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Fe²⁺/Fe³⁺ charge ordering in contact layers of lamellar magnetism: Bond valence arguments

¹ Geological Survey of Norway, N-7491, Trondheim, Norway
² Department of Earth Sciences, University of Cambridge, Cambridge CB2 3EQ, U.K.
³ Department of Geosciences, University of Massachusetts, Amherst, Massachusetts 01003, U.S.A.

Correspondence: ^* E-mail: peter.robinson{at}ngu.no

Fe²⁺/Fe³⁺ charge ordering in the contact layers of lamellar magnetism in the hematite-ilmenite series is not a postulate of the lamellar magnetism hypothesis. Such ordering is possible, however, and a model was suggested earlier in which contact layer Fe²⁺ octahedra share faces with ilmenite layer Ti⁴⁺ octahedra, and contact layer Fe³⁺ octahedra share faces with hematite layer Fe³⁺ octahedra, thus copying the shared-face configurations of ilmenite and hematite, respectively. This model and related charge-balance matters could be explored using bond-valence theory, a simplified picture of complex bonding which takes into account the relationship between bond strength and bond distance, but ignores magnetism. This has now been done, and shows that local oxygen charge satisfaction is strongly favored by a different charge-ordering scheme, in which contact layer Fe³⁺ octahedra share faces with ilmenite layer Ti⁴⁺ octahedra, and contact layer Fe²⁺ octahedra share faces with hematite layer Fe³⁺ octahedra. A new, more sophisticated, Monte Carlo simulation of the interface, including electrostatic and magnetic interaction parameters of cations, reported in detail elsewhere, independently shows the same charge-ordering scheme. For the cation ordered metastable ilmenite 50 composition, bond-valence theory indicates that, unlike the contact layers, the favored charge ordering scheme in Fe layers would have the same shared-face configurations as ilmenite and hematite.

Key Words: Crystal chemistry • bond valence • hematite • ilmenite • magnetic properties • lamellar magnetism • order-disorder • Fe charge ordering

This article has been cited by other articles:

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				R. J. Harrison Microstructure and magnetism in the ilmenite-hematite solid solution: A Monte Carlo simulation study American Mineralogist, July 1, 2006; 91(7): 1006 - 1024. [Abstract] [Full Text] [PDF]