Solvent Dependence on Cooperative Vibrational Strong Coupling and Cavity Catalysis**

Abstract

AbstractStrong light‐matter coupling offers a unique way to control chemical reactions at the molecular level. Here, we compare the solvent effect on an ester solvolysis process under cooperative vibrational strong coupling (VSC). Three reactants, para‐nitrophenylacetate, 3‐methyl‐para‐nitrophenylbenzoate, and bis‐(2, 4‐dinitrophenyl) oxalate are chosen to study the effect of VSC on the solvolysis reaction rates. Two solvents, ethyl acetate and cyclopentanone, are also considered to compare the cavity catalysis by coupling the C=O stretching band of the reactant and the solvent molecules to a Fabry‐Perot cavity mode. Interestingly, both solvents enhance the chemical reaction rate of para‐nitrophenylacetate and 3‐methyl‐para‐nitrophenylbenzoate under cooperative VSC conditions. However, the resonance effect is observed at different temperatures for different solvents, which is further confirmed by thermodynamic studies. Bis‐(2, 4‐dinitrophenyl) oxalate doesn′t respond to VSC in either of the solvent systems due to poor overlap of reactant and solvent C=O vibrational bands. Cavity detuning and other control experiments suggest that cooperative VSC of the solvent plays a crucial role in modifying the activation free‐energy of the reaction. These findings, along with other observations, cement the concept of polaritonic chemistry.