Super-Reaction Enhancement of Polariton-Mediated Electron Transfer

Abstract

We investigate the enhancement of polariton-mediated electron transfer (PMET) using a general super-reaction mechanism where multiple donor sites locally couple to individual acceptors. We demonstrate that this enhancement extends to the collective light–matter coupling regime with a large number of acceptors and cavity-coupled donors. We use analytic rate theory and quantum dynamics simulations to show that the local super-reaction mechanism serves as an additional enhancement to the delocalized driving force enhancement of PMET. We further incorporate bath-induced disorder in the donors to investigate precisely how collective light–matter coupling protects the coherent super-reaction enhancement against disorder. The results show that ET from bright polariton states, which are separated enough from the dark state manifold, is enhanced by the super-reaction mechanism in any ET regime, offering another avenue to realize cavity modification of photochemistry.