Role of Cavity Strong Coupling on Single Electron Transfer Reaction at Electrode-Electrolyte Interface

Physicochemical properties of molecules can be modulated through the polariton formation under strong electromagnetic confinement. Here, we discuss the possibility of exploiting this phenomenon to increase the electron transfer rate at an electrode–electrolyte interface. Electron transfer theory under strong electromagnetic confinement can be extended to the electrode–electrolyte interface, and single–electron transfer reaction can be simulated using Gerischer’s theory. Although single electron transfer in free space is well described using Marcus theory, the vacuum electric field can facilitate an additional electron transfer pathway via virtual photon excitation under cavity strong coupling conditions. Therefore, this binary reaction pathway for single electron transfer can yield a quasi-two-particle electron transfer process. This quantum behavior can dominate when the mode volume is small and there is a large number of molecules in the vacuum electric field. Exploitation of polaritons in single electron transfer reactions can lead to enhanced electrochemical energy conversion systems.