Impact of noble-gas filler atoms on the lattice thermal conductivity of CoSb3 skutterudites: first-principles modelling.

We present a systematic first-principles modelling study of the structural dynamics and thermal transport in the CoSb3 skutterudites with a series of noble-gas filler atoms. Filling with chemically-inert atoms provides an idealised model for isolating the effects of the fillers from the impact of redox changes to the host electronic structure. A range of analysis techniques are proposed to estimate the filler rattling frequencies, to quantify the separate impacts of the filler on the phonon group velocities and lifetimes, and to show how changes to the phonon spectra and interaction strengths lead to suppressed lifetimes. The noble-gas fillers are found to reduce the thermal conductivity of the CoSb3 framework by up to 15 % primarily by suppressing the group velocities of low-lying optic modes. The filler rattling frequencies are determined by a detailed balance of increasing atomic mass and stronger interactions with the framework, and are found to be a good predictor of the impact on the heat transport. Lowering the rattling frequency below ~1.5 THz by selecting heavy fillers that interact weakly with the framework is predicted to lead to a much larger suppression of the thermal transport, by inducing avoided crossings in the acoustic-mode dispersion and facilitating enhanced scattering and a consequent large reduction in phonon lifetimes. Approximate rattling frequencies determined from the harmonic force constants may therefore provide a useful metric for selecting filler atoms to optimise the thermal transport in skutterudites and other cage compounds such as clathrates.