title: 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.
authors.affiliation: Department of Materials Science and Engineering, Rensselaer Polytechnic Institute, 110 8th St, Troy, New York 12180, USA.
authors.forename: Ravishankar
authors.identifier: 0000000206254592
authors.initials: R
authors.lastname: Sundararaman
authors.affiliation: National Institute of Standards and Technology, Material Measurement Laboratory, 100 Bureau Dr, Gaithersburg, Maryland 20899, USA.
authors.forename: Kathleen
authors.identifier: 0000000215394511
authors.initials: K
authors.lastname: Schwarz