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Title: Solvation at metal/water interfaces: An ab initio molecular dynamics benchmark of common computational approaches

Abstract

Determining the influence of the solvent on electrochemical reaction energetics is a central challenge in our understanding of electrochemical interfaces. To date, it is unclear how well existing methods predict solvation energies at solid/liquid interfaces, since they cannot be assessed experimentally. Ab initio molecular dynamics (AIMD) simulations present a physically highly accurate, but also a very costly approach. In this work, we employ extensive AIMD simulations to benchmark solvation at charge-neutral metal/water interfaces against commonly applied continuum solvent models. We consider a variety of adsorbates including *CO, *CHO, *COH, *OCCHO, *OH, and *OOH on Cu, Au, and Pt facets solvated by water. The surfaces and adsorbates considered are relevant, among other reactions, to electrochemical CO2 reduction and the oxygen redox reactions. We determine directional hydrogen bonds and steric water competition to be critical for a correct description of solvation at the metal/water interfaces. As a consequence, we find that the most frequently applied continuum solvation methods, which do not yet capture these properties, do not presently provide more accurate energetics over simulations in vacuum. We find most of the computed benchmark solvation energies to linearly scale with hydrogen bonding or competitive water adsorption, which strongly differ across surfaces. Furthermore, wemore » determine solvation energies of adsorbates to be non-transferable between metal surfaces, in contrast to standard practice.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Technical Univ. of Denmark, Lyngby (Denmark)
  2. Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1633615
Grant/Contract Number:  
AC02-76SF00515; SC0004993; FG02-97ER25308; 9455
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 152; Journal Issue: 14; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ab-initio molecular dynamics; surface and interface chemistry; electrochemical reactions; implicit solvation

Citation Formats

Heenen, Hendrik H., Gauthier, Joseph A., Kristoffersen, Henrik H., Ludwig, Thomas, and Chan, Karen. Solvation at metal/water interfaces: An ab initio molecular dynamics benchmark of common computational approaches. United States: N. p., 2020. Web. doi:10.1063/1.5144912.
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Heenen, Hendrik H., Gauthier, Joseph A., Kristoffersen, Henrik H., Ludwig, Thomas, & Chan, Karen. Solvation at metal/water interfaces: An ab initio molecular dynamics benchmark of common computational approaches. United States. https://doi.org/10.1063/1.5144912
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Heenen, Hendrik H., Gauthier, Joseph A., Kristoffersen, Henrik H., Ludwig, Thomas, and Chan, Karen. Thu . "Solvation at metal/water interfaces: An ab initio molecular dynamics benchmark of common computational approaches". United States. https://doi.org/10.1063/1.5144912. https://www.osti.gov/servlets/purl/1633615.
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@article{osti_1633615,
title = {Solvation at metal/water interfaces: An ab initio molecular dynamics benchmark of common computational approaches},
author = {Heenen, Hendrik H. and Gauthier, Joseph A. and Kristoffersen, Henrik H. and Ludwig, Thomas and Chan, Karen},
abstractNote = {Determining the influence of the solvent on electrochemical reaction energetics is a central challenge in our understanding of electrochemical interfaces. To date, it is unclear how well existing methods predict solvation energies at solid/liquid interfaces, since they cannot be assessed experimentally. Ab initio molecular dynamics (AIMD) simulations present a physically highly accurate, but also a very costly approach. In this work, we employ extensive AIMD simulations to benchmark solvation at charge-neutral metal/water interfaces against commonly applied continuum solvent models. We consider a variety of adsorbates including *CO, *CHO, *COH, *OCCHO, *OH, and *OOH on Cu, Au, and Pt facets solvated by water. The surfaces and adsorbates considered are relevant, among other reactions, to electrochemical CO2 reduction and the oxygen redox reactions. We determine directional hydrogen bonds and steric water competition to be critical for a correct description of solvation at the metal/water interfaces. As a consequence, we find that the most frequently applied continuum solvation methods, which do not yet capture these properties, do not presently provide more accurate energetics over simulations in vacuum. We find most of the computed benchmark solvation energies to linearly scale with hydrogen bonding or competitive water adsorption, which strongly differ across surfaces. Furthermore, we determine solvation energies of adsorbates to be non-transferable between metal surfaces, in contrast to standard practice.},
doi = {10.1063/1.5144912},
journal = {Journal of Chemical Physics},
number = 14,
volume = 152,
place = {United States},
year = {Thu Apr 09 00:00:00 EDT 2020},
month = {Thu Apr 09 00:00:00 EDT 2020}
}
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https://doi.org/10.1063/1.5144912
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