Accounting for Dispersion Effects in the DFT Framework of Electrocatalysis: A Hybrid Solvation Model-Based Case Study of the Oxygen Reduction Reaction

Abstract

Density functional theory (DFT) is a pivotal tool in the field of computational electrocatalysis. Dispersion effects, which are not incorporated in the regular DFT framework, play a significant role in improving the accuracy of DFT-based catalytic simulations. We perform a calibration study for addressing the role of different dispersion-corrected DFT methods in determining the electrocatalytic properties by conducting a case study of the oxygen reduction reaction (ORR). The distinct trends of these methods toward determining the structural, energetic, and electronic properties of catalysis are scrutinized. By systematically incorporating an upgraded solvation model, the importance of the inclusion of dispersion effects for the accurate prediction of chemical and physical properties governing the catalytic activity is illustrated. The combined thermodynamic and kinetic analysis predicts a uniform ORR activity trend, with semiempirical dispersion-corrected DFT methods emerging as optimal choices with accuracy comparable to or higher than that of advanced van der Waals methods. © 2022 American Chemical Society.