Eliminating Delocalization Error to Improve Heterogeneous Catalysis Predictions with Molecular DFT + U

• DOI: 10.48550/arxiv.2111.11614
• Publication Date: 2022-01-27
• Authors: Akash Bajaj; Heather J. Kulik
• Keywords: Physiology; like projectors; multilayer models; 01 natural sciences; highly delocalized across; tio; Environmental Sciences not elsewhere classified; cost dft; Condensed Matter - Materials Science; early transition; Ecology; oxygen sites; projectors within dft; representative early; centered molecular; paradoxical description; e .; catalytic transition; tune properties; surface stability; site dft; systematically construct multi; u </; Chemical Sciences not elsewhere classified; FOS: Physical sciences; conventional usage; tuning adsorption energies; standard dft; Physics - Chemical Physics; centered atomic orbitals; inefficacy arises due; adsorption energies; Chemical Physics (physics.chem-ph); Evolutionary Biology; surface formation; semilocal dft; pto; Computational Biology; Materials Science (cond-mat.mtrl-sci); rutile transition; rutile tio; minimal two; 541; dimensional models; 0104 chemical sciences; surface properties simultaneously; surface reactivity; delocalization error; surface formation energies; corresponding density rearrangement; molecular dft; Physical Sciences not elsewhere classified; eliminating delocalization error

Approximate semi-local density functional theory (DFT) is known to underestimate surface formation energies yet paradoxically overbind adsorbates on catalytic transition-metal oxide surfaces due to delocalization error. The low-cost DFT+U approach only improves surface formation energies for early transition-metal oxides or adsorption energies for late transition-metal oxides. In this work, we demonstrate that this inefficacy arises due to the conventional usage of metal-centered atomic orbitals as projectors within DFT+U. We analyze electron density rearrangement during surface formation and O atom adsorption on rutile transition-metal oxides to highlight that a standard DFT+U correction fails to tune properties when the corresponding density rearrangement is highly delocalized across both metal and oxygen sites. To improve both surface properties simultaneously while retaining the simplicity of a single-site DFT+U correction, we systematically construct multi-atom-centered molecular-orbital-like projectors for DFT+U. We demonstrate this molecular DFT+U approach for tuning adsorption energies and surface formation energies of minimal two-dimensional models of representative early (i.e., TiO2) and late (i.e., PtO2) transition-metal oxides. Molecular DFT+U simultaneously corrects adsorption energies and surface formation energies of multi-layer models of rutile TiO2(110) and PtO2(110) to resolve the paradoxical description of surface stability and surface reactivity of semi-local DFT.