Practical Considerations for Continuum Models Applied to Surface Electrochemistry

Joseph Gauthier, Colin Dickens, Stefan Ringe, Karen Chan*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

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. How- ever, 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.
Original languageEnglish
JournalChemPhysChem
ISSN1439-4235
DOIs
Publication statusAccepted/In press - 2019

Cite this

@article{10d5f35c15404142b8674ca8790f866b,
title = "Practical Considerations for Continuum Models Applied to Surface Electrochemistry",
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. How- ever, 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.",
author = "Joseph Gauthier and Colin Dickens and Stefan Ringe and Karen Chan",
year = "2019",
doi = "10.1002/cphc.201900536",
language = "English",
journal = "ChemPhysChem",
issn = "1439-4235",
publisher = "Wiley - V C H Verlag GmbH & Co. KGaA",

}

Practical Considerations for Continuum Models Applied to Surface Electrochemistry. / Gauthier, Joseph; Dickens, Colin; Ringe, Stefan; Chan, Karen.

In: ChemPhysChem, 2019.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Practical Considerations for Continuum Models Applied to Surface Electrochemistry

AU - Gauthier, Joseph

AU - Dickens, Colin

AU - Ringe, Stefan

AU - Chan, Karen

PY - 2019

Y1 - 2019

N2 - 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. How- ever, 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.

AB - 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. How- ever, 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.

U2 - 10.1002/cphc.201900536

DO - 10.1002/cphc.201900536

M3 - Journal article

JO - ChemPhysChem

JF - ChemPhysChem

SN - 1439-4235

ER -