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

Title: Exploring chemical speciation at electrified interfaces using detailed continuum models

Abstract

We present a local free-energy functional-based generic continuum model for material interfaces with a specific emphasis on electrified solid/liquid interfaces. The model enables a description of multicomponent phases at interfaces and includes the effects of specific non-electrostatic interactions (specific adsorption), ion size disparity, and the explicit presence of neutral species. In addition to the optimization of electrostatic, non-electrostatic, and steric forces, the model can be easily modified to explore the effects of other channels for equilibration, including local chemical transformations driven by equilibrium constants and electrochemical reactions driven by the electrode potential. In this way, we show that, upon accounting for these effects, local speciation in the vicinity of the interface can be drastically different from what is expected from restricted models and minor species (from the bulk perspective) may become dominant due to the effects of local pH. We evaluate the ionic contribution to the surface tension at the interface and show how this could impact the structure of air/liquid interfaces. On the same footing, an attempt to describe electrochemical metal dissolution is made. The model allows estimates of the mutual population of newly produced ions depending on their charge and size and could be useful for interpretation ofmore » electrochemical and spectroscopic measurements if the dissolution involves different metal ions (species). With these advances, the proposed model may be used as an ingredient within a hybrid ab initio-continuum methodology to model biased interfaces.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). The Joint Center for Energy Storage Research, The Molecular Foundry
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1543894
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 4; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics

Citation Formats

Baskin, Artem, and Prendergast, David. Exploring chemical speciation at electrified interfaces using detailed continuum models. United States: N. p., 2019. Web. doi:10.1063/1.5058159.
Baskin, Artem, & Prendergast, David. Exploring chemical speciation at electrified interfaces using detailed continuum models. United States. doi:10.1063/1.5058159.
Baskin, Artem, and Prendergast, David. Fri . "Exploring chemical speciation at electrified interfaces using detailed continuum models". United States. doi:10.1063/1.5058159. https://www.osti.gov/servlets/purl/1543894.
@article{osti_1543894,
title = {Exploring chemical speciation at electrified interfaces using detailed continuum models},
author = {Baskin, Artem and Prendergast, David},
abstractNote = {We present a local free-energy functional-based generic continuum model for material interfaces with a specific emphasis on electrified solid/liquid interfaces. The model enables a description of multicomponent phases at interfaces and includes the effects of specific non-electrostatic interactions (specific adsorption), ion size disparity, and the explicit presence of neutral species. In addition to the optimization of electrostatic, non-electrostatic, and steric forces, the model can be easily modified to explore the effects of other channels for equilibration, including local chemical transformations driven by equilibrium constants and electrochemical reactions driven by the electrode potential. In this way, we show that, upon accounting for these effects, local speciation in the vicinity of the interface can be drastically different from what is expected from restricted models and minor species (from the bulk perspective) may become dominant due to the effects of local pH. We evaluate the ionic contribution to the surface tension at the interface and show how this could impact the structure of air/liquid interfaces. On the same footing, an attempt to describe electrochemical metal dissolution is made. The model allows estimates of the mutual population of newly produced ions depending on their charge and size and could be useful for interpretation of electrochemical and spectroscopic measurements if the dissolution involves different metal ions (species). With these advances, the proposed model may be used as an ingredient within a hybrid ab initio-continuum methodology to model biased interfaces.},
doi = {10.1063/1.5058159},
journal = {Journal of Chemical Physics},
number = 4,
volume = 150,
place = {United States},
year = {2019},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide
journal, January 2007

  • Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 111, Issue 2
  • DOI: 10.1021/jp065403l

Towards understanding the structure and capacitance of electrical double layer in ionic liquids
journal, October 2008


Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations
journal, April 2018

  • Sundararaman, Ravishankar; Letchworth-Weaver, Kendra; Schwarz, Kathleen A.
  • The Journal of Chemical Physics, Vol. 148, Issue 14
  • DOI: 10.1063/1.5024219

The Surface Tension of Solutions of Electrolytes as a Function of the Concentration. I. A Differential Method for Measuring Relative Surface Tension
journal, January 1937

  • Jones, Grinnell; Ray, Wendell A.
  • Journal of the American Chemical Society, Vol. 59, Issue 1
  • DOI: 10.1021/ja01280a048

The influence of image interactions on the structure of water and electrolytes in front of a metal surface
journal, February 1997

  • Krämer, A.; Vossen, M.; Forstmann, F.
  • The Journal of Chemical Physics, Vol. 106, Issue 7
  • DOI: 10.1063/1.473378

