Abstract
AbstractA surface‐integrated form of the widely used (anharmonic) Lennard‐Jones 12–6 interaction potential, the Lennard‐Jones 9–3 potential, is used to develop a quadratic activation/driving force relationship that gives rise to asymmetric Tafel plots for electron transfer occurring with simultaneous interaction rupture. The Tafel plots are shown to exhibit linearity over a wide potential range, depending on the ratio of the Gibbs interaction well to the solvent reorganisation free energy. The fit of the model to experimental data for a ferrocene‐based self‐assembled monolayer (SAM) bathed by aqueous perchloric acid suggests ion pairing between ferricenium and perchlorate ions. This crude and primitive model readily enables experimentalists to obtain a parametric understanding of the physicochemical dynamics underpinning interaction rupture in concert with electron transfer, which may empower routes to improve the efficiency of a plethora of topical electrochemical technologies.
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