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


Melander, M. 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), Article 116518. https://doi.org/10.1149/1945-7111/aba54b


JYU authors or editors


Publication details

All authors or editorsMelander, Marko M.

Journal or seriesJournal of the Electrochemical Society

ISSN0013-4651

eISSN1945-7111

Publication year2020

Volume167

Issue number11

Article number116518

PublisherElectrochemical Society

Publication countryUnited States

Publication languageEnglish

DOIhttps://doi.org/10.1149/1945-7111/aba54b

Publication open accessNot open

Publication channel open access

Publication is parallel published (JYX)https://jyx.jyu.fi/handle/123456789/73407


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.


Keywordselectrochemistrythermodynamicsquantum chemistrydensity functional theorytheoretical research


Contributing organizations


Ministry reportingYes

Reporting Year2020

JUFO rating1


Last updated on 2024-03-04 at 20:46