First-principles molecular dynamics simulations in a continuum solvent
journal, January 2003

  • Fattebert, Jean-Luc; Gygi, François
  • International Journal of Quantum Chemistry, Vol. 93, Issue 2
  • DOI: 10.1002/qua.10548

Modeling the electrified solid–liquid interface
journal, November 2008


Nonlocal electrostatic approach to the double layer and adsorption at the electrode-electrolyte interface
journal, December 1980


How Voltage Drops Are Manifested by Lithium Ion Configurations at Interfaces and in Thin Films on Battery Electrodes
journal, May 2015


Continuous Self-Energy of Ions at the Dielectric Interface
journal, April 2014


The adsorption of iodide ion from aqueous KI + KF of constant ionic strength
journal, February 1966


Electrical double layers. V. Asymmetric ion–wall interactions
journal, December 1984

  • Valleau, J. P.; Torrie, G. M.
  • The Journal of Chemical Physics, Vol. 81, Issue 12
  • DOI: 10.1063/1.447535

A generalized van der Waals model for solvation forces between solute particles in a colloidal suspension
journal, November 1983

  • Freasier, Ben C.; Nordholm, Sture
  • The Journal of Chemical Physics, Vol. 79, Issue 9
  • DOI: 10.1063/1.446328

Density functional theory for differential capacitance of planar electric double layers in ionic liquids
journal, March 2011


Avoiding pitfalls in the modeling of electrochemical interfaces
journal, January 2013


Unravelling the electrochemical double layer by direct probing of the solid/liquid interface
journal, August 2016

  • Favaro, Marco; Jeong, Beomgyun; Ross, Philip N.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12695

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


XXXIX. Structure and capacity of electrical double layer
journal, May 1942

  • Bikerman, J. J.
  • The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, Vol. 33, Issue 220
  • DOI: 10.1080/14786444208520813

Modeling the Electrochemical Hydrogen Oxidation and Evolution Reactions on the Basis of Density Functional Theory Calculations
journal, October 2010

  • Skúlason, Egill; Tripkovic, Vladimir; Björketun, Mårten E.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 42
  • DOI: 10.1021/jp1048887

Influence of cation adsorption on the kinetics of electrode processes
journal, January 1959


Frontiers in first principles modelling of electrochemical simulations
journal, August 2018


The structure of water at a planar wall: An integral equation approach with the central force model
journal, August 1994

  • Vossen, M.; Forstmann, F.
  • The Journal of Chemical Physics, Vol. 101, Issue 3
  • DOI: 10.1063/1.467679

Improving Continuum Models to Define Practical Limits for Molecular Models of Electrified Interfaces
journal, January 2017

  • Baskin, Artem; Prendergast, David
  • Journal of The Electrochemical Society, Vol. 164, Issue 11
  • DOI: 10.1149/2.0461711jes

Unequal size of ions in modified Wicke-Eigen model of electric double layer
journal, January 2017

  • Gongadze, Ekaterina; Kralj-Iglič, Veronika; Iglič, Aleš
  • General physiology and biophysics, Vol. 36, Issue 02
  • DOI: 10.4149/gpb_2016045

Chemisorbed Molecules under Potential Bias: Detailed Insights from First-Principles Vibrational Spectroscopies
journal, March 2014


Classical solvent dynamics and electron transfer. 1. Continuum theory
journal, September 1983

  • Calef, Daniel F.; Wolynes, Peter G.
  • The Journal of Physical Chemistry, Vol. 87, Issue 18
  • DOI: 10.1021/j100241a008

Computational electrochemistry: aqueous one-electron oxidation potentials for substituted anilines
journal, January 2000

  • Winget, Paul; Weber, Eric J.; Cramer, Christopher J.
  • Physical Chemistry Chemical Physics, Vol. 2, Issue 6
  • DOI: 10.1039/a909076b

Computational electrochemistry: prediction of liquid-phase reduction potentials
journal, January 2014

  • Marenich, Aleksandr V.; Ho, Junming; Coote, Michelle L.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 29
  • DOI: 10.1039/c4cp01572j

Adsorption of bromide ions on single crystals of gold
journal, August 1983

  • Nguyen Van Huong, C.; Hinnen, C.; Rousseau, A.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 151, Issue 1-2
  • DOI: 10.1016/s0022-0728(83)80430-6

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


Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry
journal, March 2017

  • Sundararaman, Ravishankar; Goddard, William A.; Arias, Tomas A.
  • The Journal of Chemical Physics, Vol. 146, Issue 11
  • DOI: 10.1063/1.4978411

