Collision-induced spectroscopy and radiative association in microcavities

Polariton chemistry has emerged as a new approach to directing molecular systems via strong light-matter interactions in confined photonic media. In this work, we implement a classical electrodynamics-molecular dynamics method to investigate collision-induced emission and radiative association in planar microcavities under variable light-matter coupling strength. We focus on the argon-xenon (Ar-Xe) gas mixture as a representative system, simulating collisions coupled to the confined multimode electromagnetic field. We find that while the effects of a microcavity on collision-induced emission spectra are subtle, even at extremely large coupling strengths, radiative association can be significantly enhanced in a microcavity. Our results also indicate that microcavities may be designed to induce changes in the statistical distribution of Ar-Xe complex lifetimes. These findings provide new insights into the control of intermolecular interactions and radiative kinetics with microcavities.