Microscopic Theory of Vibrational Polariton Chemistry

TL;DR

This paper develops a microscopic analytic theory explaining how vibrational strong coupling (VSC) influences chemical reaction rates, accounting for resonance, collective effects, and making verifiable predictions.

Contribution

It introduces a mechanistic microscopic theory that explains VSC effects on reaction rates, including resonance and collective phenomena, with experimentally testable predictions.

Findings

Resonance effect at normal incident angle explained

Collective vibrational effects accounted for

Predictions made for experimental verification

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.