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

Abstract

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]
+ Show Author Affiliations
  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:
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)
OSTI Identifier:
1506084
Grant/Contract Number:  
SC0001137; SC0003871; AC02-98CH10886
Resource 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
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

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., 2017. Web. doi:10.1039/c7sc02208e.
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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. https://doi.org/10.1039/c7sc02208e
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Pedroza, Luana S., Brandimarte, Pedro, Rocha, Alexandre Reily, and Fernández-Serra, M. -V. Wed . "Bias-dependent local structure of water molecules at a metallic interface". United States. https://doi.org/10.1039/c7sc02208e. https://www.osti.gov/servlets/purl/1506084.
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@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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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1039/c7sc02208e
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Cited by: 5 works
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Figures / Tables:

Fig. 1 Fig. 1: (a) A schematic view of the metal–water system used for the non-equilibrium calculations; the left (right) electrodes (LE/RE) and scattering region (SR) are indicated. (b) A sketch of the effect of a positive bias potential on a parallel plate capacitor; the corresponding charge accumulated in each plate, asmore » well as the bias ramp, is shown.« less
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