Challenges in Modeling Electrochemical Reaction Energetics with Polarizable Continuum Models

By Joseph A. Gauthier, Stefan Ringe, Colin F. Dickens, Alejandro J Garza, A. Bell, M. Head‐Gordon, Jens K. Nørskov, Karen Chan. ACS Catalysis, 2018

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A major challenge in the modeling of electrochemical phenomena is the accurate description of the interface between an electrolyte and a charged conductor. Polarizable continuum models (PCM) have been gaining popularity because they offer a computationally inexpensive method of modeling the electrolyte. In this Perspective, we discuss challenges from using one such model which treats the ions using a linearized Poisson–Boltzmann (LPB) distribution. From a physical perspective, this model places charge unphysically close to the surface and adsorbates, and it includes excessively steep ramping of the dielectric constant from the surface to the bulk solvent. Both of these issues can be somewhat mitigated by adjusting parameters built into the model, but in doing so, the resultant capacitance deviates from experimental values. Likewise, hybrid explicit-implicit approaches to the solvent may offer a more realistic description of hydrogen bonding and solvation to reaction intermediates, but the corresponding ca...

Subfields: Electrical and Electronic Engineering, Materials Chemistry, Renewable Energy, Sustainability and the Environment

View Paper: https://www.semanticscholar.org/paper/eca17e7458776069547ca5e176f68b1abe8cd125