Nonequilibrium effects of vibrational strong coupling on chemical reactions

Vibrational strong coupling (VSC), or the strong interaction between molecular vibrations and an optical cavity photon, gives rise to hybrid light-matter states called polaritons. Experiments find that VSC can drastically alter the kinetics of organic reactions. However, transition-state theory (TST), the most commonly used reaction-rate theory, has been unsuccessful at explaining such "VSC catalysis." One assumption of TST is that internal thermal equilibrium (i.e., within the states of each chemical species) is maintained throughout the reaction. Here, we explore how VSC affects chemical reactions in the limit where the equilibrium assumption breaks down.