Access to enhanced differences in Marcus–Hush and Butler–Volmer electron transfer theories by systematic analysis of higher order AC harmonics

Literature Information

Publication Date 2012-11-12
DOI 10.1039/C2CP43193A
Impact Factor 3.676
Authors

Gareth P. Stevenson, Ruth E. Baker, Gareth F. Kennedy, Alan M. Bond, David J. Gavaghan, Kathryn Gillow


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Abstract

The potential-dependences of the rate constants associated with heterogeneous electron transfer predicted by the empirically based Butler–Volmer and fundamentally based Marcus–Hush formalisms are well documented for dc cyclic voltammetry. However, differences are often subtle, so, presumably on the basis of simplicity, the Butler–Volmer method is generally employed in theoretical–experimental comparisons. In this study, the ability of Large Amplitude Fourier Transform AC Cyclic Voltammetry to distinguish the difference in behaviour predicted by the two formalisms has been investigated. The focus of this investigation is on the difference in the profiles of the first to sixth harmonics, which are readily accessible when a large amplitude of the applied ac potential is employed. In particular, it is demonstrated that systematic analysis of the higher order harmonic responses in suitable kinetic regimes provides predicted deviations of Marcus–Hush from Butler–Volmer behaviour to be established from a single experiment under conditions where the background charging current is minimal.

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DOI: 10.1039/CS99726BP013

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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