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- W2921799963 abstract "In this paper we investigate the high-temperature structure of ${mathrm{Co}}_{3}{mathrm{O}}_{4}$, a compound that has been studied extensively over the last 60 years due to its unresolved high-temperature structure. In situ thermal analysis and x-ray diffraction confirm previously reported high-temperature structural changes and show that these changes are unrelated to the high-temperature decomposition to CoO. Raman-active peaks are also extinguished over the same temperature range. By considering the changing lattice parameter, $A$-O, and $B$-O bond lengths as well as cation size we are able to calculate the degree of inversion which reaches a maximum of 0.6. To further study the structure in this experimentally inaccessible range we quench samples and perform ex situ measurements including redox titration, x-ray photoelectron spectroscopy, and neutron diffraction. We do not observe any evidence of large oxygen vacancy concentrations or octahedral ${mathrm{Co}}_{B}{}^{3+}$ ions with high spin state. However, we do show an evolution in the magnetic moment from magnetic structure refinement from ($2.4phantom{rule{0.28em}{0ex}}{ensuremath{mu}}_{text{B}}$) to ($2.7phantom{rule{0.28em}{0ex}}{ensuremath{mu}}_{text{B}}$) that coincides exactly with the high-temperature anomaly and suggests partial inversion (0.46) of the spinel structure in fairly good agreement with the inversion calculated from bond lengths." @default.
- W2921799963 created "2019-03-22" @default.
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- W2921799963 date "2019-03-13" @default.
- W2921799963 modified "2023-10-16" @default.
- W2921799963 title "High-temperature structure of <mml:math xmlns:mml=http://www.w3.org/1998/Math/MathML><mml:mrow><mml:msub><mml:mi>Co</mml:mi><mml:mn>3</mml:mn></mml:msub><mml:msub><mml:mi mathvariant=normal>O</mml:mi><mml:mn>4</mml:mn></mml:msub></mml:mrow></mml:math> : Understanding spinel inversion using <i>in situ</i> and <i>ex situ</i> measurements" @default.
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- W2921799963 doi "https://doi.org/10.1103/physrevb.99.104104" @default.
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