Superreaction: the collective enhancement of a reaction rate by molecular polaritons in the presence of energy fluctuations

TL;DR

This paper demonstrates that molecular polaritons can induce a superreaction, significantly enhancing charge transfer rates through collective quantum coherence, with potential implications for controlling chemical reactions via light-matter interactions.

Contribution

It introduces the concept of superreaction driven by molecular polaritons and explains how strong light-matter coupling enhances reaction rates through quantum coherence.

Findings

Reaction rate increases with the number of molecules under strong light-matter coupling.

Quantum coherence between donors is enhanced by polariton formation.

Without strong coupling, reaction rates decrease due to decoherence.

Abstract

Recent experiments have demonstrated that molecular polaritons, hybrid states of light and matter formed by the strong coupling between molecular electronic or vibrational excitations and an optical cavity, can substantially modify the physical and chemical properties of molecular systems. Here, we show that, by exploiting the collective character of molecular polaritons in conjunction with the effect of polaron decoupling, i.e., the suppression of environmental influence on the polariton, a superreaction can be realized, involving a collective enhancement of charge or excitation-energy transfer reaction rate in a system of donors all coupled to a common acceptor. This effect is analogous to the phenomenon of superradiation. Since the polariton is a superposition state of excitations of all the molecules coupled to the cavity, it is vulnerable to the effect of decoherence caused by energy fluctuations in molecular systems. Consequently, in the absence of a strong light-matter interaction, the reaction rate decreases significantly as the number of molecules increases, even if the system starts from the polariton state. By turning on the light-matter interaction, the dynamic behavior of the system changes dramatically, and the reaction rate increases with the number of molecules, as expected for a superreaction. The underlying mechanism is shown to be the enhancement of quantum coherence between different donors as the light-matter interaction becomes stronger.