Advances in the theoretical understanding of interfacial electrochemistry have, over the past decade, permitted the extension of periodic Density Functional Theory studies, which have traditionally been applied to probe chemistry at gas/solid interfaces, to electrochemical systems where potential-dependent structural and chemical phase transformations occur at liquid/solid interfaces. Indeed, such techniques have been employed to study a surprisingly wide class of electrochemical processes, ranging from electrocatalysis to corrosion.

In this talk, we will discuss how these strategies can be applied to predict the detailed, atomic-scale properties of monolayer (hydroxy)oxide base metal films on precious metal and precious metal alloy substrates as a function of applied potential. We will describe the analysis of Moire patterns, variable oxidation states, and three-phase boundaries of these films, and we will demonstrate how these results may be used to predict the shape and oxidation states of supported two-dimensional nanoislands as a function of electrochemical conditions. We will next discuss how the three-phase boundaries may promote hydrogen evolution rates in alkaline environments, and we will close with some perspectives on the possibilities for electrocatalyst design offered by these systems.

If time permits, we will also discuss a new approach, based on a combination of DFT and kinetic Monte Carlo simulations, that permits direct simulation of polarization curves as a function of sweep rate and that rigorously predicts intrinsic reaction pathways for both electroreduction of nitrates and NO in acidic environments.