Recent experiments have demonstrated the control of chemical reactivities and mode-selectivities by coupling molecular vibrations with a quantized radiation field inside an optical microcavity. In contrast, transition state theory predicts no change of the reaction barrier height during this process. We present a theoretical explanation of the cavity modification of the ground-state reactivity in the vibrational strong coupling (VSC) regime in polariton chemistry. Our theoretical results suggest that the VSC kinetics modification originates from the non-Markovian dynamics of the cavity radiation mode that couples to the molecule, leading to the dynamical-caging effect of the reaction coordinate and the suppression of reaction rate constant at a specific range of photon frequency related to the barrier frequency. 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 slowdown of a given reaction. Our simulations and analytical theory provide a plausible explanation of the photon-frequency-dependent modification of the chemical reactivities chemistry in the VSC polariton chemistry, and reveal the fundamental mechanism for changing chemical selectivities through cavity quantum electrodynamics.

Cavity frequency-dependent theory for vibrational polariton chemistry

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