Fundamental measure theory for hard-sphere mixtures: a review
journal, January 2010


Ionic Components of Charge in the Electrical Double Layer
journal, March 1954

  • Grahame, David C.; Soderberg, Barbara A.
  • The Journal of Chemical Physics, Vol. 22, Issue 3
  • DOI: 10.1063/1.1740089

Finite-bias electronic transport of molecules in a water solution
journal, June 2010


Electrochemical reduction of an anion for ionic-liquid molecules on a lithium electrode studied by first-principles calculations
journal, September 2014


A generalized Poisson and Poisson-Boltzmann solver for electrostatic environments
journal, January 2016

  • Fisicaro, G.; Genovese, L.; Andreussi, O.
  • The Journal of Chemical Physics, Vol. 144, Issue 1
  • DOI: 10.1063/1.4939125

Raumbedarf und Aktivitätskoeffizienten starker Elektrolyte in wäßriger Lösung
journal, January 1953


Toward First Principles Prediction of Voltage Dependences of Electrolyte/Electrolyte Interfacial Processes in Lithium Ion Batteries
journal, November 2013

  • Leung, Kevin; Tenney, Craig M.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 46
  • DOI: 10.1021/jp408974k

Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges
journal, February 2017

  • Canepa, Pieremanuele; Sai Gautam, Gopalakrishnan; Hannah, Daniel C.
  • Chemical Reviews, Vol. 117, Issue 5
  • DOI: 10.1021/acs.chemrev.6b00614

Calculation of Solvation Free Energies of Charged Solutes Using Mixed Cluster/Continuum Models
journal, August 2008

  • Bryantsev, Vyacheslav S.; Diallo, Mamadou S.; Goddard III, William A.
  • The Journal of Physical Chemistry B, Vol. 112, Issue 32
  • DOI: 10.1021/jp802665d

On the effect of dielectric saturation on the swelling of clays
journal, March 1992


Determination of specific adsorption of some simple anions at a polycrystalline silver-aqueous interface using differential capacitance and kinetic probe techniques
journal, September 1982

  • Larkin, D.; Guyer, Kendall L.; Hupp, Joseph T.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 138, Issue 2
  • DOI: 10.1016/0022-0728(82)85091-2

Structure of electric double layers in capacitive systems and to what extent (classical) density functional theory describes it
journal, September 2017


Investigation of Dielectric Decrement and Correlation Effects on Electric Double-Layer Capacitance by Self-Consistent Field Model
journal, July 2016


The Dielectric Constant of Water and the Saturation Effect
journal, April 1951


Molecular dynamics simulations of water and ion dynamics in the electrochemical double layer
journal, September 2002


Detecting the undetectable: The role of trace surfactant in the Jones-Ray effect
journal, November 2018

  • Duignan, Timothy T.; Peng, Mengsu; Nguyen, Anh V.
  • The Journal of Chemical Physics, Vol. 149, Issue 19
  • DOI: 10.1063/1.5050421

Theory of simple classical fluids: Universality in the short-range structure
journal, September 1979


Density functional theory for inhomogeneous mixtures of polymeric fluids
journal, August 2002

  • Yu, Yang-Xin; Wu, Jianzhong
  • The Journal of Chemical Physics, Vol. 117, Issue 5
  • DOI: 10.1063/1.1491240

A model for the electrical double layer combining integral equation techniques with quantum density functional theory
journal, August 2011


The concept of absolute electrode potential an attempt at a calculation
journal, May 1974


Specific adsorption of bromide and iodide anions from nonaqueous solutions on controlled-surface polycrystalline silver electrodes
journal, August 2006

  • Falciola, Luigi; Mussini, Patrizia R.; Trasatti, Sergio
  • Journal of Electroanalytical Chemistry, Vol. 593, Issue 1-2
  • DOI: 10.1016/j.jelechem.2006.03.053

Electrochemical Windows of Room-Temperature Ionic Liquids from Molecular Dynamics and Density Functional Theory Calculations
journal, June 2011

  • Ong, Shyue Ping; Andreussi, Oliviero; Wu, Yabi
  • Chemistry of Materials, Vol. 23, Issue 11
  • DOI: 10.1021/cm200679y

The anatomy of the double layer and capacitance in ionic liquids with anisotropic ions: Electrostriction vs. lattice saturation
journal, November 2010


First-principles molecular dynamics simulation of biased electrode/solution interface
journal, November 2007


