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A germanium cage compound with barium and sodium guests. Its low-temperature heat capacity supplies an example of a rattling mode in addition to the leading electronic and acoustic contributions.^[ref]

Only states within an energy window of order $k_{B}T$ around the Fermi energy can change occupation in a degenerate metal. A Sommerfeld expansion gives electronic energy above its zero-temperature value proportional to $g(E_F)(k_{B}T{)}^2$, hence $C_e=\gamma T$. Three-dimensional linear-dispersion acoustic phonons have density of states proportional to ${\omega }^2$; integrating their Bose occupations gives thermal energy proportional to $T^4$ and the Debye heat capacity $C_{mph}=\beta T^3$. Thus $C/T=\gamma +\beta T^2$ at sufficiently low temperature in the normal state.

Reading the straight low-temperature fit gives approximately $\gamma \simeq 33\mathrm{mJ}\mathrm{mo}{\mathrm{l}}^{-1}{\mathrm{K}}^{-2}$ and $\beta \simeq 3.8\mathrm{mJ}\mathrm{mo}{\mathrm{l}}^{-1}{\mathrm{K}}^{-4}$. These estimates agree with the reported fit to this material in the original experiment.^[ref] Treating the graph values as approximate, the molar density of states isThe stipulated two electrons per formula unit give $n=2N_A/V_m\simeq 2.62\times 10^{27}{\mathrm{m}}^{-3}$. For a single spin-degenerate parabolic band, the molar density of states is $g(E_F)=3(2N_A)/(2E_F)=3N_A/E_F$. HenceThese are model-dependent effective parameters inferred from the measured heat capacity and assumed carrier count, rather than an independent determination of a unique band structure.

Using the Debye prefactor stated in the question givesThis prefactor counts three effective modes per formula unit. Consistently choosing the same count for the Debye wavevector gives $k_D=(6{\pi }^2{N}_A/V_m{)}^{1/3}\simeq 4.3\times 10^9{\mathrm{m}}^{-1}$. The corresponding average sound speed isThere is a normalization choice here: a formula unit has 31 atoms. With the conventional full atomic-mode count, the molar Debye coefficient contains an additional factor 31, and both ${\Theta }_D$ and $k_D$ increase by $31^{1/3}$. That convention gives ${\Theta }_D\simeq 251\mathrm{K}$ and $k_D\simeq 1.34\times 10^{10}{\mathrm{m}}^{-1}$, while leaving the inferred sound speed unchanged. The mode count in the Debye model must be used consistently; mixing the printed temperature with an atomic-count wavevector gives an erroneous sound speed.

The upward curvature above about $3\mathrm{K}$ indicates low-energy vibrations missing from a pure acoustic $T^3$ model. In this cage compound, the original analysis fits an additional localized mode with $\hslash \Omega /k_B\simeq 32\mathrm{K}$, assigned to a rattling mode of a barium guest atom.^[ref] At temperatures high compared with all relevant phonon energies, the full lattice approaches the Dulong-Petit law, $C_{mlattice}\to 3(31)R=93R\simeq 773\mathrm{J}\mathrm{mo}{\mathrm{l}}^{-1}{\mathrm{K}}^{-1}$. The reduced three-mode model alone approaches $3R$ and omits the other branches. An approximately linear electronic term can still be added while the carriers remain degenerate, but cannot be extrapolated beyond their Fermi temperature.

A rattling mode is a relatively soft, often localized vibration of a guest atom within a more rigid surrounding cage. An approximately harmonic narrow-frequency contribution can be modeled as an Einstein solid term with frequency $\Omega$ and degeneracy $g$, giving the heat capacity in the title. It freezes out exponentially at low temperature and approaches $gR$ per mole at high temperature, so it can bend a plot of $C/T$ versus $T^2$ away from its pure electronic-plus-acoustic straight line.

Calorimetry of Ba4Na2Ge25 shows an additional low-energy contribution fitted by an Einstein energy $\hslash \Omega /k_B\simeq 32\mathrm{K}$, assigned to a barium guest site.^[ref] This is a measured-material example; the narrow-mode description remains an approximation to a crystal's full vibrational spectrum.