We present a hybrid density functional theory (DFT) study of doping effects in α-Fe2O3, 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-Fe2O3 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.
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Research Article| June 14 2011
Hybrid density functional theory band structure engineering in hematite
Zachary D. Pozun;
Zachary D. Pozun, Graeme Henkelman; Hybrid density functional theory band structure engineering in hematite. J. Chem. Phys. 14 June 2011; 134 (22): 224706. https://doi.org/10.1063/1.3598947
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