Local structure, dynamics, and the mechanisms of oxide ionic conduction in Bi26Mo10O69

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dc.contributor.authorLing, CDen_AU
dc.contributor.authorMiiller, Wen_AU
dc.contributor.authorJohnson, MRen_AU
dc.contributor.authorRichard, Den_AU
dc.contributor.authorRols, Sen_AU
dc.contributor.authorMadge, Jen_AU
dc.contributor.authorEvans, IRen_AU
dc.date.accessioned2014-04-17T06:07:03Zen_AU
dc.date.available2014-04-17T06:07:03Zen_AU
dc.date.issued2012-12-11en_AU
dc.date.statistics2014-04-17en_AU
dc.description.abstractWe report the results of a computational and experimental study into the stabilized fluorite-type delta-Bi(2)O(3)-related phase Bi(26)Mo(10)O(69) aimed at clarifying the local and average structure, for which two distinct models have previously been proposed, and the oxide ionic diffusion mechanism, for which three distinct models have previously been proposed. Concerning the structure, we propose a new model in which some molybdenum atoms have higher coordination numbers than 4; that is, some MoO(5) trigonal bipyramids coexist with MoO(4) tetrahedra. This accounts for the additional oxygen required to achieve the nominal composition (a tetrahedrononly model gives Bi(26)Mo(10)O(68)) without invoking a previously proposed unbonded interstitial site, which we found to be energetically unfavorable. All these MoO(x) units are rotationally disordered above a first-order transition at 310 degrees C, corresponding to a first-order increase in conductivity. Concerning oxide ionic diffusion above that transition temperature, we found excellent agreement between the results of ab initio molecular dynamics simulations and quasielastic neutron scattering experiments. Our results indicate a mechanism related to that proposed by Holmes et al. (Chem. Mater. 2008, 20, 3638), with the role previously assigned to partially occupied interstitial oxygen sites played instead by transient but stable MoO(5) trigonal bipyramids and with more relaxed requirements in terms of the orientation and timing of the diffusive jumps. © 2012, American Chemical Society.en_AU
dc.identifier.citationLing, C. D., Miiller, W., Johnson, M. R., Richard, D., Rols, S., Madge, J., & Evans, I. R. (2012). Local structure, dynamics, and the mechanisms of oxide ionic conduction in Bi26Mo10O69. Chemistry of Materials, 24(23), 4607-4614. doi:10.1021/cm303202ren_AU
dc.identifier.govdoc4751en_AU
dc.identifier.issn0897-4756en_AU
dc.identifier.issue23en_AU
dc.identifier.journaltitleChemistry of Materialsen_AU
dc.identifier.pagination4607-4614en_AU
dc.identifier.urihttp://dx.doi.org/10.1021/cm303202ren_AU
dc.identifier.urihttp://apo.ansto.gov.au/dspace/handle/10238/5453en_AU
dc.identifier.volume24en_AU
dc.language.isoenen_AU
dc.publisherAmerican Chemical Societyen_AU
dc.subjectSynchrotronsen_AU
dc.subjectX-ray diffractionen_AU
dc.subjectX-ray lasersen_AU
dc.subjectNeutronsen_AU
dc.subjectCrystalsen_AU
dc.subjectSupportsen_AU
dc.titleLocal structure, dynamics, and the mechanisms of oxide ionic conduction in Bi26Mo10O69en_AU
dc.typeJournal Articleen_AU
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