Quantum Dynamics of Vibrational Polariton Chemistry

TL;DR

This paper uses exact quantum simulations to study how optical cavities influence chemical reaction rates, revealing quantum effects like state splittings and resonances that align well with experimental observations.

Contribution

It demonstrates the necessity of quantum mechanical modeling to accurately predict cavity-modified reaction rates in vibrational polariton chemistry.

Findings

Quantum effects cause sharp changes in reaction rates.

Quantum simulations match experimental results better than previous models.

Cavity coupling significantly alters chemical reactivity.

Abstract

We employ an exact quantum mechanical simulation technique to investigate a model of cavity-modified chemical reactions in the condensed phase. The model contains the coupling of the reaction coordinate to a generic solvent, cavity coupling to either the reaction coordinate or a non-reactive mode, and the coupling of the cavity to lossy modes. Thus, many of the most important features needed for realistic modeling of the cavity modification of chemical reactions are included. We find that when a molecule is coupled to an optical cavity it is essential to treat the problem quantum mechanically in order to obtain a quantitative account of alterations to reactivity. We find sizable and sharp changes in the rate constant that are associated with quantum mechanical state splittings and resonances. The features that emerge from our simulations are closer to those observed in experiments than are previous calculations, even for realistically small values of coupling and cavity loss. This work highlights the importance of a fully quantum treatment of vibrational polariton chemistry.