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Title: Solvent–Adsorbate Interactions and Adsorbate-Specific Solvent Structure in Carbon Dioxide Reduction on a Stepped Cu Surface

Abstract

In this work, the structure of water and its interactions with various carbon dioxide reduction intermediates adsorbed on a Cu(211) surface is investigated using density functional theory. We find that the presence of adsorbates has a significant and adsorbate-specific effect on the local water structure and that solvation can stabilize adsorbate conformations different from those found in vacuum. We describe relationships between the hydrogen bonding capability of an adsorbate, the dipole moment of the adsorbate, the energetic strength of water–adsorbate interactions, and the change induced in the local water orientation by the adsorbate. Mechanistic implications are discussed. Here, we investigate and quantify the error associated with using arbitrary locally optimized solvent structures in calculations of relevant physical quantities, such as solvated binding energies and work functions. Possible effects of thermal motion on calculations of the work function are investigated using ab initio molecular dynamics.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [1];  [2]; ORCiD logo [2]
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, 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)
OSTI Identifier:
1529086
Grant/Contract Number:  
AC02-76SF00515; SC0008685; FG02-97ER25308
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 123; Journal Issue: 10; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

Citation Formats

Ludwig, Thomas, Gauthier, Joseph A., Brown, Kristopher S., Ringe, Stefan, Nørskov, Jens K., and Chan, Karen. Solvent–Adsorbate Interactions and Adsorbate-Specific Solvent Structure in Carbon Dioxide Reduction on a Stepped Cu Surface. United States: N. p., 2019. Web. doi:10.1021/acs.jpcc.8b11571.
Ludwig, Thomas, Gauthier, Joseph A., Brown, Kristopher S., Ringe, Stefan, Nørskov, Jens K., & Chan, Karen. Solvent–Adsorbate Interactions and Adsorbate-Specific Solvent Structure in Carbon Dioxide Reduction on a Stepped Cu Surface. United States. doi:10.1021/acs.jpcc.8b11571.
Ludwig, Thomas, Gauthier, Joseph A., Brown, Kristopher S., Ringe, Stefan, Nørskov, Jens K., and Chan, Karen. Fri . "Solvent–Adsorbate Interactions and Adsorbate-Specific Solvent Structure in Carbon Dioxide Reduction on a Stepped Cu Surface". United States. doi:10.1021/acs.jpcc.8b11571.
@article{osti_1529086,
title = {Solvent–Adsorbate Interactions and Adsorbate-Specific Solvent Structure in Carbon Dioxide Reduction on a Stepped Cu Surface},
author = {Ludwig, Thomas and Gauthier, Joseph A. and Brown, Kristopher S. and Ringe, Stefan and Nørskov, Jens K. and Chan, Karen},
abstractNote = {In this work, the structure of water and its interactions with various carbon dioxide reduction intermediates adsorbed on a Cu(211) surface is investigated using density functional theory. We find that the presence of adsorbates has a significant and adsorbate-specific effect on the local water structure and that solvation can stabilize adsorbate conformations different from those found in vacuum. We describe relationships between the hydrogen bonding capability of an adsorbate, the dipole moment of the adsorbate, the energetic strength of water–adsorbate interactions, and the change induced in the local water orientation by the adsorbate. Mechanistic implications are discussed. Here, we investigate and quantify the error associated with using arbitrary locally optimized solvent structures in calculations of relevant physical quantities, such as solvated binding energies and work functions. Possible effects of thermal motion on calculations of the work function are investigated using ab initio molecular dynamics.},
doi = {10.1021/acs.jpcc.8b11571},
journal = {Journal of Physical Chemistry. C},
number = 10,
volume = 123,
place = {United States},
year = {2019},
month = {2}
}

Journal Article:
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This content will become publicly available on February 15, 2020
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