Theory of Vibrational Polariton Chemistry in the Collective Coupling Regime

TL;DR

This paper theoretically shows that coupling molecular vibrations with an optical cavity can significantly suppress chemical reaction rates through collective effects and cavity modifications, with implications for controlling chemical kinetics.

Contribution

It introduces a theoretical framework demonstrating how collective vibrational coupling and cavity effects can suppress chemical reaction rates, highlighting the role of dynamical caging and cavity loss.

Findings

Reaction rate constant can be suppressed by vibrational coupling.

Collective coupling enhances the suppression effect.

Cavity loss amplifies the reaction rate suppression.

Abstract

We theoretically demonstrate that chemical reaction rate constant can be significantly suppressed by coupling molecular vibrations with an optical cavity, exhibiting both the collective coupling effect and the cavity-frequency modification of the rate constant. When a reaction coordinate is strongly coupled to the solvent molecules, the reaction rate constant is reduced due to the dynamical caging effect. We demonstrate that collectively coupling the solvent to the cavity can further enhance this dynamical caging effect, leading to additional suppression of the chemical kinetics. This effect is further amplified when cavity loss is considered.