With microstate energies held fixed when differentiating,Since ,The canonical ensemble fixes volume and particle number, and any other external Hamiltonian parameters. Thus the derivative is ; pressure-fixed fluctuations would naturally involve enthalpy in a different ensemble.
The translational and two-level energy variance follows because translation and internal states factorize for this dilute classical gas:Differentiating twice yieldsThe terms are independent translational and two-level binomial variances. At , excitation freezes out exponentially and translation dominates. At , the internal variance tends to while the translational variance grows as ; the internal heat capacity consequently tends to zero. Fractional total-energy fluctuations are of order for large . The low-temperature statement presumes translation is still nondegenerate; at strictly zero temperature the classical-gas model fails.