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

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/1.5024219 · OSTI ID:1459895

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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; Rensselaer Polytechnic Institute; USDOE
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1459895
Alternate ID(s):
OSTI ID: 1432740
Journal Information:
Journal of Chemical Physics, Vol. 148, Issue 14; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 33 works
Citation information provided by
Web of Science

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Continuum embeddings in condensed-matter simulations journal October 2018
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A first-principles roadmap and limits to design efficient supercapacitor electrode materials journal January 2019
Grand-canonical approach to density functional theory of electrocatalytic systems: Thermodynamics of solid-liquid interfaces at constant ion and electrode potentials journal January 2019
Continuum models of the electrochemical diffuse layer in electronic-structure calculations journal January 2019
The Poisson–Boltzmann model for implicit solvation of electrolyte solutions: Quantum chemical implementation and assessment via Sechenov coefficients journal December 2019
Toward a quantitative theoretical method for infrared and Raman spectroscopic studies on single-crystal electrode/liquid interfaces journal January 2020