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Stabilization of trivalent Mn in natural tetragonal hydrogarnets on the join ‘hydrogrossular’—henritermierite, Ca3Mn23+ [SiO4]2[H4O4]

Published online by Cambridge University Press:  05 July 2018

U. Hålenius
U. Hålenius*
Affiliation:
Department of Mineralogy, Swedish Museum of Natural History, Box 50007, SE-104 05 Stockholm, Sweden
*
*E-mail: ulf.halenius@nrm.se
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Abstract

Four relatively intense and broad absorption bands centred at ∼12500, ∼19500, ∼21500 and ∼23000 cm–1 were recorded in polarized electronic single-crystal spectra of natural, optically uniaxial and pleochroic hydrogarnets with henritermierite contents ranging from 35 to 97 mol.%. These absorption bands arise from spin-allowed electronic d-d transitions in trivalent Mn located at the axially distorted six-coordinated site of the tetragonal hydrogarnet structure.

The crystal field stabilization energy (CFSE) for trivalent Mn at the Mn site, as derived from band energies, is ∼185 kJ/mol. This considerably higher CFSE for Mn3+ in tetragonal hydrogarnets as compared to cubic garnets (130 –145 kJ/mol) explains the natural occurrence of close to end-member tetragonal Mn3+-hydrogarnets while only limited Mn3+-substitution is observed in natural cubic garnets.

The fact that incorporation of Mn3+ at intermediate concentrations stabilizes the tetragonal hydrogarnets indicates the potential natural existence of a number of new, partially Mn3+-substituted, hydrogarnets, e.g. tetragonal Mn3+-bearing ‘hydroandradite’.

Keywords

chemical analysiselectronic spectratrivalent manganesehenritermierite‘hydrogrossular’
Type
Research Article
Information
Mineralogical Magazine , Volume 68 , Issue 2 , April 2004 , pp. 335 - 341
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2004

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