Evaluating continuum solvation models for the electrode-electrolyte interface: challenges and strategies for improvement

Abstract

Ab initio modeling of electrochemical systems is becoming a key tool for understanding and predicting electrochemical behavior. Development and careful benchmarking of computational electrochemical methods are essential to ensure their accuracy. Here, using charging curves for an electrode in the presence of an inert aqueous electrolyte, we demonstrate that most continuum models, which are parameterized and benchmarked for molecules, anions, and cations in solution, undersolvate metal surfaces, and underestimate the surface charge as a function of applied potential. We examine features of the electrolyte and interface that are captured by these models, and identify improvements necessary for realistic electrochemical calculations of metal surfaces. Finally, we reparameterize popular solvation models using the surface charge of Ag(100) as a function of voltage to find improved accuracy for metal surfaces without significant change in utility for molecular and ionic solvation.

References in corpus (4)

• The charge-asymmetric nonlocally-determined local-electric (CANDLE) solvation model
• Ideal regularization of the Coulomb singularity in exact exchange by Wigner-Seitz truncated interactions: towards chemical accuracy in non-trivial systems
• Differential capacitance of the electric double layer: The interplay between ion finite size and dielectric decrement
• Surface Tension of Electrolyte Interfaces: Ionic Specificity within a Field-Theory Approach

Cited by in corpus (2)

• JDFTx: software for joint density-functional theory
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