Quartic Anharmonicity of Rattlers and Its Effect on Lattice Thermal Conductivity of Clathrates from First Principles

Abstract

We investigate the role of the quartic anharmonicity in the lattice dynamics and thermal transport of the type-I clathrate Ba_8Ga_16Ge_30 based on ab initio self-consistent phonon calculations. We show that the strong quartic anharmonicity of rattling guest atoms causes the hardening of vibrational frequencies of low-lying optical modes and thereby affects calculated lattice thermal conductivities $ąppa$_L significantly, resulting in an improved agreement with experimental results including the deviation from $p̨pa$_L∝T^-1 at high temperature. Moreover, our static simulations with various different cell volumes shows a transition from crystal-like to glasslike $kp̨a$_L around 20 K. Our analyses suggest that the resonance dip of $kaą$_L observed in clathrates with large guest free spaces is attributed mainly to the strong three-phonon scattering of acoustic modes along with the presence of higher-frequency dispersive optical modes.

Terumasa Tadano

Researcher of Materials Science

My research interests include development of computational methods and softwares for predicting thermal properties of solids, and application of machine-learning methods to material science study