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.

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• Improving Accuracy of Electrochemical Capacitance and Solvation Energetics in First-Principles Calculations
• The Poisson-Boltzmann model for implicit solvation of electrolyte solutions: Quantum chemical implementation and assessment via Sechenov coefficients
• Electrochemical Capacitance of CO-terminated Pt(111) is Dominated by CO-Solvent Gap
• Gaussian-Based Periodic Grand Canonical Density Functional Theory with Implicit Solvation for Computational Electrochemistry
• Study on the free corrosion potential at an interface between an Al electrode and an acidic aqueous NaCl solution through density functional theory combined with the reference interaction site model
• Uncoupling System and Environment Simulation Cells for Fast-Scaling Modeling of Complex Continuum Embeddings