Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations

Sundararaman, Ravishankar; Letchworth-Weaver, Kendra; Schwarz, Kathleen A.

doi:10.1063/1.5024219

Title: Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations

Abstract

Here, reliable first-principles calculations of electrochemical processes require accurate prediction of the interfacial capacitance, a challenge for current computationally efficient continuum solvation methodologies. We develop a model for the double layer of a metallic electrode that reproduces the features of the experimental capacitance of Ag(100) in a non-adsorbing, aqueous electrolyte, including a broad hump in the capacitance near the potential of zero charge and a dip in the capacitance under conditions of low ionic strength. Using this model, we identify the necessary characteristics of a solvation model suitable for first-principles electrochemistry of metal surfaces in non-adsorbing, aqueous electrolytes: dielectric and ionic nonlinearity, and a dielectric-only region at the interface. The dielectric nonlinearity, caused by the saturation of dipole rotational response in water, creates the capacitance hump, while ionic nonlinearity, caused by the compactness of the diffuse layer, generates the capacitance dip seen at low ionic strength. We show that none of the previously developed solvation models simultaneously meet all these criteria. We design the nonlinear electrochemical soft-sphere solvation model which both captures the capacitance features observed experimentally and serves as a general-purpose continuum solvation model.

Authors:

^[1]; Letchworth-Weaver, Kendra ^[2];

^[3]

Rensselaer Polytechnic Inst., Troy, NY (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)

Publication Date:: 2018-04-11

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; Rensselaer Polytechnic Institute

OSTI Identifier:: 1459895

Alternate Identifier(s):: OSTI ID: 1432740

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 148; Journal Issue: 14; 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

Citation Formats


                    Sundararaman, Ravishankar, Letchworth-Weaver, Kendra, and Schwarz, Kathleen A. Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations.  United States: N. p., 2018. 
Web.  doi:10.1063/1.5024219.

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                    Sundararaman, Ravishankar, Letchworth-Weaver, Kendra, & Schwarz, Kathleen A. Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations.  United States.  https://doi.org/10.1063/1.5024219

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                    Sundararaman, Ravishankar, Letchworth-Weaver, Kendra, and Schwarz, Kathleen A. Wed .  
"Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations".  United States.  https://doi.org/10.1063/1.5024219.  https://www.osti.gov/servlets/purl/1459895.

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@article{osti_1459895,

  title        = {Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations},

  author       = {Sundararaman, Ravishankar and Letchworth-Weaver, Kendra and Schwarz, Kathleen A.},

  abstractNote = {Here, reliable first-principles calculations of electrochemical processes require accurate prediction of the interfacial capacitance, a challenge for current computationally efficient continuum solvation methodologies. We develop a model for the double layer of a metallic electrode that reproduces the features of the experimental capacitance of Ag(100) in a non-adsorbing, aqueous electrolyte, including a broad hump in the capacitance near the potential of zero charge and a dip in the capacitance under conditions of low ionic strength. Using this model, we identify the necessary characteristics of a solvation model suitable for first-principles electrochemistry of metal surfaces in non-adsorbing, aqueous electrolytes: dielectric and ionic nonlinearity, and a dielectric-only region at the interface. The dielectric nonlinearity, caused by the saturation of dipole rotational response in water, creates the capacitance hump, while ionic nonlinearity, caused by the compactness of the diffuse layer, generates the capacitance dip seen at low ionic strength. We show that none of the previously developed solvation models simultaneously meet all these criteria. We design the nonlinear electrochemical soft-sphere solvation model which both captures the capacitance features observed experimentally and serves as a general-purpose continuum solvation model.},

  doi          = {10.1063/1.5024219},

  journal      = {Journal of Chemical Physics},

  number       = 14,

  volume       = 148,

  place        = {United States},

  year         = {2018},

  month        = {4}

}

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Works referencing / citing this record:

Influence of Van der Waals Interactions on the Solvation Energies of Adsorbates at Pt‐Based Electrocatalysts
journal, August 2019

Granda‐Marulanda, Laura P.; Builes, Santiago; Koper, Marc T. M.
ChemPhysChem, Vol. 20, Issue 22
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Continuum embeddings in condensed-matter simulations
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Andreussi, Oliviero; Fisicaro, Giuseppe
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A first-principles roadmap and limits to design efficient supercapacitor electrode materials
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Ali, Basant A.; Allam, Nageh K.
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Baskin, Artem; Prendergast, David
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The Poisson–Boltzmann model for implicit solvation of electrolyte solutions: Quantum chemical implementation and assessment via Sechenov coefficients
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Title: Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations

