Abstract
HOMONUCLEAR intervalcncc-transfer absorption of the first transition series cations has aroused considerable interest for two reasons1. First, it may give rise to intense colour which is not predicted by the addition of the colours of either of the individual ions. Second, it may lead in some chain structures to strong anisotropy in electronic conduction. A classic example is vivianite, Fe23+(H2O)8 [PO4]2: although colourless when fresh, upon partial oxidation of the transition metal the compound assumes a deep blue which is at its maximum intensity when the electric vector of polarised light is parallel to the axis of the two iron atoms in the octahedral edge-sharing dimer of the crystal structure. Extensive study on this and on other systems has led to a considerable body of literature1.
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References
Allen, G. C., and Hush, N. S., Progress in Inorganic Chemistry, 8, (edit by Cotton F. A.), 357 (Wiley, New York, 1967).
Moore, P. B., Amer. Mineral, 56, 1 (1971).
P. B., Lithos, 4, 93 (1971).
Larsen, E. S., and Berman, H., US geol. Surv. Bull., 848, 31 (1934).
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MOORE, P. Evidence for a complete mixed valence solid solution series in Fe23+ (H2O)3 [PO4]2 (phosphoferrite) Fe33+(OH)3 [PO4]2 (kryzhanovskite). Nature 251, 305–306 (1974). https://doi.org/10.1038/251305a0
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DOI: https://doi.org/10.1038/251305a0
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