119Sn MAS NMR and first-principles calculations for the investigation of disorder in stannate pyrochlores

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dc.contributor.authorMitchell, MRen_AU
dc.contributor.authorReader, SWen_AU
dc.contributor.authorJohnston, KEen_AU
dc.contributor.authorPickard, CJen_AU
dc.contributor.authorWhittle, KRen_AU
dc.contributor.authorAshbrook, SEen_AU
dc.date.accessioned2011-02-02T23:46:45Zen_AU
dc.date.available2011-02-02T23:46:45Zen_AU
dc.date.issued2011-01-14en_AU
dc.date.statistics2011-01-14en_AU
dc.description.abstractThe local structure and cation disorder in Y2Ti2−xSnxO7 pyrochlores, materials proposed for the encapsulation of lanthanide- and actinide-bearing radioactive waste, is studied using 119Sn (I = 1/2) NMR spectroscopy. NMR provides an excellent probe of disorder, as it is sensitive to the atomic scale environment without the need for any long-range periodicity. However, the complex and overlapping spectral resonances that often result can be difficult to interpret. Here, we demonstrate how 119Sn DFT calculations can be used to aid the spectral interpretation and assignment, confirming that Sn occupies only the six-coordinate pyrochlore B site, and that the Sn chemical shift is sensitive to the number of Sn/Ti on the neighbouring B sites. Although distinct resonances are resolved experimentally when the Ti content is low, there is significant spectral overlap for Ti-rich compositions. We establish that this is a result of two competing contributions to the Sn chemical shift; an upfield shift resulting from the incorporation of the more polarizing Ti4+ cation onto the neighbouring B sites, and a concomitant downfield shift arising from the decrease in unit cell size. Despite the considerably easier spectral acquisition, the lower resolution in the 119Sn spectra hinders the extraction of the detailed structural information previously obtained using 89Y NMR. However, the spectra we obtain are consistent with a random distribution of Sn/Ti on the pyrochlore B sites. Finally, we consider whether an equilibrium structure has been achieved by investigating materials that have been annealed for different durations. © 2011, Royal Society of Chemistryen_AU
dc.identifier.citationMitchell, M. R., Reader, S. W., Johnston, K. E., Pickard, C. J., Whittle, K. R. & Ashbrook, S. E. (2011). 119Sn MAS NMR and first-principles calculations for the investigation of disorder in stannate pyrochlores. Physical Chemistry Chemical Physics, 13(2), 488-497. doi:10.1039/c0cp01274ben_AU
dc.identifier.govdoc3175en_AU
dc.identifier.issn1463-9076en_AU
dc.identifier.issue2en_AU
dc.identifier.journaltitlePhysical Chemistry Chemical Physicsen_AU
dc.identifier.pagination488-497en_AU
dc.identifier.urihttp://dx.doi.org/10.1039/c0cp01274ben_AU
dc.identifier.urihttp://apo.ansto.gov.au/dspace/handle/10238/2982en_AU
dc.identifier.volume13en_AU
dc.language.isoenen_AU
dc.publisherRoyal Society of Chemistryen_AU
dc.subjectPyrochloreen_AU
dc.subjectNuclear magnetic resonanceen_AU
dc.subjectStannatesen_AU
dc.subjectTin 119en_AU
dc.subjectTitaniumen_AU
dc.subjectEncapsulationen_AU
dc.title119Sn MAS NMR and first-principles calculations for the investigation of disorder in stannate pyrochloresen_AU
dc.typeJournal Articleen_AU
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