Complex 5d magnetism in a novel S= 1/2 trimer system, the 12L hexagonal perovskite ba4biir3o12

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dc.contributor.authorMiiller, Wen_AU
dc.contributor.authorDunstan, MTen_AU
dc.contributor.authorHuang, Zen_AU
dc.contributor.authorMohamed, Zen_AU
dc.contributor.authorKennedy, BJen_AU
dc.contributor.authorAvdeev, Men_AU
dc.contributor.authorLing, CDen_AU
dc.date.accessioned2014-09-16T02:14:12Zen_AU
dc.date.available2014-09-16T02:14:12Zen_AU
dc.date.issued2013-10-21en_AU
dc.date.statistics2014-09-16en_AU
dc.description.abstractThe 12L hexagonal perovskite Ba4BiIr3O12 has been synthesized for the first time and characterized using high-resolution neutron and synchrotron X-ray diffraction as well as physical properties measurements. The structure contains Ir3O12 linear face-sharing octahedral trimer units, bridged by corner-sharing BiO6 octahedra. The average electronic configurations of Ir and Bi are shown to be +4(d5) and +4(s1), respectively, the same as for the S = 1/2 dimer system Ba3BiIr2O9, which undergoes a spin-gap opening with a strong magnetoelastic effect at T* = 74 K. Anomalies in magnetic susceptibility, heat capacity, electrical resistivity, and unit cell parameters indeed reveal an analogous effect at T* ≈ 215 K in Ba4BiIr3O12. However, the transition is not accompanied by the opening of a gap in spin excitation spectrum, because antiferromagnetic coupling among S = 1/2 Ir4+ (d5) cations leads to the formation of a S = 1/2 doublet within the trimers, vs S = 0 singlets within dimers. The change in magnetic state of the trimers at T* leads to a structural distortion, the energy of which is overcompensated for by the formation of S = 1/2 doublets. Extending this insight to the dimer system Ba3BiIr2O9 sheds new light on the more pronounced low-temperature anomalies observed for that compound. © 2013, American Chemical Society.en_AU
dc.identifier.citationMiiller, W., Dunstan, M.T., Huang, Z.X., Mohamed, Z., Kennedy, B.J., Avdeev, M., & Ling, C.D. (2013). Complex 5d magnetism in a novel S =1/2 trimer system, the 12L hexagonal perovskite ba4biir3o12. Inorganic Chemistry, 52(21), 12461-12467. doi:10.1021/ic4014619en_AU
dc.identifier.govdoc5410en_AU
dc.identifier.issn0020-1669en_AU
dc.identifier.issue21en_AU
dc.identifier.journaltitleInorganic Chemistryen_AU
dc.identifier.pagination12461-12467en_AU
dc.identifier.urihttp://dx.doi.org/10.1021/ic4014619en_AU
dc.identifier.urihttp://apo.ansto.gov.au/dspace/handle/10238/5862en_AU
dc.identifier.volume52en_AU
dc.language.isoenen_AU
dc.publisherAmerican Chemical Societyen_AU
dc.subjectBariumen_AU
dc.subjectBismuthen_AU
dc.subjectLawrenciumen_AU
dc.subjectPerovskiteen_AU
dc.subjectNeutron diffractionen_AU
dc.subjectRare earthsen_AU
dc.titleComplex 5d magnetism in a novel S= 1/2 trimer system, the 12L hexagonal perovskite ba4biir3o12en_AU
dc.typeJournal Articleen_AU
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