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Title: Bias-dependent local structure of water molecules at a metallic interface

Understanding the local structure of water at the interfaces of metallic electrodes is a key issue in aqueous-based electrochemistry. Nevertheless a realistic simulation of such a setup is challenging, particularly when the electrodes are maintained at different potentials. To correctly compute the effect of an external bias potential applied to truly semi-infinite surfaces, we combine Density Functional Theory (DFT) and Non-Equilibrium Green’s Function (NEGF) methods. This framework allows for the out-of-equilibrium calculation of forces and dynamics, and directly correlates to the chemical potential of the electrodes, which is introduced experimentally. In this work, we apply this methodology to study the electronic properties and atomic forces of a water molecule at the interface of a gold surface. We find that the water molecule tends to align its dipole moment with the electric field, and it is either repelled or attracted to the metal depending on the sign and magnitude of the applied bias, in an asymmetric fashion.
Authors:
 [1] ; ORCiD logo [2] ; ORCiD logo [3] ; ORCiD logo [4]
  1. Sao Paulo State Univ., Sao Paulo (Brazil); Federal Univ. of ABC, Santo Andre (Brazil)
  2. Center of Materials Physics (CFM), San Sebastian (Spain); Donostia International Physics Center, San Sebastian (Spain)
  3. Sao Paulo State Univ., Sao Paulo (Brazil)
  4. Stony Brook Univ., Stony Brook, NY (United States)
Publication Date:
Grant/Contract Number:
SC0001137; SC0003871; AC02-98CH10886
Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Research Org:
Brookhaven National Lab. (BNL), Upton, NY (United States); Research Foundation for the State Univ. of New York (SUNYRF), Albany, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1506084

Pedroza, Luana S., Brandimarte, Pedro, Rocha, Alexandre Reily, and Fernández-Serra, M. -V.. Bias-dependent local structure of water molecules at a metallic interface. United States: N. p., Web. doi:10.1039/c7sc02208e.
Pedroza, Luana S., Brandimarte, Pedro, Rocha, Alexandre Reily, & Fernández-Serra, M. -V.. Bias-dependent local structure of water molecules at a metallic interface. United States. doi:10.1039/c7sc02208e.
Pedroza, Luana S., Brandimarte, Pedro, Rocha, Alexandre Reily, and Fernández-Serra, M. -V.. 2017. "Bias-dependent local structure of water molecules at a metallic interface". United States. doi:10.1039/c7sc02208e. https://www.osti.gov/servlets/purl/1506084.
@article{osti_1506084,
title = {Bias-dependent local structure of water molecules at a metallic interface},
author = {Pedroza, Luana S. and Brandimarte, Pedro and Rocha, Alexandre Reily and Fernández-Serra, M. -V.},
abstractNote = {Understanding the local structure of water at the interfaces of metallic electrodes is a key issue in aqueous-based electrochemistry. Nevertheless a realistic simulation of such a setup is challenging, particularly when the electrodes are maintained at different potentials. To correctly compute the effect of an external bias potential applied to truly semi-infinite surfaces, we combine Density Functional Theory (DFT) and Non-Equilibrium Green’s Function (NEGF) methods. This framework allows for the out-of-equilibrium calculation of forces and dynamics, and directly correlates to the chemical potential of the electrodes, which is introduced experimentally. In this work, we apply this methodology to study the electronic properties and atomic forces of a water molecule at the interface of a gold surface. We find that the water molecule tends to align its dipole moment with the electric field, and it is either repelled or attracted to the metal depending on the sign and magnitude of the applied bias, in an asymmetric fashion.},
doi = {10.1039/c7sc02208e},
journal = {Chemical Science},
number = 1,
volume = 9,
place = {United States},
year = {2017},
month = {10}
}

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