Surface hopping simulations show valley depolarization driven by exciton-phonon resonance

Abstract: Monolayer MoS$_2$ has long served as a prototypical material exhibiting valleytronic behavior, yet it remains unclear exactly how phonons induce a valley depolarization of its excitonic states. Here, we apply a mixed quantum--classical simulation framework to study the phonon-induced mechanisms affecting valley polarization at short times. Our framework combines reciprocal-space surface hopping with microscopic models of the quasiparticle band structure as well as the electron-hole and carrier-phonon interactions, parametrized against ab initio calculations, while retaining explicit information on transient phonon occupancies. By means of such occupancies, our simulations show a resonance between the lowest exciton band and the dominant optical phonon branch to largely drive valley depolarization, by activating a Maialle-Silva-Sham mechanism. Resulting valley polarization times are consistent with experimental measurements across temperatures.