Spin state equilibria and localized versus collective d-electron behaviour in neodymium and gadolinium trioxocobaltate(III)
- 1 January 1974
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics
- Vol. 70, 512-523
- https://doi.org/10.1039/f29747000512
Abstract
Magnetic susceptibility measurements and Mössbauer spectra show that NdCoO3 and GdCoO3 contain predominantly low-spin CoIII ions at low temperatures which transform partially to high-spin Co3+ until a certain temperature. Beyond this temperature, there is a transfer of eg electrons from Co3+ to CoIII giving rise to di- and tetra-valent Co species followed by short-range ordering. Co3+ ions completely disappear at about 1000 K where there is a gradual transition from localized electron behaviour to collective behaviour. The cobaltates are semi-metals beyond this transition. The spin state equilibria and the electronic transition described here find support from electron transport properties, Mössbauer parameters as well as differential thermal analysis and X-ray data.Keywords
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