Debye heat capacity ($C_V=9N{k}_B(T/{\Theta }_D{)}^3{\int }_0^{{\Theta }_D/T}{x}^4{e}^x/(e^x-1{)}^{2}dx$)

The three-dimensional Debye model normalizes its phonon density of states to $3N$ modes: $g(\omega )=9N{\omega }^2/{\omega }_D^3$ below the Debye frequency ${\omega }_D$. The thermal energy is $U={\int }_0^{{\omega }_D}g(\omega )\hslash \omega /[e^{\hslash \omega /(k_{B}T)}-1]d\omega$. Differentiate at fixed volume and substitute $x=\hslash \omega /(k_{B}T)$ to obtain the displayed heat capacity at constant volume.

At $T\ll {\Theta }_D$, integration by parts gives ${\int }_0^{\infty }{x}^4{e}^x/(e^x-1{)}^{2}dx=4{\int }_0^{\infty }{x}^3/(e^x-1)dx=4{\pi }^4/15$. Therefore $C_V\sim (12{\pi }^4/5)N{k}_B(T/{\Theta }_D{)}^3$. At $T\gg {\Theta }_D$, each mode approaches the equipartition theorem value $k_B$ of heat capacity, so $C_V\to 3N{k}_B$, the Dulong-Petit law. Fixed harmonic zero-point energy does not contribute to either limit.

A neutral two-dimensional linear electronic spectrum has heat capacity proportional to $A{T}^2$, while three-dimensional acoustic phonons have Debye heat capacity proportional to $N{T}^3/{\Theta }_D^3$. Thus their ratio scales as $A{k}_B^2{\Theta }_D^3/({\hslash }^2{v}^{2}NT)$. At fixed crystal composition and shape, $A/N\propto 1/L$ for linear size $L$, favoring the electronic surface contribution in smaller or colder specimens. The continuum laws require thermally populated wavelengths small compared with sample size; their formal low-temperature crossover need not lie inside that regime.