Nonequilibrium Photocarrier and Phonon Dynamics from First Principles: a Unified Treatment of Carrier-Carrier, Carrier-Phonon, and Phonon-Phonon Scattering

Abstract

We develop a first-principles many-body framework to describe the dynamics of photocarriers and phonons in semiconductors following ultrafast excitation. Our approach incorporates explicit ab initio light-matter coupling and first-principles collision integrals for carrier-carrier, carrier-phonon, and phonon-phonon scattering. It also yields time-dependent quasiparticle and phonon frequency renormalizations, along with light-induced coherent atomic motion. The equations of motion are solved in a maximally localized Wannier basis, ensuring gauge-consistent scattering integrals and ultradense momentum sampling, thereby enabling direct comparison with pump-probe experiments. The method can be coupled to constrained density-functional theory to access light-induced structural phase transitions at longer times after the light pulse. We showcase the capabilities and predictive power of this framework on MoS$_2$ and h-BN monolayers. For MoS$_2$, we resolve photoinduced renormalizations of electronic and lattice properties, ultrafast carrier relaxation, hot-phonon dynamics, and displacive coherent atomic motion. Including carrier-carrier scattering is crucial to obtain realistic photocarrier equilibration times, while omitting phonon-phonon scattering leads to incorrect long-time lattice thermalization and a factor of two larger A$_{1g}$ coherent phonon damping time. For h-BN, we quantify photoinduced changes in the electronic, optical, and lattice responses in quasi-equilibrium, demonstrating a fluence-dependent enhancement of screening and melting of excitonic features.