Phonon Quasiparticles and Anharmonic Free Energy in Complex Systems

Abstract

We use a hybrid strategy to obtain anharmonic frequency shifts and lifetimes of phonon quasiparticles from first principles molecular dynamics simulations in modest size supercells. This approach is effective irrespective of crystal structure complexity and facilitates calculation of full anharmonic phonon dispersions, as long as phonon quasiparticles are well defined. We validate this approach to obtain anharmonic effects with calculations in MgSiO3 perovskite, the major Earth forming mineral phase. First, we reproduce irregular thermal frequency shifts of well characterized Raman modes. Second, we combine the phonon gas model (PGM) with quasiparticle frequencies and reproduce free energies obtained using thermodynamic integration. Combining thoroughly sampled quasiparticle dispersions with the PGM we then obtain first-principles anharmonic free energy in the thermodynamic limit (N→∞).