(297b) Electronic Structure Modeling of Electrocatalysis at the Electrode-Electrolyte Interface

The use of electronic structure methods, mainly density functional theory (DFT), to examine electrocatalytic behavior has become widespread. In this tutorial talk, I will overview the approaches used to apply DFT to investigate processes at the complex electrode-electrolyte interface. This interface, in low-temperature electrochemical systems, contains an electrically-conductive electrode in contact with a liquid electrolyte. The length and time scales associated with the dynamic interface make construction of DFT models challenging, as these models are restricted to order ~100 atoms. Modeling choices are made on how to represent the solvating interactions of electrolyte with electrocatalytic intermediates: continuum solvation, static explicit solvent, or dynamic explicit solvent. The separation of charge between the electrode-electrolyte similarly requires model approximations. Thermodynamic and kinetic frameworks are needed to consider processes that transfer ions from/to the electrolyte and electrons from/to the electrode at a variable electrode potential. This tutorial will target researchers interesting in gaining atomic-level insights into electrocatalytic phenomena, with an assumed background of a novice to electrochemistry.