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Polariton chemistry has emerged as a new approach for 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.