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.

Automated summary

Recent experiments have shown significant mode-selective reactivities by coupling molecular vibrations with a quantized radiation field inside an optical cavity. However, the fundamental mechanism behind these effects remains mysterious. Theoretical explanation in this work reveals that the dynamics of the radiation mode leads to a cavity frequency-dependent dynamical caging effect of a reaction coordinate, resulting in a suppression of the rate constant. It is possible to selectively slow down a given reaction by preferentially caging a reaction coordinate in the presence of competitive reactions with different barrier frequencies.