A simple density functional theory for inhomogeneous liquids: Wetting by gas at a solid-liquid interface
journal, July 1984


Reactivity at the Lithium–Metal Anode Surface of Lithium–Sulfur Batteries
journal, November 2015

  • Camacho-Forero, Luis E.; Smith, Taylor W.; Bertolini, Samuel
  • The Journal of Physical Chemistry C, Vol. 119, Issue 48
  • DOI: 10.1021/acs.jpcc.5b08254

Double-layer effects on simple electrode reactions
journal, November 1977

  • Weaver, Michael J.; Anson, Fred C.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 84, Issue 1
  • DOI: 10.1016/s0022-0728(77)80227-1

Electrosorption Valency and Partial Charge Transfer in Halide and Sulfide Adsorption on Ag(111)
journal, November 1998

  • Foresti, Maria Luisa; Innocenti, Massimo; Forni, Francesca
  • Langmuir, Vol. 14, Issue 24
  • DOI: 10.1021/la980692t

The electrical double layer. III. Modified Gouy−Chapman theory with unequal ion sizes
journal, May 1982

  • Valleau, J. P.; Torrie, G. M.
  • The Journal of Chemical Physics, Vol. 76, Issue 9
  • DOI: 10.1063/1.443542

Concentration and chemical-state profiles at heterogeneous interfaces with sub-nm accuracy from standing-wave ambient-pressure photoemission
journal, November 2014

  • Nemšák, Slavomír; Shavorskiy, Andrey; Karslioglu, Osman
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6441

The relation between the capacity of the electrode double layer and the adsorption of surface-active material
journal, January 1959


The importance of nonlinear fluid response in joint density-functional theory studies of battery systems
journal, October 2013

  • Gunceler, Deniz; Letchworth-Weaver, Kendra; Sundararaman, Ravishankar
  • Modelling and Simulation in Materials Science and Engineering, Vol. 21, Issue 7
  • DOI: 10.1088/0965-0393/21/7/074005

Generic density functional for electric double layers in a molecular solvent
journal, April 1998


The Minimum Entropy Production Principle
journal, October 1980


On the theoretical description of weakly charged surfaces
journal, March 2015

  • Wang, Rui; Wang, Zhen-Gang
  • The Journal of Chemical Physics, Vol. 142, Issue 10
  • DOI: 10.1063/1.4914170

Ab Initio Molecular Dynamics for Molecules with Variable Numbers of Electrons
journal, May 2002


Toward a Unified Picture of the Water Self-Ions at the Air–Water Interface: A Density Functional Theory Perspective
journal, May 2014

  • Baer, Marcel D.; Kuo, I-Feng W.; Tobias, Douglas J.
  • The Journal of Physical Chemistry B, Vol. 118, Issue 28
  • DOI: 10.1021/jp501854h

Theoretical modeling of electrode/electrolyte interface from first-principles periodic continuum solvation method
journal, March 2013


Aqueous Solvation Free Energies of Ions and Ion−Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton
journal, August 2006

  • Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 32
  • DOI: 10.1021/jp063552y

Molecular dynamics simulations of solutions at constant chemical potential
journal, April 2015

  • Perego, C.; Salvalaglio, M.; Parrinello, M.
  • The Journal of Chemical Physics, Vol. 142, Issue 14
  • DOI: 10.1063/1.4917200

Effect of thermal motion on catalytic activity of nanoparticles in polar solvent
journal, January 2014

  • Bonnet, Nicéphore; Sugino, Osamu; Otani, Minoru
  • The Journal of Chemical Physics, Vol. 140, Issue 4
  • DOI: 10.1063/1.4862503

Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004

  • Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 46
  • DOI: 10.1021/jp047349j

Function-Space-Based Solution Scheme for the Size-Modified Poisson–Boltzmann Equation in Full-Potential DFT
journal, July 2016

  • Ringe, Stefan; Oberhofer, Harald; Hille, Christoph
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 8
  • DOI: 10.1021/acs.jctc.6b00435

Towards an understanding of induced-charge electrokinetics at large applied voltages in concentrated solutions
journal, November 2009

  • Bazant, Martin Z.; Kilic, Mustafa Sabri; Storey, Brian D.
  • Advances in Colloid and Interface Science, Vol. 152, Issue 1-2
  • DOI: 10.1016/j.cis.2009.10.001

Double-Layer in Ionic Liquids:  Paradigm Change?
journal, May 2007

  • Kornyshev, Alexei A.
  • The Journal of Physical Chemistry B, Vol. 111, Issue 20
  • DOI: 10.1021/jp067857o