- Title
- The Hubbard-U correction and optical properties of d⁰ metal oxide photocatalysts
- Creator
- Brown, Joshua J.; Page, Alister J.
- Relation
- ARC. LE17010003 http://purl.org/au-research/grants/arc/FL170100032
- Relation
- Journal of chemical Physics Vol. 153, Issue 22, no. 224116
- Publisher Link
- http://dx.doi.org/10.1063/5.0027080
- Publisher
- American Institute of Physics (AIP)
- Resource Type
- journal article
- Date
- 2020
- Description
- We report a systematic investigation of individual and multisite Hubbard-U corrections for the electronic, structural, and optical properties of the metal titanate oxide d0 photocatalysts SrTiO3 and rutile/anatase TiO2. Accurate bandgaps for these materials can be reproduced with local density approximation and generalized gradient approximation exchange-correlation density functionals via a continuous series of empirically derived Ud and Up combinations, which are relatively insensitive to the choice of functional. On the other hand, lattice parameters are much more sensitive to the choice of Ud and Up, but in a systematic way that enables the Ud and Up corrections to be used to qualitatively gauge the extent of self-interaction error in the electron density. Modest Ud corrections (e.g., 4 eV–5 eV) yield the most reliable dielectric response functions for SrTiO3 and are comparable to the range of Ud values derived via linear response approaches. For r-TiO2 and a-TiO2, however, the Ud,p corrections that yield accurate bandgaps fail to accurately describe both the parallel and perpendicular components of the dielectric response function. Analysis of individual Ud and Up corrections on the optical properties of SrTiO3 suggests that the most consequential of the two individual corrections is Ud, as it predominately determines the accuracy of the dominant excitation from O-2p to the Ti-3d t2g/eg orbitals. Up, on the other hand, can be used to shift the entire optical response uniformly to higher frequencies. These results will assist high-throughput and machine learning approaches to screening photoactive materials based on d0 photocatalysts.
- Subject
- optical properties; oxide minerals; metal-oxide photocatalysts; Hubbard
- Identifier
- http://hdl.handle.net/1959.13/1445804
- Identifier
- uon:42677
- Identifier
- ISSN:0021-9606
- Rights
- This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Brown, Joshua J.; Page, Alister J. ' The Hubbard-U correction and optical properties of d⁰ metal oxide photocatalysts’. Published in Journal of chemical Physics Vol. 153, Issue 22, no. 224116 (2020) and may be found at http://dx.doi.org/10.1063/5.0027080.
- Language
- eng
- Full Text
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