Ab initio time-dependent GW approach for nonequilibrium exciton-phonon coupled dynamics across momentum space

Abstract

The dynamics of optical excitations in materials generally involves intertwined electron-hole (e-h) and electron-phonon (e-ph) interactions out of equilibrium. However, a full theoretical description of such nonequilibrium dynamics requires a systematic treatment of the coherent excitonic excitations and exciton-phonon interactions across the entire crystal momentum space in real time, which remains a major challenge and out of reach for first-principles approaches. Here, we present a new ab initio time-dependent adiabatic GW methodology that incorporates full finite-momentum e-h and e-ph couplings, enabling real-time simulations of the coherently coupled exciton-phonon dynamics. The excitonic excitations are naturally described by the equation of motion of the interacting single-particle density matrix, whereas their couplings to phonons are formulated within a linear-response framework, hence the simulations can be efficiently carried out within a primitive unit cell. We demonstrate the capabilities of this new approach by investigating the direct-to-indirect exciton transitions in monolayer WSe2 in a pump-probe setup of time-resolved and angle-resolved photoemission spectroscopy. Our results reveal that the phonon-mediated ultrafast intervalley dynamics of excitons of this system is within ~0.5 ps, manifested as in-gap photoemission intensity transfer from the K-valley to the Q-valley. This work establishes a comprehensive and practical nonequilibrium Green's function framework for accurately simulating nonequilibrium and coherent excitations involving coupled excitons and phonons from first principles.