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Title: Practical Considerations for Continuum Models Applied to Surface Electrochemistry

Abstract

Abstract Modelling the electrolyte at the electrochemical interface remains a major challenge in ab initio simulations of charge transfer processes at surfaces. Recently, the development of hybrid polarizable continuum models/ ab initio models have allowed for the treatment of solvation and electrolyte charge in a computationally efficient way. However, challenges remain in its application. Recent literature has reported that large cell heights are required to reach convergence, which presents a serious computational cost. Furthermore, calculations of reaction energetics require costly iterations to tune the surface charge to the desired potential. In this work, we present a simple capacitor model of the interface that illuminates how to circumvent both of these challenges. We derive a correction to the energy for finite cell heights to obtain the large cell energies at no additional computational expense. We furthermore demonstrate that the reaction energetics determined at constant charge are easily mapped to those at constant potential, which eliminates the need to apply iterative schemes to tune the system to a constant potential. These developments together represent more than an order of magnitude reduction of the computational overhead required for the application of polarizable continuum models to surface electrochemistry.

Authors:
 [1];  [1];  [1];  [2]
+ Show Author Affiliations
  1. Stanford Univ., CA (United States)
  2. Technical Univ. of Denmark, Lyngby (Denmark)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1560678
Alternate Identifier(s):
OSTI ID: 1576648
Grant/Contract Number:  
AC02-76SF00515; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ChemPhysChem
Additional Journal Information:
Journal Volume: 20; Journal Issue: 22; Journal ID: ISSN 1439-4235
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Gauthier, Joseph A., Dickens, Colin F., Ringe, Stefan, and Chan, Karen. Practical Considerations for Continuum Models Applied to Surface Electrochemistry. United States: N. p., 2019. Web. doi:10.1002/cphc.201900536.
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Gauthier, Joseph A., Dickens, Colin F., Ringe, Stefan, & Chan, Karen. Practical Considerations for Continuum Models Applied to Surface Electrochemistry. United States. https://doi.org/10.1002/cphc.201900536
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Gauthier, Joseph A., Dickens, Colin F., Ringe, Stefan, and Chan, Karen. Wed . "Practical Considerations for Continuum Models Applied to Surface Electrochemistry". United States. https://doi.org/10.1002/cphc.201900536. https://www.osti.gov/servlets/purl/1560678.
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@article{osti_1560678,
title = {Practical Considerations for Continuum Models Applied to Surface Electrochemistry},
author = {Gauthier, Joseph A. and Dickens, Colin F. and Ringe, Stefan and Chan, Karen},
abstractNote = {Abstract Modelling the electrolyte at the electrochemical interface remains a major challenge in ab initio simulations of charge transfer processes at surfaces. Recently, the development of hybrid polarizable continuum models/ ab initio models have allowed for the treatment of solvation and electrolyte charge in a computationally efficient way. However, challenges remain in its application. Recent literature has reported that large cell heights are required to reach convergence, which presents a serious computational cost. Furthermore, calculations of reaction energetics require costly iterations to tune the surface charge to the desired potential. In this work, we present a simple capacitor model of the interface that illuminates how to circumvent both of these challenges. We derive a correction to the energy for finite cell heights to obtain the large cell energies at no additional computational expense. We furthermore demonstrate that the reaction energetics determined at constant charge are easily mapped to those at constant potential, which eliminates the need to apply iterative schemes to tune the system to a constant potential. These developments together represent more than an order of magnitude reduction of the computational overhead required for the application of polarizable continuum models to surface electrochemistry.},
doi = {10.1002/cphc.201900536},
journal = {ChemPhysChem},
number = 22,
volume = 20,
place = {United States},
year = {Wed Jul 17 00:00:00 EDT 2019},
month = {Wed Jul 17 00:00:00 EDT 2019}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1002/cphc.201900536
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Cited by: 33 works
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Figures / Tables:

Figure 1 Figure 1: Illustration of the different potential levels in VASPsol using the example of adsorbed CO2 on Pt(111 ).
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