Computational Electrosynthesis: A Perspective on Mechanistic Questions, Methodological Approaches, and Elucidating the Role of the Electrical Double Layer.

In this perspective, we discuss how modern computational chemistry techniques are utilized to elucidate electrosynthesis reaction mechanisms via the computation of kinetic rate parameters that depend on reaction conditions. The specific focus is on elementary reaction steps that occur within the electrical double layer (EDL) environment at the working electrode/electrolyte interface, for which the governing free energy profiles and rate constants can be explicitly computed from classical molecular dynamics and hybrid quantum mechanics/molecular mechanics (QM/MM) computer simulations with atomistic resolution of the EDL environment. We focus on direct electrolysis reactions at inert electrodes with prototypical "E-C-E" mechanisms, in which the reaction yield and selectivity may depend on whether the full process occurs heterogeneously within the EDL, or rather the steps following the initial electron transfer proceed homogeneously with the second electron transfer occurring via disproportionation (DISP pathway). For short-lived radical intermediates with lifetimes of ∼10