Accounting for Dispersion Effects in DFT Framework of Electrocatalysis: A Case Study of Solvent Mediated Oxygen Reduction Reaction

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 effect of different dispersion corrected DFT methods in determining the electrocatalytic properties by conducting a case study of oxygen reduction reaction (ORR). The distinct trends of these methods towards 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 semi-empirical dispersion corrected DFT methods emerging as optimal choices with comparable or higher accuracy than advanced van der Waal’s methods.