We report electrochemical models based on periodic Kohn-Sham Density Functional Theory (DFT) that includes the effects of the electrochemical potential, solvent, and electrolyte. In these models, the electrode surface and all adsorbates are treated using DFT. The electrode potential is set using the Fermi energy from the KS-DFT calculations. The Fermi energy can be varied by changing the number of electrons in the simulation cell; therefore, the electrochemical potential was set by calculating the number of electrons the simulation cell required for a specific Fermi energy. With this treatment of the electrode and electrochemical potential, we then compare different treatments of the solvent and electrolyte. These include explicit solvent and electrolyte to various treatments of implicit solvent and implicit electrolytes. The focus of this work is to develop electrolyte models beyond the linearized Poisson-Boltzmann model.

Developing DFT-based models for describing electrochemical reactions: implicit treatments of electrolytes

2019 Spring National Meeting

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