Abstract

Citation Formats

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Theory of Electrified Interfaces: A Combined Analysis Using the Density Functional Approach and Bethe Approximation journal, July 1998

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Evaluating continuum solvation models for the electrode-electrolyte interface: Challenges and strategies for improvement journal, February 2017

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JDFTx: Software for joint density-functional theory journal, January 2017

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Regularization of the Coulomb singularity in exact exchange by Wigner-Seitz truncated interactions: Towards chemical accuracy in nontrivial systems journal, April 2013

Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111) journal, January 2016

Quantum Mechanical Continuum Solvation Models journal, August 2005

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Structuring of the solvent at metal/solution interfaces and components of the electrode potential journal, July 1983

The electrical double layer: recent experimental and theoretical developments journal, July 1990

Thermochemical Radii of Complex Ions journal, November 1999

Double layer on silver single-crystal electrodes in contact with electrolytes having anions which present a slight specific adsorption journal, May 1981

Pseudopotentials for high-throughput DFT calculations journal, January 2014

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Ionic radii in aqueous solutions journal, April 1983

Double layer on silver single crystal electrodes in contact with electrolytes having anions which are slightly specifically adsorbed journal, September 1989

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Ideal regularization of the Coulomb singularity in exact exchange by Wigner-Seitz truncated interactions: towards chemical accuracy in non-trivial systems text, January 2013

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UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations
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Raman spectra from electrode surfaces
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The interphase between mercury and aqueous sodium dihydrogen phosphate
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The interphase between jellium and a hard sphere electrolyte: Capacity–charge characteristics and dipole potentials
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Efficient classical density-functional theories of rigid-molecular fluids and a simplified free energy functional for liquid water
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Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
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The Electrical Double Layer and the Theory of Electrocapillarity.
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Revised self-consistent continuum solvation in electronic-structure calculations
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Regularization of the Coulomb singularity in exact exchange by Wigner-Seitz truncated interactions: Towards chemical accuracy in nontrivial systems
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Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111)
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Quantum Mechanical Continuum Solvation Models
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Preparation of monocrystalline Pt microelectrodes and electrochemical study of the plane surfaces cut in the direction of the 111 and 110 planes
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Structuring of the solvent at metal/solution interfaces and components of the electrode potential
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The electrical double layer: recent experimental and theoretical developments
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Thermochemical Radii of Complex Ions
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Double layer on silver single-crystal electrodes in contact with electrolytes having anions which present a slight specific adsorption
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Pseudopotentials for high-throughput DFT calculations
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Quantum Mechanical Continuum Solvation Models
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Ionic radii in aqueous solutions
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Double layer on silver single crystal electrodes in contact with electrolytes having anions which are slightly specifically adsorbed
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The importance of nonlinear fluid response in joint density-functional theory studies of battery systems
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Ideal regularization of the Coulomb singularity in exact exchange by Wigner-Seitz truncated interactions: towards chemical accuracy in non-trivial systems
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Pseudopotentials for high-throughput DFT calculations
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A recipe for free-energy functionals of polarizable molecular fluids
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Grand canonical electronic density-functional theory: algorithms and applications to electrochemistry
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JDFTx: software for joint density-functional theory
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Influence of Van der Waals Interactions on the Solvation Energies of Adsorbates at Pt‐Based Electrocatalysts
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Continuum embeddings in condensed-matter simulations
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A first-principles roadmap and limits to design efficient supercapacitor electrode materials
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Understanding cation effects in electrochemical CO ₂ reduction
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Toward a quantitative theoretical method for infrared and Raman spectroscopic studies on single-crystal electrode/liquid interfaces
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Grand-canonical approach to density functional theory of electrocatalytic systems: Thermodynamics of solid-liquid interfaces at constant ion and electrode potentials
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Exploring chemical speciation at electrified interfaces using detailed continuum models
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The Poisson–Boltzmann model for implicit solvation of electrolyte solutions: Quantum chemical implementation and assessment via Sechenov coefficients
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Substrate effects on charged defects in two-dimensional materials
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