Exciton-Exciton Annihilation Mediated by Many-Body Coulomb and Phonon Interactions: An Ab Initio Study

Abstract: Exciton-exciton annihilation (EEA), in which two excitons interact to generate high-energy excitations, is an important non-radiative channel in light-induced excited-state relaxation. When efficient, this process offers an alternative route to exciton emission, potentially allowing extended energetically excited particles' lifetime and coherence. These properties are significant in designing and understanding materials-based quantum devices, particularly for low-dimensional semiconductors. Here, we present a first-principles framework to compute EEA mechanisms and rates using many-body perturbation theory within the GW and Bethe-Salpeter Equation (GW-BSE) formalism. Our method explicitly accounts for Coulomb-driven and phonon-assisted exciton-exciton scattering by explicitly evaluating the interaction channels between the constituent electrons and holes composing the BSE excitons. We apply this framework to monolayer WSe$_2$ and explore the $A$, $B$ excitation manifolds, finding picosecond-scale annihilation between bright and dark states, cross valleys, and cross peak manifolds. These channels become allowed due to scattering into free electron-hole pairs across the Brillouin zone. Our results supply new insights into non-radiative exciton relaxation mechanisms in two-dimensional materials, providing a predictive and general tool for modeling these interactions in excitonic materials.