2021/11/23 by Akash Bajaj, Heather J. Kulik, Bajaj, Akash +1
Materials Science · Physics and Astronomy · #Advanced Chemical Physics Studies #Catalytic Processes in Materials Science #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Machine Learning in Materials Science #Materials Science (cond-mat.mtrl-sci)
paper · pdf · doi:10.48550/arxiv.2111.11614
openalex publication_date 2021/11/23 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
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.