Nathan S. Lawrence
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.
Professor Jay Wadhawan J.Wadhawan@hull.ac.uk
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.
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|
|Peer Reviewed||Peer Reviewed|
|Keywords||Anharmonicity; Asymmetry; Dissociation; Electrochemistry; Electron transfer; Marcus theory; Self-assembled monolayer|
©2021 The authors. All rights reserved.
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