Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La)
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 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.
- Authors:
-
- Univ. of California, Berkeley, CA (United States)
- Univ. of Tennessee, Knoxville, TN (United States)
- Univ. of California, Davis, CA (United States)
- Publication Date:
- Research Org.:
- 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 Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1373548
- Grant/Contract Number:
- AC02-06CH11357; SC0001089
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Scientific Reports
- Additional Journal Information:
- Journal Volume: 6; Journal Issue: 1; Journal ID: ISSN 2045-2322
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; materials for energy and catalysis; theory and computation
Citation Formats
Solomon, Jonathan M., Shamblin, Jacob, Lang, Maik, Navrotsky, Alexandra, and Asta, Mark. Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La). United States: N. p., 2016.
Web. doi:10.1038/srep38772.
Solomon, Jonathan M., Shamblin, Jacob, Lang, Maik, Navrotsky, Alexandra, & Asta, Mark. Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La). United States. https://doi.org/10.1038/srep38772
Solomon, Jonathan M., Shamblin, Jacob, Lang, Maik, Navrotsky, Alexandra, and Asta, Mark. Mon .
"Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La)". United States. https://doi.org/10.1038/srep38772. https://www.osti.gov/servlets/purl/1373548.
@article{osti_1373548,
title = {Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La)},
author = {Solomon, Jonathan M. and Shamblin, Jacob and Lang, Maik and Navrotsky, Alexandra and Asta, Mark},
abstractNote = {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.},
doi = {10.1038/srep38772},
journal = {Scientific Reports},
number = 1,
volume = 6,
place = {United States},
year = {Mon Dec 12 00:00:00 EST 2016},
month = {Mon Dec 12 00:00:00 EST 2016}
}
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