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
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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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
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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