Collective rovibronic dynamics of a diatomic gas coupled by cavity

Abstract

We consider an ensemble of homonuclear diatomic molecules coupled to the two polarization directions of a Fabry-Pérot cavity via fully quantum simulations. Accompanied by analytical results, we identify a coupling mechanism mediated simultaneously by the two perpendicular polarizations, and inducing polaritonic relaxation towards molecular rotations. This mechanism is related to the concept of light-induced conical intersections (LICIs). However, unlike LICIs, these nonadiabatic pathways are of a collective nature, since they depend on the intermolecular orientation of all electronic transition dipoles in the polarization plane. Notably, this rotational mechanism directly couples the bright upper and lower polaritonic states, and it stays in direct competition with the collective relaxation towards dark states. Published by the American Physical Society 2024