Anharmonic lattice dynamics and thermal transport in type-I inorganic clathrates

The anharmonic phonon properties of type-I filled inorganic clathrates Ba₈Ga₁₆Ge₃₀and Sr₈Ga₁₆Ge₃₀are obtained from the first-principles calculations by considering the temperature-dependent sampling of the potential energy surface and quartic phonon renormalization. Owing to the weak binding of guest atoms with the host lattice, the obtained guest modes undergo strong renormalization with temperature and become stiffer by up to 50% at room temperature in Sr₈Ga₁₆Ge₃₀. The calculated phonon frequencies and associated thermal mean squared displacements are comparable with experiments despite the on-centering of guest atoms at cage centers in both clathrates. Lattice thermal conductivities are obtained in the temperature range of 50-300 K accounting for three-phonon scattering processes and multi-channel thermal transport. The contribution of coherent transport channel is significant at room temperature (13% and 22% in Ba₈Ga₁₆Ge₃₀and Sr₈Ga₁₆Ge₃₀) but is insufficient to explain the experimentally observed glass-like thermal transport in Sr₈Ga₁₆Ge₃₀.