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

TL;DR

This study uses first-principles calculations to analyze anharmonic phonon behavior and thermal transport in type-I inorganic clathrates, revealing temperature-dependent phonon renormalization and partial coherence in thermal conductivity.

Contribution

It provides detailed insights into anharmonic lattice dynamics and thermal transport mechanisms in inorganic clathrates, highlighting the role of guest-host interactions and coherent transport channels.

Findings

Guest modes undergo strong temperature-dependent renormalization.

Calculated thermal conductivities match experimental data.

Coherent transport contributes significantly but does not fully explain glass-like behavior.

Abstract

The anharmonic phonon properties of type-I filled inorganic clathrates Ba8 Ga16 Ge30 and Sr8 Ga16 Ge30 are 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 Ba8Ga16Ge30 and Sr8Ga16Ge30) but is insufficient to explain the experimentally observed glass-like thermal transport in Sr8Ga16Ge30.