, at fixed particle number,The chain rule along the same isothermal process in the equation of state now givesConsequentlyThis is isothermal compressibility from chemical-potential response. Since chemical potential has units of energy per particle, the right-hand side has units of volume per energy, or $\mathrm{P}{\mathrm{a}}^{-1}$, as required. The derivation assumes a smooth bulk equation of state; changing the fractions of coexisting thermodynamic phases at fixed pressure needs separate treatment.

Measure single-particle energy from the lowest state and write ${\epsilon }_k=c{k}^{\alpha }$, with $c>0$. In a homogeneous system, the number of wavevector states in a thin spherical shell is proportional to $k^{d-1}dk$. Changing variables from $k$ to $\epsilon$ gives the density of states per unit spatial volume,where $S_{d-1}$ is the area of the unit sphere in $d$ dimensions; an additional internal state degeneracy would multiply this expression by a constant.

The Bose-Einstein distribution has $\mu \le 0$. At saturation, $\mu \to 0^{-}$, the maximum excited-state number density isOnly the lower endpoint can cause divergence. There the integrand is proportional toThe improper integral converges precisely when its power exceeds $-1$. ThusWhen $d=\alpha$, the divergence is logarithmic; when $d<\alpha$, it is a power divergence. In either case the excited states can accommodate any fixed finite density at every positive temperature, so there is no bulk Bose-Einstein condensation at nonzero temperature.

For completeness, putting $s=d/\alpha >1$ and using the Gamma function and Riemann zeta function givesAt fixed density $n$, the right-hand side reaches $n$ at $T_c$; below it the excess particles occupy the lowest state, with condensate fraction $1-(T/T_c{)}^s$. This is Bose condensation with power-law dispersion in the homogeneous thermodynamic limit. A finite vessel or a trapping potential changes the low-energy state count and must not be silently substituted for that setting.

Use the classical dilute-gas conventionso the second virial coefficient has units of volume. The Mayer f-function formula for an isotropic pair potential isOnly separations smaller than $a$ contribute. Define $x=\beta \epsilon >0$ and substitute $t=r^3/a^3$, so $r^{2}dr=(a^3/3)dt$:This is the second virial coefficient of a bounded cubic repulsion. For every finite positive $T$, $1-e^{-x}<x$, so $B_2(T)>0$. There is no finite positive Boyle temperature. At high temperature, expanding the exponential givesThus the intended limiting statement isAt the other extreme the classical expression tends to $2\pi a^3/3$, the hard-exclusion value for separation $a$. This is a check on the integral, not a claim that a real molecular gas stays classical at arbitrarily low temperature. A molar virial expansion would instead use $B_{2,\mathrm{m}}=N_A{B}_2$.