How Quantum is the Resonance Behavior in Vibrational Polariton Chemistry?

Abstract

Recent experiments in polariton chemistry have demonstrated that reaction rates can be modified by vibrational strong coupling to an optical cavity mode. Importantly, this modification occurs only when the frequency of the cavity mode is tuned to closely match a molecular vibrational frequency. This sharp resonance behavior has proved to be difficult to capture theoretically. Only recently did Lindoy et al. [ Nat. Commun. 2023, 14, 2733 ] report the first instance of a sharp resonant effect in the cavity-modified rate simulated in a model system using exact quantum dynamics. We investigate the same model system with a different method, ring-polymer molecular dynamics (RPMD), which captures quantum statistics but treats dynamics classically. We find that RPMD does not reproduce this sharp resonant feature at the well frequency, and we discuss the implications of this finding for future studies of vibrational polariton chemistry.