The current state-of-the-art electron-transfer modeling primarily focuses on the kinetics of charge transfer between an electroactive species and an inert electrode. Experimental studies have revealed that the existing Butler–Volmer model fails to satisfactorily replicate experimental voltammetry results for both solution-based and surface-bound redox couples. Consequently, experimentalists lack an accurate tool for predicting electron-transfer kinetics. In response to this challenge, we developed a density functional theory-based approach for accurately predicting current peak potentials by using the Marcus–Hush model. Through extensive cyclic voltammetry simulations, we conducted a thorough exploration that offers valuable insights for conducting well-informed studies in the field of electrochemistry.

Electrocatalytic reduction of organic halides and subsequent carboxylation are promising methods for the valorization of CO2 as a C1 source in synthetic organic chemistry. The reaction mechanism underlying the selectivity and reduction mechanism of benzyl halides is highly dependent on the nature of the electrode material as well as the processes, composition, and structure of the liquid phase at the electrode–solution interface. Herein, we present a computational study on the influence of the electric double layer (EDL) on the activation of benzyl halides at different applied potentials over the Au (111) cathode. Using a multiscale modeling approach, we demonstrate that, under realistic electrocatalytic conditions, the formation of a dense EDL over the cathode hampers the diffusion of benzyl halides toward the electrode surface. A combination of classical molecular dynamics simulations and density functional theory calculations reveals the most favorable benzyl halide electro-carboxylation pathway over the EDL that does not require direct substrate adsorption to the cathode surface. The dense EDL promotes the dissociative reduction of the benzyl halides via the outer-sphere electron transfer from the cathode surface to the electrolyte. Such a reduction mechanism results in a benzyl radical intermediate, which is then converted to benzyl anions in the EDL via an additional electron transfer step.