(304d) DFT+U-Inspired Functional for Improved Modeling of Molecules and Solids
Herein, we reveal the inadequacy of the PBE functional for describing experimental trends on metal oxide surfaces (e.g., RuO2, TiO2) for the vacancy-catalyzed1 furfuryl alcohol hydrodeoxygenation, using first principles microkinetic modeling. We attribute the error to nonsystematic deviations of metal-oxygen bond energetics from experimental values. By utilizing adiabatic connection and the nth order perturbation theory, we arrive at an orbital-occupancy-dependent correction to the PBE functional that holds promise in mitigating the DFT accuracy problem. Corrections are formulated in the spirit of the DFT+U method. The new PBE-based parameter-free functional demonstrates clear improvement over pure PBE in describing dissociation energetics of molecules, NiO local magnetic moment and density of states, and cohesive energies of metal oxides, at minimal extra computational cost.
1. Mironenko, A.V., Vlachos, D.G. "Conjugation-Driven âReverse Marsâvan Krevelenâ-Type Radical Mechanism for Low-Temperature CâO Bond Activation."Â Journal of the American Chemical SocietyÂ 138.26 (2016): 8104-8113.