Pressure-Induced Charge Disorder-Order Transition in the Cs4O6 Sesquioxide

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dc.authorid0000-0003-3439-0716en_US
dc.contributor.authorOkur Kutay, Havva Esma
dc.contributor.authorColman, Ross H.
dc.contributor.authorOhish, Yasuo
dc.contributor.authorSans, Annette
dc.contributor.authorFelser, Claudia
dc.contributor.authorJansen, Martin
dc.date.accessioned2021-03-20T20:12:20Z
dc.date.available2021-03-20T20:12:20Z
dc.date.issued2020
dc.departmentBTÜ, Mühendislik ve Doğa Bilimleri Fakültesi, Kimya Mühendisliği Bölümüen_US
dc.description.abstractCs4O6 adopts two distinct crystal structures at ambient pressure. At temperatures below similar to 200 K, its ground state structure is tetragonal, incorporating two symmetry-distinct dioxygen anions, diamagnetic peroxide, O-2(2-), and paramagnetic superoxide, O-2(-), units in a 1:2 ratio, consistent with the presence of charge and orbital order. At high temperatures, its ground state structure is cubic, comprising symmetry-equivalent dioxygen units with an average oxidation state of -4/3, consistent with the adoption of a charge-disordered state. The pressure dependence of the structure of solid Cs4O6 at 300 K and at 13.4 K was followed up to similar to 12 GPa by synchrotron X-ray powder diffraction. When a pressure of similar to 2 GPa is reached at ambient temperature, an incomplete phase transition that is accompanied by a significant volume reduction (similar to 2%) to a more densely packed highly anisotropic tetragonal structure, isostructural with the low-temperature ambient-pressure phase of Cs4O6, is encountered. A complete transformation of the cubic (charge-disordered) to the tetragonal (charge-ordered) phase of Cs4O6 is achieved when the hydrostatic pressure exceeds 6 GPa. In contrast, the pressure response of the Cs4O6 cubic/tetragonal phase assemblage at 13.4 K is distinctly different with the cubic and tetragonal phases coexisting over the entire pressure range (to similar to 12 GPa) accessed in the present experiments and with only a small fraction of the cubic phase converting to tetragonal. Pressure turns out to be an inefficient stimulus to drive the charge disorder-order transition in Cs4O6 at cryogenic temperatures, presumably due to the high activation barriers (much larger than the thermal energy at 13.4 K) associated with the severe steric hindrance for a rotation of the molecular oxygen units necessitated in the course of the structural transformation.en_US
dc.description.sponsorshipJSPS KAKENHI Grants from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan [JP17H05139, JP18H04303, JP18K18724, JP19H04590]; KAKENHI Specific Support Operation of Osaka Prefecture University; 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.sponsorshipThis work was financially supported by Grants-in-Aid for Scientific Research (JSPS KAKENHI Grants JP17H05139, JP18H04303, JP18K18724, and JP19H04590) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan, by the KAKENHI Specific Support Operation of Osaka Prefecture University, by Czech OP VVV Project MATFUN (Grant CZ.02.1.01/0.0/0.0/15_003/0000487), and by European Union/JST FP7-NMP-2011-EU-Japan Project LEMSUPER (Contract NMP3-SL-2011-283214).en_US
dc.identifier.doi10.1021/acs.inorgchem.9b02974en_US
dc.identifier.endpage1264en_US
dc.identifier.issn0020-1669
dc.identifier.issn1520-510X
dc.identifier.issue2en_US
dc.identifier.pmid31904961en_US
dc.identifier.scopusqualityQ1en_US
dc.identifier.startpage1256en_US
dc.identifier.urihttp://doi.org/10.1021/acs.inorgchem.9b02974
dc.identifier.urihttps://hdl.handle.net/20.500.12885/491
dc.identifier.volume59en_US
dc.identifier.wosWOS:000509420100036en_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/closedAccessen_US
dc.subject[No Keywords]en_US
dc.titlePressure-Induced Charge Disorder-Order Transition in the Cs4O6 Sesquioxideen_US
dc.typeArticleen_US

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