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Molecular orbital (SCF-X??-SW) theory of metal-metal charge transfer processes in minerals - I. application to Fe2+???Fe3+ charge transfer and "electron delocalization" in mixed-valence iron oxides and silicates

Physics and Chemistry of Minerals

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DOI: 10.1007/BF00309810

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Abstract

A number of mixed valence iron oxides and silicates (e.g., magnetite, ilvaite) exhibit thermally induced electron delocalization between adjacent Fe2+ and Fe3+ ions and optically induced electronic transitions which are assigned to Fe2+???Fe3+ intervalence charge transfer. In this paper, the mechanism of electron delocalization (i.e., polarons versus itinerant electrons) and the nature of optically induced intervalence charge-transfer in minerals are investigated using molecular orbital theory. SCF-X??-SW molecular orbital calculations were done for several mixed-valence (Fe2O10)15- clusters corresponding to edgesharing Fe2+ and Fe3+ coordination polyhedra. A spinunrestricted formalism was used so that the effect of ferromagnetic versus antiferromagnetic coupling of adjacent Fe2+ and Fe3+ cations could be determined. The molecular orbital results can be related to the polaron theory of solid state physics and the perturbation theory formalism used by Robin and Day (1967) and others to describe electron transfer in mixed valence compounds. Intervalence charge-transfer results from the overlap of Fe(3d) orbitals across the shared edges of adjacent FeO6 polyhedra to give weak Fe-Fe bonds. Electron delocalization, however, requires that adjacent Fe cations be ferromagnetically coupled. Antiferromagnetic coupling results in distinguishable Fe2+ and Fe3+ cations. Electronic transitions between the Fe-Fe bonding and Fe-Fe antibonding orbitals results in the optically-induced intervalence charge transfer bands observed in the electronic spectra of mixed valence minerals. Such transitions are predicted to be polarized along the metal-metal bond direction, in agreement with experimental observations. ?? 1987 Springer-Verlag.

Additional Publication Details

Publication type:
Article
Publication Subtype:
Journal Article
Title:
Molecular orbital (SCF-X??-SW) theory of metal-metal charge transfer processes in minerals - I. application to Fe2+???Fe3+ charge transfer and "electron delocalization" in mixed-valence iron oxides and silicates
Series title:
Physics and Chemistry of Minerals
DOI:
10.1007/BF00309810
Volume
14
Issue:
4
Year Published:
1987
Language:
English
Publisher location:
Springer-Verlag
Larger Work Type:
Article
Larger Work Subtype:
Journal Article
First page:
355
Last page:
363
Number of Pages:
9