skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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.
Copy to clipboard
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:https://doi.org/10.1039/c7sc02208e
Copy to clipboard
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. doi:https://doi.org/10.1039/c7sc02208e. https://www.osti.gov/servlets/purl/1506084.
Copy to clipboard
@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}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI:  https://doi.org/10.1039/c7sc02208e
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

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
All figures and tables (6 total)
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

The interaction of water with solid surfaces: Fundamental aspects
journal, October 1987

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Anomalous Wetting Layer at the Au(111) Surface
journal, September 2011

  • Cicero, G.; Calzolari, A.; Corni, S.
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 20
  • DOI: 10.1021/jz200989n

Water at an electrochemical interface—a simulation study
journal, January 2009

  • Willard, Adam P.; Reed, Stewart K.; Madden, Paul A.
  • Faraday Discuss., Vol. 141
  • DOI: 10.1039/B805544K

Electron and phonon drag in thermoelectric transport through coherent molecular conductors
journal, May 2016

Stretching of BDT-gold molecular junctions: thiol or thiolate termination?
journal, January 2014

  • Souza, Amaury de Melo; Rungger, Ivan; Pontes, Renato Borges
  • Nanoscale, Vol. 6, Issue 23
  • DOI: 10.1039/C4NR04081C

Current-induced energy barrier suppression for electromigration from first principles
journal, August 2011

Ab initio study of electron transport in dry poly(G)-poly(C) A -DNA strands
journal, September 2010

The road from animal electricity to green energy: combining experiment and theory in electrocatalysis
journal, January 2012

  • Greeley, Jeffrey; Markovic, Nenad M.
  • Energy & Environmental Science, Vol. 5, Issue 11
  • DOI: 10.1039/c2ee21754f

The role of hydrogen bonding in water–metal interactions
journal, January 2011

  • Poissier, Adrien; Ganeshan, Sriram; Fernández-Serra, M. V.
  • Phys. Chem. Chem. Phys., Vol. 13, Issue 8
  • DOI: 10.1039/C0CP00994F

Spin and molecular electronics in atomically generated orbital landscapes
journal, February 2006

Hellmann-Feynman theorem and the definition of forces in quantum time-dependent and transport problems
journal, June 2000

Self-consistent order- N density-functional calculations for very large systems
journal, April 1996

Insight from first principles into the nature of the bonding between water molecules and 4d metal surfaces
journal, January 2009

  • Carrasco, Javier; Michaelides, Angelos; Scheffler, Matthias
  • The Journal of Chemical Physics, Vol. 130, Issue 18
  • DOI: 10.1063/1.3125002

Direct calculation of the tunneling current
journal, June 1971

  • Caroli, C.; Combescot, R.; Nozieres, P.
  • Journal of Physics C: Solid State Physics, Vol. 4, Issue 8
  • DOI: 10.1088/0022-3719/4/8/018

Density, structure, and dynamics of water: The effect of van der Waals interactions
journal, January 2011

  • Wang, Jue; Román-Pérez, G.; Soler, Jose M.
  • The Journal of Chemical Physics, Vol. 134, Issue 2
  • DOI: 10.1063/1.3521268

Water at Interfaces
journal, April 2016

Towards molecular spintronics
journal, March 2005

  • Rocha, Alexandre R.; García-suárez, Víctor M.; Bailey, Steve W.
  • Nature Materials, Vol. 4, Issue 4
  • DOI: 10.1038/nmat1349

Density-functional method for nonequilibrium electron transport
journal, March 2002

  • Brandbyge, Mads; Mozos, José-Luis; Ordejón, Pablo
  • Physical Review B, Vol. 65, Issue 16, Article No. 165401
  • DOI: 10.1103/PhysRevB.65.165401

Renormalization of Optical Excitations in Molecules near a Metal Surface
journal, May 2011

Interaction of Water Molecule with Au(111) and Au(110) Surfaces under the Influence of an External Electric Field
journal, February 2014

  • Huzayyin, Ahmed; Chang, Jin Hyun; Lian, Keryn
  • The Journal of Physical Chemistry C, Vol. 118, Issue 7
  • DOI: 10.1021/jp408001t

Influence of surface topology and electrostatic potential on water/electrode systems
journal, January 1995

  • Siepmann, J. Ilja; Sprik, Michiel
  • The Journal of Chemical Physics, Vol. 102, Issue 1
  • DOI: 10.1063/1.469429

First-principles calculations of charged surfaces and interfaces: A plane-wave nonrepeated slab approach
journal, March 2006

Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965

Self-consistent GW calculations of electronic transport in thiol- and amine-linked molecular junctions
journal, March 2011

Efficient pseudopotentials for plane-wave calculations
journal, January 1991

Nonconservative generalized current-induced forces
journal, February 2010

Renormalization of Molecular Electronic Levels at Metal-Molecule Interfaces
journal, November 2006

Elucidation of the Electrochemical Activation of Water over Pd by First Principles
journal, January 2006

  • Filhol, Jean-Sébastien; Neurock, Matthew
  • Angewandte Chemie International Edition, Vol. 45, Issue 3
  • DOI: 10.1002/anie.200502540

First-Principles Molecular Dynamics at a Constant Electrode Potential
journal, December 2012

