Thermal physics of the lead chalcogenides PbS, PbSe, and PbTe from first principles

The lead chalcogenides represent an important family of functional materials, in particular due to the benchmark high-temperature thermoelectric performance of PbTe. A number of recent investigations, experimental and theoretical, have aimed to gather insight into their unique lattice dynamics and electronic structure. However, the majority of first-principles modeling has been performed at fixed temperatures, and there has been no comprehensive and systematic computational study of the effect of temperature on the material properties. We report a comparative lattice-dynamics study of the temperature dependence of the properties of PbS, PbSe, and PbTe, focusing particularly on those relevant to thermoelectric performance, viz. phonon frequencies, lattice thermal conductivity, and electronic band structure. Calculations are performed within the quasiharmonic approximation, with the inclusion of phonon-phonon interactions from many-body perturbation theory, which are used to compute phonon lifetimes and predict the lattice thermal conductivity. The results are critically compared against experimental data and other calculations, and add insight to ongoing research on the PbX compounds in relation to the off-centering of Pb at high temperatures, which is shown to be related to phonon softening. The agreement with experiment suggests that this method could serve as a straightforward, powerful, and generally applicable means of investigating the temperature dependence of material properties from first principles.