Chemical reactivity under collective vibrational strong coupling

TL;DR

This paper investigates how collective vibrational strong coupling in optical cavities influences chemical reaction rates, revealing that increasing molecule numbers can slow reactions and establishing a scaling relation for predicting these effects.

Contribution

It introduces a simple scaling relation linking collective Rabi splitting to reaction rate modifications, supported by numerical simulations of up to 10,000 molecules.

Findings

Reaction rates can slow down with more aligned molecules under resonance.

A scaling relation predicts the onset of reaction rate changes.

Numerical demonstrations for up to 10,000 molecules support the theory.

Abstract

Recent experiments of chemical reactions in optical cavities have shown great promise to alter and steer chemical reactions but still remain poorly understood theoretically. In particular the origin of resonant effects between the cavity and certain vibrational modes in the collective limit is still subject to active research. In this paper, we study unimolecular dissociation reactions of many molecules collectively interacting with an infrared cavity mode through their vibrational dipole moment. We find that the reaction rate can slow down by increasing the number of aligned molecules if the cavity mode is resonant with a vibrational frequency of the molecules. We also discover a simple scaling relation that scales with the collective Rabi splitting to estimate the onset of reaction rate modification by collective vibrational strong coupling and numerically demonstrate these effects for up to 10,000 molecules.