 Solution

For a dilute linear diatomic gas with fixed molecular number, translation contributes molar $C_V=3R/2$. Rotational levels are $E_J={\hslash }^{2}J(J+1)/(2I)$ with degeneracy $2J+1$:At $T\ll {\theta }_r$ rotational excitation is frozen out; at $T\gg {\theta }_r$ the partition function is proportional to $T$, giving $U_{\mathrm{rot}}=N{k}_{B}T$ and $C_{V,\mathrm{rot}}=N{k}_B$. Nuclear-spin populations and molecular symmetry modify detailed low-temperature behaviour. The high-temperature result corresponds to two quadratic rotational degrees of freedom; a nonlinear molecule has three and contributes $3N{k}_B/2$.

For each independent harmonic vibration, write $x=\hslash \omega /(k_{B}T)$. Its energy and heat capacity areThe contribution is exponentially small at low temperature and approaches $N{k}_B$ per mode at high temperature. zero-point energy does not contribute to $dU/dT$. Typically rotations activate before bond stretching, producing diatomic plateaus $C_V/R=3/2,5/2,7/2$ as temperature increases within the molecular regime; ideal-gas $C_P=C_V+R$. Dissociation, electronic excitation and nonideal interactions eventually invalidate this simple sequence. Polyatomic gases sum over their distinct vibrational frequencies; no single activation temperature describes all modes.