An abinitio study of electrochemical vs. electromechanical properties: the case of CO adsorbed on a Pt(111) surface
journal, January 2011

  • Mamatkulov, M.; Filhol, J. -S.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 17
  • DOI: 10.1039/c0cp01444c

Effect of Adsorbed Helium on Electron Tunneling between Metal Electrodes
journal, February 1996

The structure of interfacial water on gold electrodes studied by x-ray absorption spectroscopy
journal, October 2014

Forces in Molecules
journal, August 1939

Local order of liquid water at metallic electrode surfaces
journal, January 2015

  • Pedroza, Luana S.; Poissier, Adrien; Fernández-Serra, M. -V.
  • The Journal of Chemical Physics, Vol. 142, Issue 3
  • DOI: 10.1063/1.4905493

Water adsorption and the wetting of metal surfaces
journal, September 2009

Self-Interaction Errors in Density-Functional Calculations of Electronic Transport
journal, September 2005

Inhomogeneous Electron Gas
journal, November 1964

A Computationally Efficient Treatment of Polarizable Electrochemical Cells Held at a Constant Potential
journal, February 2012

  • Petersen, Matt K.; Kumar, Revati; White, Henry S.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 7
  • DOI: 10.1021/jp210252g

Constrained-DFT method for accurate energy-level alignment of metal/molecule interfaces
journal, October 2013

Van der Waals Density Functional for General Geometries
journal, June 2004

Towards first principles modeling of electrochemical electrode–electrolyte interfaces
journal, January 2015

Current-induced phonon renormalization in molecular junctions
journal, July 2016

Addressing the Environment Electrostatic Effect on Ballistic Electron Transport in Large Systems: A QM/MM-NEGF Approach
journal, July 2017

  • Feliciano, Gustavo T.; Sanz-Navarro, Carlos; Coutinho-Neto, Mauricio Domingues
  • The Journal of Physical Chemistry B, Vol. 122, Issue 2
  • DOI: 10.1021/acs.jpcb.7b03475

Voltage-dependent ordering of water molecules at an electrode–electrolyte interface
journal, March 1994

  • Toney, Michael F.; Howard, Jason N.; Richer, Jocelyn
  • Nature, Vol. 368, Issue 6470
  • DOI: 10.1038/368444a0

Towards the computational design of solid catalysts
journal, April 2009

  • Nørskov, J.; Bligaard, T.; Rossmeisl, J.
  • Nature Chemistry, Vol. 1, Issue 1, p. 37-46
  • DOI: 10.1038/nchem.121

Potential-Dependent Reorientation of Water Molecules at an Electrode/Electrolyte Interface Studied by Surface-Enhanced Infrared Absorption Spectroscopy
journal, January 1996

  • Ataka, Ken-ichi; Yotsuyanagi, Takao; Osawa, Masatoshi
  • The Journal of Physical Chemistry, Vol. 100, Issue 25
  • DOI: 10.1021/jp953636z

Alignment of electronic energy levels at electrochemical interfaces
journal, January 2012

  • Cheng, Jun; Sprik, Michiel
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 32
  • DOI: 10.1039/c2cp41652b

General Model for Water Monomer Adsorption on Close-Packed Transition and Noble Metal Surfaces
journal, May 2003

First-principles computational electrochemistry: Achievements and challenges
journal, December 2012

First principles reaction modeling of the electrochemical interface: Consideration and calculation of a tunable surface potential from atomic and electronic structure
journal, April 2006

  • Taylor, Christopher D.; Wasileski, Sally A.; Filhol, Jean-Sebastien
  • Physical Review B, Vol. 73, Issue 16
  • DOI: 10.1103/PhysRevB.73.165402

Capacitive DNA Detection Driven by Electronic Charge Fluctuations in a Graphene Nanopore
journal, March 2015

  • Feliciano, Gustavo T.; Sanz-Navarro, Carlos; Coutinho-Neto, Mauricio Domingues
  • Physical Review Applied, Vol. 3, Issue 3
  • DOI: 10.1103/PhysRevApplied.3.034003

Imaging Pauli Repulsion in Scanning Tunneling Microscopy
journal, August 2010

    [ × clear filter / sort ]

    Works referencing / citing this record:

    Interfacial structural crossover and hydration thermodynamics of charged C 60 in water
    journal, January 2018

    • Sarhangi, Setare Mostajabi; Waskasi, Morteza M.; Hashemianzadeh, Seyed Majid
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 42
    • DOI: 10.1039/c8cp05422c

    Circular current and induced force in a molecular ring junction
    journal, January 2019

    Dissecting energy level renormalization and polarizability enhancement of molecules at surfaces with subsystem TDDFT
    journal, October 2018

    • Umerbekova, Alina; Zhang, Shou-Feng; Kumar P., Sudheer
    • The European Physical Journal B, Vol. 91, Issue 10
    • DOI: 10.1140/epjb/e2018-90145-2
      [ × clear filter / sort ]

      Figures / Tables found in this record:

      Fig. 1 (p. 3)figure
      Fig. 2 (p. 5)figure
      Fig. 3 (p. 6)figure
      Fig. 4 (p. 6)figure
      Fig. 5 (p. 6)figure
      Fig. 6 (p. 7)figure
        [ × clear filter / sort ]
        Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

        Similar Records in DOE PAGES and OSTI.GOV collections: