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

• DOI: 10.1021/acs.jctc.1c01178
• Publication Date: 2022-01-27T09:25:39Z
• Authors: Akash Bajaj; Heather J. Kulik
• Keywords: Rutile

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