Polariton Mediated Charge Transfer Reaction through Cavity-Quantum Electrodynamics*

We study the polariton mediated electron transfer in a three-state model molecular system that describes the the photoinduced charge transfer process from an optically bright donor to an optically dark acceptor. With direct quantum dynamical simulations and analytical rate expressions, we demonstrate that coupling the molecular system to the quantized radiation field in an optical cavity can significantly enhance or suppress the photoinduced charge transfer process. Moreover, we also assess the accuracy of commonly used approximations in the field of polariton photochemistry such as the rotating wave approximation and the effect of ignoring the dipole self-energy term. We find that both terms are equally important to accurately describe the charge transfer process, especially in the ultra-strong coupling regime.