We theoretically demonstrate that the 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.
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Indeed, if represents the identity of the full electronic Hilbert space, then is properly confined in the subspace , whereas contains the terms outside the subspace . More numerical evidence can be found in Fig. S2 of the supplementary material in Ref. 28.