Implications of the fractional charge of hydroxide at the electrochemical interface

Gauthier, Joseph A.; Chen, Leanne D.; Bajdich, Michal; Chan, Karen

doi:10.1039/c9cp05952k

Title: Implications of the fractional charge of hydroxide at the electrochemical interface

Journal Article · 03 March 2020 · Physical Chemistry Chemical Physics. PCCP

DOI: https://doi.org/10.1039/c9cp05952k · OSTI ID:1616750

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Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Stanford Univ., CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Technical Univ. of Denmark, Lyngby (Denmark)

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. Finally, we 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.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE; VILLUM FONDEN

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515; SC0004993

OSTI ID:: 1616750

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 13 Vol. 22; ISSN 1463-9076; ISSN PPCPFQ

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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