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

Lawrence, Nathan S.; Schöllhorn, Bernd; Wadhawan, Jay D.

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.

Citation

Lawrence, N. S., Schöllhorn, B., & Wadhawan, J. D. (2021). Asymmetric and Anharmonic Electrode Kinetics: Evaluation of a Model for Electron Transfer with Concerted Rupture of Weak, Inner Shell Interactions. ChemistrySelect, 6(46), 13331-13335. https://doi.org/10.1002/slct.202103526

• Journal Article Type: Article
• Acceptance Date: Dec 2, 2021
• Online Publication Date: Dec 8, 2021
• Publication Date: Dec 13, 2021
• Deposit Date: Jan 11, 2023
• Publicly Available Date: Jan 16, 2023
• Journal: ChemistrySelect
• Electronic ISSN: 2365-6549
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 6
• Issue: 46
• Pages: 13331-13335
• DOI: https://doi.org/10.1002/slct.202103526
• Keywords: Anharmonicity; Asymmetry; Dissociation; Electrochemistry; Electron transfer; Marcus theory; Self-assembled monolayer
• Public URL: https://hull-repository.worktribe.com/output/3887726