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Title: Unified Approach to Implicit and Explicit Solvent Simulations of Electrochemical Reaction Energetics

Abstract

One of the major open challenges in ab initio simulations of the electrochemical interface is the determination of electrochemical barriers under a constant driving force. Existing methods to do so include extrapolation techniques based on fully explicit treatments of the electrolyte, as well as implicit solvent models which allow for a continuous variation in electrolyte charge. Emerging hybrid continuum models have the potential to revolutionize the field, since they account for the electrolyte with little computational cost while retaining some explicit electrolyte, representing a “best of both worlds” method. In this work, we present a unified approach to determine reaction energetics from fully explicit, implicit, and hybrid treatments of the electrolyte based on a new multicapacitor model of the electrochemical interface. A given electrode potential can be achieved by a variety of interfacial structures; a crucial insight from this work is that the effective surface charge gives a good proxy of the local potential, the true driving force of electrochemical processes. In contrast, we show that the traditionally considered work function gives rise to multivalued functions depending on the simulation cell size. Furthermore, we show that the reaction energetics are largely insensitive to the countercharge distribution chosen in hybrid implicit/explicitmore » models, which means that any of the myriad implicit electrolyte models can be equivalently applied. Furthermore, this work thus paves the way for the accurate treatment of ab initio reaction energetics of general surface electrochemical processes using both implicit and explicit electrolytes.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2];  [2];  [1]; ORCiD logo [2]
  1. Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Technical Univ. of Denmark, Kongens Lyngby (Denmark)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
OSTI Identifier:
1595243
Grant/Contract Number:  
AC02-76SF00515; DGE-114747; 9455; SC0004993; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 15; Journal Issue: 12; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Gauthier, Joseph A., Dickens, Colin F., Heenen, Hendrik H., Vijay, Sudarshan, Ringe, Stefan, and Chan, Karen. Unified Approach to Implicit and Explicit Solvent Simulations of Electrochemical Reaction Energetics. United States: N. p., 2019. Web. doi:10.1021/acs.jctc.9b00717.
Gauthier, Joseph A., Dickens, Colin F., Heenen, Hendrik H., Vijay, Sudarshan, Ringe, Stefan, & Chan, Karen. Unified Approach to Implicit and Explicit Solvent Simulations of Electrochemical Reaction Energetics. United States. doi:10.1021/acs.jctc.9b00717.
Gauthier, Joseph A., Dickens, Colin F., Heenen, Hendrik H., Vijay, Sudarshan, Ringe, Stefan, and Chan, Karen. Tue . "Unified Approach to Implicit and Explicit Solvent Simulations of Electrochemical Reaction Energetics". United States. doi:10.1021/acs.jctc.9b00717.
@article{osti_1595243,
title = {Unified Approach to Implicit and Explicit Solvent Simulations of Electrochemical Reaction Energetics},
author = {Gauthier, Joseph A. and Dickens, Colin F. and Heenen, Hendrik H. and Vijay, Sudarshan and Ringe, Stefan and Chan, Karen},
abstractNote = {One of the major open challenges in ab initio simulations of the electrochemical interface is the determination of electrochemical barriers under a constant driving force. Existing methods to do so include extrapolation techniques based on fully explicit treatments of the electrolyte, as well as implicit solvent models which allow for a continuous variation in electrolyte charge. Emerging hybrid continuum models have the potential to revolutionize the field, since they account for the electrolyte with little computational cost while retaining some explicit electrolyte, representing a “best of both worlds” method. In this work, we present a unified approach to determine reaction energetics from fully explicit, implicit, and hybrid treatments of the electrolyte based on a new multicapacitor model of the electrochemical interface. A given electrode potential can be achieved by a variety of interfacial structures; a crucial insight from this work is that the effective surface charge gives a good proxy of the local potential, the true driving force of electrochemical processes. In contrast, we show that the traditionally considered work function gives rise to multivalued functions depending on the simulation cell size. Furthermore, we show that the reaction energetics are largely insensitive to the countercharge distribution chosen in hybrid implicit/explicit models, which means that any of the myriad implicit electrolyte models can be equivalently applied. Furthermore, this work thus paves the way for the accurate treatment of ab initio reaction energetics of general surface electrochemical processes using both implicit and explicit electrolytes.},
doi = {10.1021/acs.jctc.9b00717},
journal = {Journal of Chemical Theory and Computation},
number = 12,
volume = 15,
place = {United States},
year = {2019},
month = {11}
}

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