Solvent Dependence on Cooperative Vibrational Strong Coupling and Cavity Catalysis

Strong light-matter coupling offers a unique way to control chemical reactions at the molecular level. Here, we try to compare the solvent effect on a solvolysis process under cooperative vibrational strong coupling (VSC). Two solvents, ethyl acetate and cyclopentanone are chosen to study cavity catalysis by coupling the C=O stretching band of the reactant and the solvent molecules to a Fabry-Perot cavity mode. Interestingly, both the solvent system catalyze the chemical reaction under cooperative VSC conditions. However, the resonance effect on catalysis is observed at different temperatures for the two solvent systems, which is further confirmed by thermodynamic studies. Cavity detuning and other control experiments suggest that cooperative VSC of the solvent plays a crucial role in modifying the transition state energy of the reaction. These findings, along with other observations, cement the concept of polaritonic chemistry.