Kinetics of Dissociative Electron Transfer in Electrocarboxylation of Benzyl Chloride

In this paper, we introduce a method for calculating potential-dependent electron transfer barriers and illustrate its utilization with the electrochemical carboxylation of benzyl chloride (BnCl) as a relevant showcase reaction. We applied density functional theory (DFT) to provide a comprehensive analysis of the free energy landscape for the benzyl chloride electrocarboxylation reaction on an inert electrode as influenced by an applied bias. By incorporating elements of Marcus theory, our model enables the calculation of the kinetic barriers of electron transfer. This approach allows for distinguishing between thermodynamic and kinetic contributions to the overpotential in the benzyl chloride electrocarboxylation reaction, offering a molecular-level understanding of electrochemical processes in aprotic environments.