Implications of the fractional charge of hydroxide at the electrochemical interface
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. 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.
- Authors:
-
[1];
[2];
[3];
[4]
- 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)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE; Villum Foundation
- OSTI Identifier:
- 1616750
- Alternate Identifier(s):
- OSTI ID: 1605297
- Grant/Contract Number:
- AC02-76SF00515; 9455; SC0004993; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 22; Journal Issue: 13; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Gauthier, Joseph A., Chen, Leanne D., Bajdich, Michal, and Chan, Karen. Implications of the fractional charge of hydroxide at the electrochemical interface. United States: N. p., 2020.
Web. doi:10.1039/c9cp05952k.
Gauthier, Joseph A., Chen, Leanne D., Bajdich, Michal, & Chan, Karen. Implications of the fractional charge of hydroxide at the electrochemical interface. United States. https://doi.org/10.1039/c9cp05952k
Gauthier, Joseph A., Chen, Leanne D., Bajdich, Michal, and Chan, Karen. Tue .
"Implications of the fractional charge of hydroxide at the electrochemical interface". United States. https://doi.org/10.1039/c9cp05952k. https://www.osti.gov/servlets/purl/1616750.
@article{osti_1616750,
title = {Implications of the fractional charge of hydroxide at the electrochemical interface},
author = {Gauthier, Joseph A. and Chen, Leanne D. and Bajdich, Michal and Chan, Karen},
abstractNote = {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.},
doi = {10.1039/c9cp05952k},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 13,
volume = 22,
place = {United States},
year = {Tue Mar 03 00:00:00 EST 2020},
month = {Tue Mar 03 00:00:00 EST 2020}
}
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