Abstract
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 Ho2 Zr2 O7. 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 RE2 Th2 O7 fluorite compounds, spanning a range of values for the ratio of the tetravalent and trivalent (RE) cation radii. 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.
| Original language | English (US) |
|---|---|
| Article number | 38772 |
| Journal | Scientific reports |
| Volume | 6 |
| DOIs | |
| State | Published - Dec 12 2016 |
ASJC Scopus subject areas
- General
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Solomon, J. M., Shamblin, J., Lang, M., Navrotsky, A., & Asta, M. (2016). Chemical ordering in substituted fluorite oxides: A computational investigation of Ho2 Zr2 O7 and RE2 Th2 O7 (RE=Ho, Y, Gd, Nd, La). Scientific reports, 6, [38772]. https://doi.org/10.1038/srep38772
Chemical ordering in substituted fluorite oxides: A computational investigation of Ho2 Zr2 O7 and RE2 Th2 O7 (RE=Ho, Y, Gd, Nd, La). / Solomon, Jonathan M.; Shamblin, Jacob; Lang, Maik et al.
In: Scientific reports, Vol. 6, 38772, 12.12.2016.
Research output: Contribution to journal › Article › peer-review
Solomon, JM, Shamblin, J, Lang, M, Navrotsky, A & Asta, M 2016, 'Chemical ordering in substituted fluorite oxides: A computational investigation of Ho2 Zr2 O7 and RE2 Th2 O7 (RE=Ho, Y, Gd, Nd, La)', Scientific reports, vol. 6, 38772. https://doi.org/10.1038/srep38772
Solomon JM, Shamblin J, Lang M, Navrotsky A, Asta M. Chemical ordering in substituted fluorite oxides: A computational investigation of Ho2 Zr2 O7 and RE2 Th2 O7 (RE=Ho, Y, Gd, Nd, La). Scientific reports. 2016 Dec 12;6:38772. doi: https://doi.org/10.1038/srep38772
Solomon, Jonathan M. ; Shamblin, Jacob ; Lang, Maik et al. / Chemical ordering in substituted fluorite oxides : A computational investigation of Ho2 Zr2 O7 and RE2 Th2 O7 (RE=Ho, Y, Gd, Nd, La). In: Scientific reports. 2016 ; Vol. 6.
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abstract = "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 Ho2 Zr2 O7. 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 RE2 Th2 O7 fluorite compounds, spanning a range of values for the ratio of the tetravalent and trivalent (RE) cation radii. 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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AU - Shamblin, Jacob
AU - Lang, Maik
AU - Navrotsky, Alexandra
AU - Asta, Mark
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AB - 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 Ho2 Zr2 O7. 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 RE2 Th2 O7 fluorite compounds, spanning a range of values for the ratio of the tetravalent and trivalent (RE) cation radii. 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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