Interference between Molecular and Photon Field-Mediated Electron Transfer in Cavities

Cavity polaritonics creates novel opportunities to direct chemical reactions. Electron transfer (ET) reactions are among the simplest reactions, and they underpin energy conversion. New strategies to manipulate and direct electron flow at the nanoscale are of particular interest in biochemistry, energy science, bioinspired materials science, and chemistry. We show that optical cavities can modulate electron transfer pathway interferences and ET rates in donor-bridge-acceptor (DBA) systems. We derive the rate for DBA electron transfer when the molecules are coupled to cavity modes, emphasizing novel cavity -induced pathway interferences with the molecular electronic coupling pathways, as these interferences allow a new kind of ET rate tuning. The interference between the cavity-induced coupling pathways and the intrinsic molecular coupling pathway is dependent on the cavity properties. Thus, manipulating the interference between the cavity-induced DA coupling and the bridge -mediated coupling offers an approach to direct and manipulate charge flow at the nanoscale.