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

TL;DR

This paper introduces a molecular DFT+U method with multi-atom projectors to better predict surface formation and adsorption energies on transition-metal oxides, addressing limitations of traditional DFT+U.

Contribution

It develops a multi-atom-centered projector approach for DFT+U, improving accuracy in surface and adsorption energy predictions for transition-metal oxides.

Findings

Molecular DFT+U corrects both surface formation and adsorption energies.

The approach resolves the delocalization error in semi-local DFT.

Improved predictions for TiO2 and PtO2 surfaces.

Abstract

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.