Abstract
A series of 21 cordierites with 0.06 E-5(g) transition of octahedral Fe2+. The integral intensity of the beta- and gamma -polarized nu (3) band correlates linearly with the concentration of non-octahedral Fe2+. Its high molar extinction coefficient, ca. 150 cm(-2) 1 mol(-1), and temperature independence are best explained by its assignment to dd transitions of Fe2+ in tetrahedral coordination. There occurs also a broad band at 18,000 cm(-1) polarized predominantly along b. Its properties are typical of a metal-metal charge transfer (CT) band involving Fe2+ on the octahedra and Fe3+ on the T(1)1-tetrahedra, the two of which are edge-shared. All spectroscopic data, including changes in the electronic spectra caused by heating at 1,000 degreesC in air, as well as crystal-chemical considerations, suggest that the ring-connecting T(1)1-tetrahedra contain small amounts of Fe2+.
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