title: Hybrid density functional theory band structure engineering in hematite.
abstract: We present a hybrid density functional theory (DFT) study of doping effects in α-Fe(2)O(3), hematite. Standard DFT underestimates the band gap by roughly 75% and incorrectly identifies hematite as a Mott-Hubbard insulator. Hybrid DFT accurately predicts the proper structural, magnetic, and electronic properties of hematite and, unlike the DFT+U method, does not contain d-electron specific empirical parameters. We find that using a screened functional that smoothly transitions from 12% exact exchange at short ranges to standard DFT at long range accurately reproduces the experimental band gap and other material properties. We then show that the antiferromagnetic symmetry in the pure α-Fe(2)O(3) crystal is broken by all dopants and that the ligand field theory correctly predicts local magnetic moments on the dopants. We characterize the resulting band gaps for hematite doped by transition metals and the p-block post-transition metals. The specific case of Pd doping is investigated in order to correlate calculated doping energies and optical properties with experimentally observed photocatalytic behavior.
authors.affiliation: Department of Chemistry and Biochemistry and the Institute for Computational Engineering and Sciences, University of Texas at Austin, 1 University Station A5300, Austin, Texas 78712-0165, USA.
authors.forename: Zachary D
authors.initials: ZD
authors.lastname: Pozun
authors.forename: Graeme
authors.initials: G
authors.lastname: Henkelman