Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La)

Solomon, Jonathan M.; Shamblin, Jacob; Lang, Maik; Navrotsky, Alexandra; Asta, Mark

doi:10.1038/srep38772

Title: Chemical ordering in substituted fluorite oxides: a computational investigation of Ho₂Zr₂O₇ and RE₂Th₂O₇ (RE=Ho, Y, Gd, Nd, La)

Journal Article · Mon Dec 12 00:00:00 EST 2016 · Scientific Reports

DOI:https://doi.org/10.1038/srep38772· OSTI ID:1373548

Solomon, Jonathan M. ^[1]; Shamblin, Jacob ^[2]; Lang, Maik ^[2]; Navrotsky, Alexandra ^[3]; Asta, Mark ^[1]

Univ. of California, Berkeley, CA (United States)
Univ. of Tennessee, Knoxville, TN (United States)
Univ. of California, Davis, CA (United States)

Fluorite-structured oxides find widespread use for applications spanning nuclear energy and waste containment, energy conversion, and sensing. In such applications the host tetravalent cation is often partially substituted by trivalent cations, with an associated formation of charge-compensating oxygen vacancies. The stability and properties of such materials are known to be influenced strongly by chemical ordering of the cations and vacancies, and the nature of such ordering and associated energetics are thus of considerable interest. Here we employ density-functional theory (DFT) calculations to study the structure and energetics of cation and oxygen-vacancy ordering in Ho₂Zr₂O₇. In a recent neutron total scattering study, solid solutions in this system were reported to feature local chemical ordering based on the fluorite-derivative weberite structure. The calculations show a preferred chemical ordering qualitatively consistent with these findings, and yield values for the ordering energy of 9.5 kJ/mol-cation. Similar DFT calculations are applied to additional RE₂Th₂O₇'' fluorite compounds, spanning a range of values for the ratio of the tetravalent and trivalent (RE) cation radii. Finally, the results demonstrate that weberite-type order becomes destabilized with increasing values of this size ratio, consistent with an increasing energetic preference for the tetravalent cations to have higher oxygen coordination.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; SC0001089

OSTI ID:: 1373548

Journal Information:: Scientific Reports, Vol. 6, Issue 1; ISSN 2045-2322

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 16 works

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Title: Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La)

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Title: Chemical ordering in substituted fluorite oxides: a computational investigation of Ho₂Zr₂O₇ and RE₂Th₂O₇ (RE=Ho, Y, Gd, Nd, La)