Density functional theory calculations of defective UO2 at U3O7 stoichiometry

Nicholas A. Brincat, M. Molinari, Geoffrey C. Allen, Mark T. Storr, Stephen C. Parker

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

UO2 is particularly susceptible to oxidation. The oxidation processes and the phases formed as a result are widely studied. In the oxidised phases defect clusters form, although their structure and properties are unclear. Thus, we examine fluorite based U3O7 phases to identify the types of defect present in a 36 atom unit cell. We predict that at this stoichiometry, defective structures form oxygen clusters and that split quad-interstitial clusters are the most thermodynamically stable defects. These are associated with a volume contraction compared to UO2, in line with experimental measurements. Incorporation of oxygen is always associated with oxidation of uranium atoms to U5+, although a single calculation leads to a U6+ ion as well. As this system is relatively unstable, it is proposed that U4+ and U5+ are the preferred oxidation states at U3O7 stoichiometry.

LanguageEnglish
Pages724-729
Number of pages6
JournalJournal of Nuclear Materials
Volume467
Issue numberPart 2
Early online date13 Oct 2015
DOIs
Publication statusPublished - 1 Dec 2015
Externally publishedYes

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Stoichiometry
Density functional theory
stoichiometry
density functional theory
Oxidation
oxidation
Defects
defects
Oxygen
Atoms
Uranium
Fluorspar
fluorite
oxygen
uranium
contraction
atoms
interstitials
Ions
cells

Cite this

Brincat, Nicholas A. ; Molinari, M. ; Allen, Geoffrey C. ; Storr, Mark T. ; Parker, Stephen C. / Density functional theory calculations of defective UO2 at U3O7 stoichiometry. In: Journal of Nuclear Materials. 2015 ; Vol. 467, No. Part 2. pp. 724-729.
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Density functional theory calculations of defective UO2 at U3O7 stoichiometry. / Brincat, Nicholas A.; Molinari, M.; Allen, Geoffrey C.; Storr, Mark T.; Parker, Stephen C.

In: Journal of Nuclear Materials, Vol. 467, No. Part 2, 01.12.2015, p. 724-729.

Research output: Contribution to journalArticle

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