Ultrafast Nonadiabatic Phonon Renormalization in Photoexcited Single-Layer MoS₂

Abstract

Comprehending nonequilibrium electron−phonon dynamics at the microscopic level and at short time scales is one of the main goals in condensed matter physics. Effective temperature models and time-dependent Boltzmann equations are standard techniques for exploring and understanding the nonequilibrium state and the corresponding scattering channels. However, these methods consider only the time evolution of the carrier occupation function, while the self-consistent phonon dressing in each time instant coming from the nonequilibrium population is ignored, which makes them less suitable for studying ultrafast phenomena where softening of the phonon modes plays an active role. Here, we combine ab initio timedependent Boltzmann equations and many-body phonon self-energy calculations to investigate the full momentum-and mode-resolved nonadiabatic phonon renormalization picture in the MoS 2 monolayer under nonequilibrium conditions. Our results show that the nonequilibrium state of photoexcited MoS 2 is governed by the multi-valley topology of valence and conduction bands that brings about characteristic anisotropic electron−phonon thermalization paths and the corresponding phonon renormalization of strongly coupled modes around high-symmetry points of the Brillouin zone. As the carrier population is thermalized toward its equilibrium state, we track in time the evolution of the remarkable phonon anomalies induced by nonequilibrium and the overall enhancement of the phonon relaxation rates. This work shows potential guidelines to tailor the electron−phonon relaxation channels and control the phonon dynamics under extreme photoexcited conditions.

Hot Electrons in Catalysis

“…The latter can affect the electron relaxation dynamics for picoseconds after the laser pulse has ended. Girotto, Caruso, and Novko also go beyond the picture of thermalized hot electrons in their study of ultrafast light-driven phonon dynamics in MoS 2 monolayers. By coupling time-dependent electron and phonon populations from ab initio time-dependent Boltzmann equation simulations with many-body phonon self-energy calculations, they study the ultrafast changes in frequencies and lifetimes of individual phonon modes.…”