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Benchmarking Density Functional Theory Functionals for Polarons in Oxides: Properties of CeO2
Nottingham Trent Univ, Sch Sci & Technol, Nottingham NG11 8NS, England;Malardalen Univ, Div Phys & Math Nat Sci Didact, Box 883, SE-72123 Vasteras, Sweden.
Nottingham Trent Univ, Sch Sci & Technol, Nottingham NG11 8NS, England.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.ORCID iD: 0000-0003-3570-0050
2019 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 123, no 9, p. 5164-5175Article in journal (Refereed) Published
Abstract [en]

We examine methods for studying polarons in metal oxides with density functional theory (DFT), using the example of cerium dioxide and the functionals, local density approximation + U (LDA+U), generalized gradient approximation + U (GGA+U) in the Perdew-Burke-Ernzerhof parametrization (PBE+U), as well as the hybrid functionals B3LYP, Heyd Scuseria Ernzerhof (HSE)03, HSE06, and PBEO. We contrast the four polaron energies commonly reported in different parts of the literature: formation energy, localization/relaxation energy, density-of-states level, and polaron-hopping activation barrier. Qualitatively, all these functionals predict "small" (Holstein) polarons on the scale of a single lattice site, although LDA +U and GGA+U are more effective than the hybrids at localizing the Ce 4f electrons. The improvements over pure LDA/GGA appear because of changes in the filled Ce 4f states when using LDA/GGA+U but due to changes in the empty Ce 4f states when using the hybrids. DFT is shown to have sufficient correlation to predict both adiabatic and (approximate) diabatic hopping barriers. Overall, LDA+U = 6 eV provides the best description in comparison to the experiment, followed by GGA+U = 5 eV. The hybrids are worse, tending to overestimate the gap and significantly underestimate the polaron-hopping barriers.

Place, publisher, year, edition, pages
2019. Vol. 123, no 9, p. 5164-5175
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-380460DOI: 10.1021/acs.jpcc.8b09134ISI: 000460996000002OAI: oai:DiVA.org:uu-380460DiVA, id: diva2:1299816
Available from: 2019-03-28 Created: 2019-03-28 Last updated: 2019-03-28Bibliographically approved

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