Thermal chemical reactivity in Frenkel exciton-polariton cavities

Abstract

Hybrid light-matter states formed under strong coupling between molecular excitations and confined electromagnetic modes provide a potential route to modify chemical properties. Here we compute and compare a thermally averaged measure of molecular chemical activity for an equilibrium ensemble of molecules inside and outside a planar microcavity, explicitly accounting for the spatial distribution (and hence the in-plane wavevector dispersion) of the coupled light-matter states. Within a generalized Tavis-Cummings description, we find that the cavity-induced change in thermal chemical activity is most pronounced for small molecular ensembles (low areal density within a given cavity mode volume) and increases with the collective coupling strength (Rabi splitting), particularly at low temperatures. These results highlight the importance of the polariton dispersion and molecular-mode counting in assessing cavity modifications of thermally driven molecular reactivity.