Electron transfer dynamics at electrode interfaces via a straightforward semiclassical fermionic mapping approach

Electron transfer between electrodes and molecules on their surface or in the electrochemical double layer are processes that are central to heterogenous catalysis and a diverse array of industrial, medical, and energy-conversion techniques. However, simulating these processes is challenging because it requires a consistent dynamical treatment of the fermionic states of electrons in the metallic electrode, their coupling to the electronic energy levels in the donor/acceptor molecule, and the modulation and dissipation of the electronic energy arising from the nuclear motion of the molecule and its surrounding solvent. Here I present a semiclassical mapping approach to treat electrochemical electron transfer processes. We show that this method, which is exact in the absence of vibrational coupling for non-interacting fermions, remains accurate in the presence of coupling to vibrational motion when benchmarked on the Anderson-Holstein Model. This semiclassical approach provides a path toward scalable atomistic simulations of electrochemical electron transfer in condensed-phase molecular systems.