Evaluating computational models of the electrode-electrolyte interface: challenges and strategies for improvement

Published

February 28, 2017

Author(s)

Kathleen A. Schwarz, Ravishankar Sundararaman

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 the 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 different models, and identify improvements that need to be made to utilize these models for electrochemical calculations of metal surfaces. We reparameterize the solvation models using the surface charge of Ag(100) as a function of voltage, and find that the new models are improved for metallic surface calculations without significant change in utility for solvation of molecules and ions.

Citation

The Journal of Chemical Physics

Pub Type

Journals

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DOI Link

Citation

Schwarz, K. and Sundararaman, R. (2017), Evaluating computational models of the electrode-electrolyte interface: challenges and strategies for improvement, The Journal of Chemical Physics, [online], https://doi.org/10.1063/1.4976971 (Accessed April 23, 2024)