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Elusive Valence Transition in Mixed-Valence Sesquioxide Cs4O6

The result's identifiers

  • Result code in IS VaVaI

    <a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F19%3A10401678" target="_blank" >RIV/00216208:11320/19:10401678 - isvavai.cz</a>

  • Result on the web

    <a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=IUc~2h-dQb" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=IUc~2h-dQb</a>

  • DOI - Digital Object Identifier

    <a href="http://dx.doi.org/10.1021/acs.inorgchem.9b02122" target="_blank" >10.1021/acs.inorgchem.9b02122</a>

Alternative languages

  • Result language

    angličtina

  • Original language name

    Elusive Valence Transition in Mixed-Valence Sesquioxide Cs4O6

  • Original language description

    Cs4O6 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.

  • Czech name

  • Czech description

Classification

  • Type

    J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database

  • CEP classification

  • OECD FORD branch

    10302 - Condensed matter physics (including formerly solid state physics, supercond.)

Result continuities

  • Project

    <a href="/en/project/EF15_003%2F0000487" target="_blank" >EF15_003/0000487: Physics of martensitic transformation for functionality enhancement of crystalline materials and nanostructures</a><br>

  • Continuities

    P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Others

  • Publication year

    2019

  • Confidentiality

    S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Data specific for result type

  • Name of the periodical

    Inorganic Chemistry

  • ISSN

    0020-1669

  • e-ISSN

  • Volume of the periodical

    58

  • Issue of the periodical within the volume

    21

  • Country of publishing house

    US - UNITED STATES

  • Number of pages

    10

  • Pages from-to

    14532-14541

  • UT code for WoS article

    000494894400027

  • EID of the result in the Scopus database

    2-s2.0-85073813928