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The modification of thermal chemical rates in Fabry-Perot cavities, asobserved in experiments, still poses theoretical challenges. While we have abetter grasp of how the reactivity of isolated molecules and model systemschanges under strong coupling, we lack a comprehensive understanding of thecombined effects and the specific roles played by activated and spectatormolecules during reactive events. In this study, we investigate an ensemble ofrandomly oriented gas-phase HONO molecules undergoing a cis-trans isomerizationreaction on an ab-initio potential energy surface. Using the classical reactiveflux method, we analyze the transmission coefficient and determine conditionsthat lead to accelerated rates within the collective regime. We identify twomain mechanisms at work: firstly, spectator molecules enhance the cavity'sability to dissipate excess energy from the activated molecule post-reactiveevent. Additionally, the interaction between spectator molecules and the cavitygives rise to the creation of polaritonic modes. These modes then interact withthe activated molecule at a shifted resonance frequency.

Modification of Thermal Chemical Rates in a Cavity via Resonant Effects in the Collective Regime