Stable Surfaces That Bind Too Tightly: Can Range-Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry?

ABSTRACT: Approximate, semilocal density functional theory (DFT) suffers from delocalization error that can lead to a paradoxical model of catalytic surfaces that both overbind adsorbates yet are also too stable. We investigate the effect of two widely applied approaches for delocalization error correction, (i) affordable DFT+U (i.e., semilocal DFT augmented with a Hubbard U) and (ii) hybrid functionals with an admixture of Hartree-Fock (HF) exchange, on surface and adsorbate energies across a range of rutile transition metal oxides widely studied for their promise as water-splitting catalysts. We observe strongly row- and period-dependent trends with DFT+U, which increases surface formation energies only in early transition metals (e.g., Ti and V) and decreases adsorbate energies only in later tran

SUBMITTER: Zhao Q 

PROVIDER: S-EPMC6748670 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature