Theory of Mode-Selective Chemistry through Polaritonic Vibrational Strong Coupling

Recent experiments have demonstrated remarkable mode-selective reactivities by coupling molecular vibrations with a quantized radiation field inside an optical cavity. The fundamental mechanism behind such effects, on the other hand, remains elusive. In this work, we provide a theoretical explanation of the basic principle of how cavity frequency can be tuned to achieve mode-selective reactivities. We find that the dynamics of the radiation mode leads to a cavity frequency-dependent dynamical caging effect of a reaction coordinate, resulting in suppression of the rate constant. In the presence of competitive reactions, it is possible to preferentially cage a reaction coordinate when the barrier frequencies of competing reactions are different, resulting in a selective slow down of a given reaction. Our theoretical results illustrate the cavity-induced mode-selective chemistry through polaritonic vibrational strong couplings, revealing the fundamental mechanism for changing chemical selectivities through cavity quantum electrodynamics.