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Co2+-doped diopside: crystal structure and optical properties
University of Parma, Italy.
University of Parma, Italy.
University of Parma, Italy.
Swedish Museum of Natural History, Department of Geology.
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2018 (English)In: Physics and chemistry of minerals, ISSN 0342-1791, E-ISSN 1432-2021, Vol. 45, no 5, p. 443-461Article in journal (Refereed) Published
Abstract [en]

Synthetic clinopyroxenes along the CaMgSi2O6– CaCoSi2O6 join were investigated by a combined chemical-structuralspectroscopic approach. Single crystals were synthesized by flux growth methods, both from Ca-saturated and Ca-deficient starting compositions. Single crystal structure refinements show that the incorporation of Co2+ at the octahedrally coordinated cation sites of diopside, increases the unit-cell as well as the M1 and the M2 polyhedral volumes. Spectroscopic investigations (UV–VIS–NIR) of the Ca-rich samples reveal three main optical absorption bands, i.e. 4T1g4T2g(F), 4T1g 4A2g(F) and 4T1g4T1g(P) as expected for Co2+ at a six-coordinated site. The bands arising from the 4T1g4T2g(F) and the 4T1g4T1g(P) electronic transitions, are each split into two components, due to the distortions of the M1 polyhedron from ideal Oh- symmetry. In spectra of both types, a band in the NIR range at ca 5000 cm−1 is caused by the 4A2g4T1g(F) electronic transition in Co2+ in a cubic field in the M2 site. Furthermore, an additional component to a band system at 14,000 cm−1, due to electronic transitions in Co2+ at the M2 site, is recorded in absorption spectra of Ca-deficient samples. No variations in Dq and Racah B parameters for Co2+ at the M1 site in response to compositional changes, were demonstrated, suggesting complete relaxation of the M1 polyhedron within the CaMgSi2O6– CaCoSi2O6 solid solution.

Place, publisher, year, edition, pages
2018. Vol. 45, no 5, p. 443-461
National Category
Geochemistry
Research subject
The changing Earth
Identifiers
URN: urn:nbn:se:nrm:diva-2799DOI: 10.1007/s00269-017-0932-zOAI: oai:DiVA.org:nrm-2799DiVA, id: diva2:1212459
Available from: 2018-06-01 Created: 2018-06-01 Last updated: 2018-06-04Bibliographically approved

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