Off-center Rattling Triggers High-Temperature Thermal Transport in Thermoelectric lathrates: Non-Perturbative Approach

TL;DR

This paper develops a non-perturbative theoretical model to explain the unusual high-temperature thermal transport behavior in off-center type-I clathrate thermoelectrics, matching experimental observations.

Contribution

It introduces a non-perturbative approach accounting for off-center rattling states, providing accurate predictions of thermal conductivity in off-center clathrates.

Findings

The theory matches observed thermal conductivities in off-center clathrates.

It explains the T-linear increase and saturation of thermal conductivity at high temperatures.

The model emphasizes the role of off-center rattling interactions with cage shells.

Abstract

Lattice thermal conductivities $\kappa_{\rm L}$ of type-I clathrates encapsulating "off-center" guest atoms behave in a way that is sharply different from those of conventional crystals such as on-center type-I clathrates. The latter decreases with increasing temperature according to 1/$T$ above a few tens\,K. While, $\kappa_{\rm L}$ of off-center clathrates increase T-linearly above a few tens K. Further increasing temperature above $T\gtrsim$100 K, $\kappa_{\rm L}$ saturates without exhibiting appreciable T-dependence. In this temperature regime, the standard formulation of $\kappa_{\rm L}$ based on the perturbation theory is unfeasible. We herein present a theory of $\kappa_{\rm L}$ based on "non-perturbative" approach by taking into account the interaction between non-vibrational off-center rattling states of guest atoms and cage shells. It is remarkable that our theory shows excellent agreement with observed $\kappa_{\rm L}(T)$ for off-center clathrates in magnitudes, the cage volume $\Omega$-dependence and T-dependence.