Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 140, Issue 2, Pages 636-641Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b09441
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Funding
- EPSRC
- STFC
- ERC
- EPSRC [EP/F02083X/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/F02083X/1] Funding Source: researchfish
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The semivalent oxyphosphate V2OPO4 is found to have long-range V2+/V(3+)charge ordering up to 605 K where a monoclinic to tetragonal structural transition and a switch from positive to negative' thermal expansion are observed. V-V bonding within orbital polymer chains is proposed as the key factor in the novel switch of thermal expansion behavior, as loss of V-V bonding enables transverse oxygen motions to dominate the thermal' expansion at high temperatures. Ferrimagnetic order of V2+ spin up and V3+ spin down states is observed below a magnetic ordering transition at 164 K, and susceptibility measurements evidence local spin pairing correlations to higher temperatures.
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