Elusive Valence Transition in Mixed-Valence Sesquioxide Cs4O6

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dc.authorid0000-0003-3439-0716en_US
dc.contributor.authorColman, Ross H.
dc.contributor.authorOkur Kutay, Havva Esma
dc.contributor.authorKockelmann, Winfried
dc.contributor.authorBrown, Craig M.
dc.contributor.authorSans, Annette
dc.contributor.authorFelser, Claudia
dc.date.accessioned2021-03-20T20:12:25Z
dc.date.available2021-03-20T20:12:25Z
dc.date.issued2019
dc.departmentBTÜ, Mühendislik ve Doğa Bilimleri Fakültesi, Kimya Mühendisliği Bölümüen_US
dc.description.abstractCs4O6 is a mixed-valence molecular oxide with a cubic structure, comprising valency-delocalized O-2(4/3-) units and with properties highly sensitive to cooling protocols. Here we use neutron powder diffraction to authenticate that, while upon deep quenching the cubic phase is kinetically arrested down to cryogenic temperatures, ultraslow cooling results in an incomplete structural transition to a contracted tetragonal phase. Two dioxygen anions in a 1:2 ratio are identified, providing evidence that the transition is accompanied by charge and orbital order and stabilizes a Robin-Day Class II mixed-valence state, comprising O-2(2-) and O-2(-) anions. The phenomenology of the phase change is consistent with that of a martensitic transition. The response of the low-temperature phase assemblage to heating is complex, involving a series of successive interconversions between the coexisting phases. Notably, a broad interconversion plateau is present near 260 K, signifying reentrant kinetic arrest tetragonal phase upon heating because of the combined effects of increased steric hindrance for molecular rotation and melting of charge and orbital order. The geometrically frustrated pyrochlore lattice adopted by the paramagnetic S = 1/2 O-2(-) units provides an intimate link between the crystal and magnetic properties of charge-ordered Cs4O6, naturally accounting for the absence of magnetic order.en_US
dc.description.sponsorshipMinistry of Education, Culture, Sports, Science and Technology, JapanMinistry of Education, Culture, Sports, Science and Technology, Japan (MEXT) [JP17H05139, JP18H04303, JP18K18724, JP19H04590]; Czech OP VVV project MATFUN [CZ.02.1.01/0.0/0.0/15_003/0000487]; European Union/JST FP7-NMP-2011-EU-Japan project LEMSUPER [NMP3-SL-2011-283214]en_US
dc.description.sponsorshipWe thank ISIS (GEM data DOI10.5286/ISIS.E.24091149) for access to neutron facilities. This work was financially supported by Grants-in-Aid for Scientific Research (JSPS KAKENHI Grants JP17H05139, JP18H04303, JP18K18724, and JP19H04590) by the Ministry of Education, Culture, Sports, Science and Technology, Japan, by the Czech OP VVV project MATFUN (Grant CZ.02.1.01/0.0/0.0/15_003/0000487), and by the European Union/JST FP7-NMP-2011-EU-Japan project LEMSUPER (Contract NMP3-SL-2011-283214).en_US
dc.identifier.doi10.1021/acs.inorgchem.9602122en_US
dc.identifier.endpage14541en_US
dc.identifier.issn0020-1669
dc.identifier.issn1520-510X
dc.identifier.issue21en_US
dc.identifier.pmid31633914en_US
dc.identifier.scopusqualityQ1en_US
dc.identifier.startpage14532en_US
dc.identifier.urihttp://doi.org/10.1021/acs.inorgchem.9602122
dc.identifier.urihttps://hdl.handle.net/20.500.12885/547
dc.identifier.volume58en_US
dc.identifier.wosWOS:000494894400027en_US
dc.identifier.wosqualityQ1en_US
dc.indekslendigikaynakWeb of Scienceen_US
dc.indekslendigikaynakScopusen_US
dc.indekslendigikaynakPubMeden_US
dc.institutionauthorOkur Kutay, Havva Esma
dc.language.isoenen_US
dc.publisherAmer Chemical Socen_US
dc.relation.ispartofInorganic Chemistryen_US
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanıen_US
dc.rightsinfo:eu-repo/semantics/openAccessen_US
dc.subject[No Keywords]en_US
dc.titleElusive Valence Transition in Mixed-Valence Sesquioxide Cs4O6en_US
dc.typeArticleen_US

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