Microscopic Theory of Vibrational Polariton Chemistry (2305.05005v2)

Abstract: We present a microscopic theory that aims to explain the vibrational strong coupling (VSC) modified reaction rate constant. The analytic theory is based on a mechanistic conjecture that cavity modes promote the transition from the ground state to the vibrational excited state of the reactant, which is the rate-limiting step of the reaction. The theory explains the observed resonance effect at the normal incident angle. Assuming the coherent vibrational energy transfer picture, the theory can also explain the collective effect and makes several predictions that are experimentally verifiable.