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Issue 13, 2020
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Implications of the fractional charge of hydroxide at the electrochemical interface

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Abstract

Rational design of materials that efficiently convert electrical energy into chemical bonds will ultimately depend on a thorough understanding of the electrochemical interface at the atomic level. Towards this goal, the use of density functional theory (DFT) at the generalized gradient approximation (GGA) level has been applied widely in the past 15 years. In the calculation of electrochemical reaction energetics using GGA-DFT, it is frequently implicitly assumed that ions in the Helmholtz plane have unit charge. However, the ion charge is observed to be fractional near the interface through both a capacitor model and through Bader charge partitioning. In this work, we show that this spurious charge transfer can be effectively mitigated by continuum charging of the electrolyte. We then show that, similar to hydronium, the observed fractional charge of hydroxide is not due to a GGA level self-interaction error, as the partial charge is observed even when using hybrid level exchange–correlation functionals.

Graphical abstract: Implications of the fractional charge of hydroxide at the electrochemical interface

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Article information


Submitted
01 Nov 2019
Accepted
14 Feb 2020
First published
03 Mar 2020

Phys. Chem. Chem. Phys., 2020,22, 6964-6969
Article type
Paper

Implications of the fractional charge of hydroxide at the electrochemical interface

J. A. Gauthier, L. D. Chen, M. Bajdich and K. Chan, Phys. Chem. Chem. Phys., 2020, 22, 6964
DOI: 10.1039/C9CP05952K

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