Maximum-entropy derivation of equilibrium ensembles Created 2026-09-24 Updated 2026-09-24
Maximizing the Gibbs entropy under normalization alone gives a uniform distribution. Adding a fixed mean-energy constraint gives the Boltzmann distribution .
Here is the probability of microstate , including all occupation data. In the grand canonical ensemble, with energy , particle number , chemical potential and ,
Substitution in the Gibbs entropy gives , where and . Differentiating at fixed gives . Therefore
The chemical potential is the change in internal energy when one particle is added at fixed entropy and volume:
Equivalently, for the Helmholtz free energy.
Let a microstate have energy and particle number . Maximizing the Gibbs entropy subject to normalization and fixed mean values of and is the maximum-entropy derivation of equilibrium ensembles. With Lagrange multipliers , , and , vary
The stationarity equation is . Normalization therefore gives the grand canonical ensemble
Here is the grand canonical partition function and is the Boltzmann constant.
For one fermionic quantum state of energy , the Pauli exclusion principle permits occupation numbers only . Its two grand-canonical weights are and , so its mean occupation is the Fermi-Dirac distribution
For a free nonrelativistic particle, . In a region of area , the number of wave-vector states in the annulus from to , including the two spin angular momentum states, is
Since , the two-dimensional free-electron density of states is constant:
We now use units in which , as in the question. At zero temperature, the Fermi-Dirac distribution is a step function, and hence
At positive temperature the same fixed particle number satisfies the exact relation
Thus
This is the low-temperature particle-number cancellation for constant density of states. Therefore, for , the mean number of particles in the energy interval is
Finally, compare the internal energy with its zero-temperature value. The thermally excited particles above and holes below have equal leading particle numbers, so their terms proportional to cancel. With ,
where the integral follows from the fermion-to-boson thermal integral ratio. Differentiation gives the linear low-temperature heat capacity of a two-dimensional Fermi gas:
The requested power law is therefore linear in , with exponent one.
For the Gibbs entropy
first maximize subject only to over accessible microstates. A Lagrange multiplier gives
so every is equal. Normalization yields the microcanonical ensemble
For the canonical ensemble, impose both normalization and the mean-energy constraint . Stationarity of
gives . The canonical partition function fixes , so
Thermodynamic consistency identifies . This is the maximum-entropy derivation of equilibrium ensembles.
Substitution of the canonical probabilities into the Gibbs entropy gives
Hence