Anharmonic phonon behavior via irreducible derivatives: Self-consistent perturbation theory and molecular dynamics

E Xiao and CA Marianetti, PHYSICAL REVIEW B, 107, 094303 (2023).

DOI: 10.1103/PhysRevB.107.094303

Cubic phonon interactions are now regularly computed from first principles, and the quartic interactions have begun to receive more attention. Given this realistic anharmonic vibrational Hamiltonian, the classical phonon Green's function can be precisely measured using molecular dynamics, which can then be used to rigorously assess the range of validity for self-consistent diagrammatic approaches in the classical limit. Here we use the bundled irreducible derivative approach to efficiently and precisely compute the cubic and quartic phonon interactions of CaF2, systematically obtaining the vibrational Hamiltonian purely in terms of irreducible derivatives. We demonstrate that the 4-phonon sunset diagram has an important contribution to the optical phonon linewidths beyond T = 500 K. Reasonable results are obtained even at T = 900 K when performing selfconsistency using the 4-phonon loop diagram and evaluating the 3-phonon bubble and 4-phonon sunset diagrams post-self-consistency. Further improvements are obtained by performing quasiparticle perturbation theory, where both the 4-phonon loop and the real part of the 3-phonon bubble are employed during self- consistency. Our irreducible derivative approach to self-consistent perturbation theory is a robust tool for studying anharmonic phonons in both the quantum and classical regimes.

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