Calculations of dynamical properties of skutterudites: Thermal conductivity, thermal expansivity, and atomic mean-square displacement

While the thermal conductivity of the filled skutterudites has been of great interest it had not been calculated within a microscopic theory. Here a central force, Guggenheim-McGlashen, model with parameters largely extracted from first-principles calculations and from spectroscopic data, specific to LaFe4Sb12 or CoSb3, is employed in a Green-Kubo/molecular dynamics calculation of thermal conductivity as a function of temperature. We find that the thermal conductivity of a filled solid is more than a factor of two lower than that of an unfilled solid, assuming the framework interatomic force parameters are the same between filled and unfilled solids, and that this decrease is almost entirely due to the cubic anharmonic interaction between filling and framework atoms. In addition, partially as a test of our models, we calculate thermal expansivity and isotropic atomic mean-square displacements using both molecular dynamics and lattice dynamics methods. These quantities are in reasonable agreement with experiment, increasing our confidence in the anharmonic parameters of our models. We also find an anomalously large filling-atom mode Gruneisen parameter that is apparently observed for a filled skutterudite and is observed in a clathrate.