Publication date: 6th November 2020
Using the electrode potential and electrolyte to manipulate reaction thermodynamics and kinetics forms the backbone of all electrochemistry and electrocatalysis. Especially important reactions to understand are proton-coupled electron transfer (PCET) reactions forming the mechanistic basis of e.g. oxygen, CO2, and N2 reduction and hydrogen evolution reactions. While clever and cheap schemes for evaluating electrochemical thermodynamics and kinetics have been developed, a rigorous treatment is needed to test the accuracy and to define well-controlled computational models.
In my contribution I will present a rigorous theory and numerical techniques to simulate electrochemical solid-liquid interfaces using grand canonical ensemble density functional theory (GCE-DFT) [1] – this approach provides an exact theory and well-defined approximations to compute thermodynamics as a function of the electrode potential and electrolyte concentration. Besides thermodynamics, I will present the newly established generally valid GCE rate theory (GCE-RT) to address PCET reaction kinetics as a function of the electrode potential.[2,3] The GCE-RT can account for (non-adiabatic) proton and electron tunneling which may significantly contribute to PCET kinetics and long-range electron transfer, respectively.[3] Besides theory, I will present how the thermodynamics, kinetics, and nuclear quantum effects of a gold-catalyzed Volmer reaction can be addressed and understood from the atomic scale with GCE-DFT and GCE-RT[2-3]. I will also show how GCE-DFT can be used for parametrizing effective Hamiltonians for predicting and explaining electron transfer kinetics and experimental measurements (in preparation).
The presentation provides an account on the recent theoretical and methodological developments in using constant potential, grand canonical ensemble DFT for simulating electrochemical interfaces and reactions. These developments enable simulating both the thermodynamics and kinetics of electrochemical reactions, including both classical adiabatic inner-sphere reactions as well as e.g. outer-sphere reactions, non-adiabaticity, and nuclear tunneling at the DFT level.
I acknowledge the CSC-IT Center for Computer Science for providing the computational resources. I also thank the Academy of Finland for funding (project number 307853)
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