A Surface Hopping View of Electrochemistry: Non-Equilibrium Electronic Transport through an Ionic Solution with a Classical Master Equation

We use a recent flavor of surface hopping dynamics to investigate the nonequilibrium transport of electrons as carried by a few ions through a solution of Lennard-Jones spheres across a finite voltage. We analyze our nonequilibrium results through a combination of equilibrium simulations and steady state rate equations. While the nonequilibrium dynamics approach in this paper is computationally demanding and likely limited to reasonably small simulation sizes (or short time scales), the present study does provide a simple means for us to understand the interplay between nuclear motion near a metal surface and charge injection into/from the metal surface. This interplay is especially interesting when the system of interest is far from the linear response regime (which might well be very common in electrochemistry).