Resonant Cavity Modification of Ground-State Chemical Kinetics

Recent experiments have suggested that ground-state chemical kinetics can be suppressed or enhanced by coupling molecular vibrations with a cavity radiation mode. Here, we develop an analytical rate theory for cavity-modified chemical kinetics based on the Pollak–Grabert–Hänggi theory. Unlike previous work, our theory covers the complete range of solvent friction values, from the energy-diffusion-limited to the spatial-diffusion-limited regimes. We show that chemical kinetics is enhanced when bath friction is weak and suppressed when bath friction is strong. For weak bath friction, the resonant photon frequency (at which the maximum modification of the chemical rate is achieved) is close to the reactant well. In the strong friction limit, the resonant photon frequency is instead close to the barrier frequency. Finally, we observe that rate changes as a function of the photon frequency are much sharper and more sizable in the weak friction limit than in the strong friction limit.