Anharmonic phonon renormalization and thermal transport in the type-I Ba8Ga16Sn30 clathrate from first principles

Effects of strong phonon anharmonicity of a type-I clathrate Ba8Ga16Sn30 induced by the quadruple-well potential of guest atoms were investigated. Phonon transport including a coherent interbranch component was analyzed using a first-principles-based self-consistent phonon (SCP) theory that gives temperature-dependent harmonic interatomic force constants and by solving off-diagonal components of group velocity operator. Experimentally observed thermal conductivities have been reasonably reproduced by considering both lattice and electron contributions. Through the analysis with the SCP theory, we found that hardening of guest modes leads to an increase in lattice thermal conductivity at frequencies below those of framework-dominant flat modes (<40 cm(-1)), which finally results in the slow decay of the total lattice thermal conductivity with increasing temperature. Detailed analyses revealed that the increase in lattice thermal conductivity at low frequency is attributed to (a) the increase in both group velocities and lifetimes of phonon modes located at frequencies below that of the flat guest modes and (b) abnormal increase in lifetimes of phonon modes located between frequencies of the flat guest and framework modes with increasing temperature.

Automated summary

The effects of strong phonon anharmonicity induced by the quadruple-well potential of guest atoms in type-I clathrate Ba8Ga16Sn30 were investigated. A first-principles-based self-consistent phonon (SCP) theory was used to analyze the phonon transport, including a coherent interbranch component. The experimental thermal conductivities were reasonably reproduced by considering both lattice and electron contributions. The analysis with the SCP theory showed that the hardening of guest modes resulted in an increase in lattice thermal conductivity at frequencies below those of the framework-dominant flat modes, leading to a slow decay of the total lattice thermal conductivity with increasing temperature. Detailed analysis revealed that the increase in low-frequency lattice thermal conductivity was attributed to the increase in group velocities and lifetimes of phonon modes below the flat guest modes, as well as the abnormal increase in lifetimes of phonon modes between the frequencies of the flat guest and framework modes with increasing temperature.