A1 Journal article (refereed)
Grand Canonical Rate Theory for Electrochemical and Electrocatalytic Systems I : General Formulation and Proton-coupled Electron Transfer Reactions (2020)


Melander, Marko M. (2020). Grand Canonical Rate Theory for Electrochemical and Electrocatalytic Systems I : General Formulation and Proton-coupled Electron Transfer Reactions. Journal of the Electrochemical Society, 167 (11), 116518. DOI: 10.1149/1945-7111/aba54b


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Publication details

All authors or editors: Melander, Marko M.

Journal or series: Journal of the Electrochemical Society

ISSN: 0013-4651

eISSN: 1945-7111

Publication year: 2020

Volume: 167

Issue number: 11

Article number: 116518

Publisher: Electrochemical Society

Publication country: United States

Publication language: English

DOI: http://doi.org/10.1149/1945-7111/aba54b

Open Access: Publication channel is not openly available


Abstract

Electrochemical interfaces present a serious challenge for atomistic modelling. Electrochemical thermodynamics are naturally addressed within the grand canonical ensemble (GCE) but the lack of a fixed potential rate theory impedes fundamental understanding and computation of electrochemical rate constants. Herein, a generally valid electrochemical rate theory is developed by extending equilibrium canonical rate theory to the GCE. The extension provides a rigorous framework for addressing classical reactions, nuclear tunneling and other quantum effects, non-adiabaticity etc. from a single unified theoretical framework. The rate expressions can be parametrized directly with self-consistent GCE-DFT methods. These features enable a well-defined first principles route to addressing reaction barriers and prefactors (proton-coupled) electron transfer reactions at fixed potentials. Specific rate equations are derived for adiabatic classical transition state theory and adiabatic GCE empirical valence bond (GCE-EVB) theory resulting in a Marcus-like expression within GCE. From GCE-EVB general free energy relations for electrochemical systems are derived. The GCE-EVB theory is demonstrated by predicting the PCET rates and transition state geometries for the adiabatic Au-catalyzed acidic Volmer reaction using (constrained) GCE-DFT. The work herein provides the theoretical basis and practical computational approaches to electrochemical rates with numerous applications in physical and computational electrochemistry.


Keywords: electrochemistry; thermodynamics; quantum chemistry; density functional theory; theoretical research


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Preliminary JUFO rating: 1


Last updated on 2020-16-10 at 11:12