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:
-
[2];
[3];
[4]
- Sao Paulo State Univ., Sao Paulo (Brazil); Federal Univ. of ABC, Santo Andre (Brazil)
- Center of Materials Physics (CFM), San Sebastian (Spain); Donostia International Physics Center, San Sebastian (Spain)
- Sao Paulo State Univ., Sao Paulo (Brazil)
- 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) (SC-22)
- 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.
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. Wed .
"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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Cited by: 4 works
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Figures / Tables:
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 »
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Works referenced in this record:
The interaction of water with solid surfaces: Fundamental aspects
journal, October 1987
- Thiel, Patricia A.; Madey, Theodore E.
- Surface Science Reports, Vol. 7, Issue 6-8, p. 211-385
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
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
Water at an electrochemical interface—a simulation study
journal, January 2009
- Willard, Adam P.; Reed, Stewart K.; Madden, Paul A.
- Faraday Discuss., Vol. 141
Electron and phonon drag in thermoelectric transport through coherent molecular conductors
journal, May 2016
- Lü, Jing-Tao; Wang, Jian-Sheng; Hedegård, Per
- Physical Review B, Vol. 93, Issue 20
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
Current-induced energy barrier suppression for electromigration from first principles
journal, August 2011
- Zhang, Ruoxing; Rungger, Ivan; Sanvito, Stefano
- Physical Review B, Vol. 84, Issue 8
Ab initio study of electron transport in dry poly(G)-poly(C) -DNA strands
journal, September 2010
- Pemmaraju, C. D.; Rungger, I.; Chen, X.
- Physical Review B, Vol. 82, Issue 12
Spin and molecular electronics in atomically generated orbital landscapes
journal, February 2006
- Rocha, A. R.; García-Suárez, V. M.; Bailey, S.
- Physical Review B, Vol. 73, Issue 8
Hellmann-Feynman theorem and the definition of forces in quantum time-dependent and transport problems
journal, June 2000
- Di Ventra, Massimiliano; Pantelides, Sokrates T.
- Physical Review B, Vol. 61, Issue 23
Self-consistent order- density-functional calculations for very large systems
journal, April 1996
- Ordejón, Pablo; Artacho, Emilio; Soler, José M.
- Physical Review B, Vol. 53, Issue 16
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
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
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
Water at Interfaces
journal, April 2016
- Björneholm, Olle; Hansen, Martin H.; Hodgson, Andrew
- Chemical Reviews, Vol. 116, Issue 13
Towards molecular spintronics
journal, March 2005
- Rocha, Alexandre R.; García-suárez, Víctor M.; Bailey, Steve W.
- Nature Materials, Vol. 4, Issue 4
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
Renormalization of Optical Excitations in Molecules near a Metal Surface
journal, May 2011
- Garcia-Lastra, J. M.; Thygesen, K. S.
- Physical Review Letters, Vol. 106, Issue 18
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
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
First-principles calculations of charged surfaces and interfaces: A plane-wave nonrepeated slab approach
journal, March 2006
- Otani, M.; Sugino, O.
- Physical Review B, Vol. 73, Issue 11
Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965
- Kohn, W.; Sham, L. J.
- Physical Review, Vol. 140, Issue 4A, p. A1133-A1138
Self-consistent GW calculations of electronic transport in thiol- and amine-linked molecular junctions
journal, March 2011
- Strange, M.; Rostgaard, C.; Häkkinen, H.
- Physical Review B, Vol. 83, Issue 11
Efficient pseudopotentials for plane-wave calculations
journal, January 1991
- Troullier, N.; Martins, José Luriaas
- Physical Review B, Vol. 43, Issue 3
Nonconservative generalized current-induced forces
journal, February 2010
- Todorov, Tchavdar N.; Dundas, Daniel; McEniry, Eunan J.
- Physical Review B, Vol. 81, Issue 7
Renormalization of Molecular Electronic Levels at Metal-Molecule Interfaces
journal, November 2006
- Neaton, J. B.; Hybertsen, Mark S.; Louie, Steven G.
- Physical Review Letters, Vol. 97, Issue 21
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
First-Principles Molecular Dynamics at a Constant Electrode Potential
journal, December 2012
- Bonnet, Nicéphore; Morishita, Tetsuya; Sugino, Osamu
- Physical Review Letters, Vol. 109, Issue 26
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
Effect of Adsorbed Helium on Electron Tunneling between Metal Electrodes
journal, February 1996
- Keijsers, R. J. P.; Voets, J.; Shklyarevskii, O. I.
- Physical Review Letters, Vol. 76, Issue 7
The structure of interfacial water on gold electrodes studied by x-ray absorption spectroscopy
journal, October 2014
- Velasco-Velez, J. -J.; Wu, C. H.; Pascal, T. A.
- Science, Vol. 346, Issue 6211
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
Water adsorption and the wetting of metal surfaces
journal, September 2009
- Hodgson, A.; Haq, S.
- Surface Science Reports, Vol. 64, Issue 9
Self-Interaction Errors in Density-Functional Calculations of Electronic Transport
journal, September 2005
- Toher, C.; Filippetti, A.; Sanvito, S.
- Physical Review Letters, Vol. 95, Issue 14
Inhomogeneous Electron Gas
journal, November 1964
- Hohenberg, P.; Kohn, W.
- Physical Review, Vol. 136, Issue 3B, p. B864-B871
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
Constrained-DFT method for accurate energy-level alignment of metal/molecule interfaces
journal, October 2013
- Souza, A. M.; Rungger, I.; Pemmaraju, C. D.
- Physical Review B, Vol. 88, Issue 16
Towards first principles modeling of electrochemical electrode–electrolyte interfaces
journal, January 2015
- Nielsen, Malte; Björketun, Mårten E.; Hansen, Martin H.
- Surface Science, Vol. 631
Current-induced phonon renormalization in molecular junctions
journal, July 2016
- Bai, Meilin; Cucinotta, Clotilde S.; Jiang, Zhuoling
- Physical Review B, Vol. 94, Issue 3
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
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
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
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
Alignment of electronic energy levels at electrochemical interfaces
journal, January 2012
- Cheng, Jun; Sprik, Michiel
- Physical Chemistry Chemical Physics, Vol. 14, Issue 32
General Model for Water Monomer Adsorption on Close-Packed Transition and Noble Metal Surfaces
journal, May 2003
- Michaelides, A.; Ranea, V. A.; de Andres, P. L.
- Physical Review Letters, Vol. 90, Issue 21
First-principles computational electrochemistry: Achievements and challenges
journal, December 2012
- Calle-Vallejo, Federico; Koper, Marc T. M.
- Electrochimica Acta, Vol. 84
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
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
Imaging Pauli Repulsion in Scanning Tunneling Microscopy
journal, August 2010
- Weiss, C.; Wagner, C.; Kleimann, C.
- Physical Review Letters, Vol. 105, Issue 8
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