Molecular electron transfer in optical cavities: From excitonic to vibronic polaritons

Strong coupling between molecular excitations and quantized electromagnetic fields in optical cavities provides a powerful means to control the physical and chemical properties of molecular systems. Here, we study electron transfer (ET) dynamics in cavity-coupled molecules using the numerically exact hierarchical equations of motion method, which captures nonperturbative and non-Markovian effects beyond standard perturbative theories. We identify distinct resonance and collective effects associated with polariton formation and show that the ET rate saturates in the strong-coupling regime, a feature not captured by perturbative approaches. We further extend the cavity-modified ET model by incorporating the nuclear-coordinate dependence of molecular electric dipole moments, which gives rise to a three-body interaction involving molecular electronic and vibrational degrees of freedom and cavity photons. This vibronic polariton formation leads to non-monotonic, oscillatory dependencies of the ET rate on the light–matter coupling strength and cavity frequency, which we attribute to quantum interference among multiple transfer pathways. These findings establish cavity-modified electron transfer as a multichannel quantum process governed by the interplay of electronic, vibrational, and photonic degrees of freedom.