Asymmetric and Anharmonic Electrode Kinetics: Evaluation of a Model for Electron Transfer with Concerted Rupture of Weak, Inner Shell Interactions

Abstract

A 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.The present demand to deploy green and sustainable technologies for a whole host of industrial sectors has encouraged process electrification, which, in turn has empowered a growth in electrochemical technologies for, inter alia, energy conversion and storage, chemical manufacture, and water treatment. [1] The efficiency of many of these technologies [a] Dr.