First-Principles Ultrafast Exciton Dynamics and Time-Domain Spectroscopies: Dark-Exciton Mediated Valley Depolarization in Monolayer WSe$_2$

TL;DR

This paper presents a first-principles method combining exciton-phonon interactions with an excitonic Boltzmann equation to simulate ultrafast exciton dynamics and spectroscopies, revealing dark excitons' role in monolayer WSe$_2$.

Contribution

It introduces a novel ab initio approach to model nonequilibrium exciton dynamics including electron-hole correlations in materials with strongly bound excitons.

Findings

Predicts sub-picosecond exciton relaxation times in WSe$_2$

Identifies the key role of dark excitons in valley depolarization

Enables quantitative simulation of ultrafast spectroscopies

Abstract

Calculations combining first-principles electron-phonon ($e$-ph) interactions with the Boltzmann equation enable studies of ultrafast carrier and phonon dynamics. However, in materials with weak Coulomb screening, electrons and holes form bound excitons and their scattering processes become correlated, posing additional challenges for modeling nonequilibrium physics. Here we show calculations of ultrafast exciton dynamics and related time-domain spectroscopies using $ab~initio$ exciton-phonon (ex-ph) interactions together with an excitonic Boltzmann equation. Starting from the nonequilibrium exciton populations, we develop simulations of time-domain absorption and photoemission spectra that take into account electron-hole correlations. We use this method to study monolayer WSe$_2$, where our calculations predict sub-picosecond timescales for exciton relaxation and valley depolarization and reveal the key role of intermediate dark excitons. The approach introduced in this work enables a quantitative description of nonequilibrium dynamics and ultrafast spectroscopies in materials with strongly bound excitons.