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Synthetic norsethite, BaMg(CO3)2: revised crystal structure, thermal behaviour and displacive phase transition

Published online by Cambridge University Press:  05 July 2018

H. Effenberger ,
T. Pippinger ,
E. Libowitzky ,
C. L. Lengauer  and
R. Miletich
H. Effenberger*
Affiliation:
Institut für Mineralogie und Kristallographie, Universität Wien, Althanstrasse 14, 1090 Vienna, Austria
T. Pippinger
Affiliation:
Institut für Mineralogie und Kristallographie, Universität Wien, Althanstrasse 14, 1090 Vienna, Austria
E. Libowitzky
Affiliation:
Institut für Mineralogie und Kristallographie, Universität Wien, Althanstrasse 14, 1090 Vienna, Austria
C. L. Lengauer
Affiliation:
Institut für Mineralogie und Kristallographie, Universität Wien, Althanstrasse 14, 1090 Vienna, Austria
R. Miletich
Affiliation:
Institut für Mineralogie und Kristallographie, Universität Wien, Althanstrasse 14, 1090 Vienna, Austria
*
* E-mail: [email protected]
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Abstract

The crystal structure of synthetic BaMg(CO3)2 whose mineral name is norsethite was re-investigated by single-crystal X-ray diffraction. Complementary in situ high- and low-temperature studies by means of vibrational spectroscopy (Raman, IR), powder X-ray diffraction techniques and thermal analyses were performed. Diffraction images (298 K) revealed weak superstructure reflections caused by the displacement of the O atoms in the earlier considered Rm structure model (a = 5.0212(9), cnew = 2 cold = 33.581(6) Å , Rc, Z = 6, R1 = 0.011, sinθ/λ < 0.99 Å –1). Thermal analyses reveal decarbonatization in two decomposition steps above 750 K, and the heat-flow curves (difference scanning calorimetry) give clear evidence of a weak and reversible endothermal change at 343±1 K. This agrees with a discontinuity in the IR and single-crystal Raman spectra. The changing trend of the c/a ratio supports this discontinuity indicating a temperature-induced structural transition in the range between 343 and 373 K. As the change of the unit-cell volume is almost linear, the character of the transition is apparently second order and matches the mechanism of a subtle displacement of the oxygen atom position. The apparent instability of the Rc structure is also evidenced by the remarkably larger anisotropic displacement of the oxygen atom.

Keywords

norsethitespace-group symmetrysingle-crystal X-ray dataRaman spectroscopyIR spectroscopydifference scanning calorimetrypowder X-ray diffractometrycrystal chemistrynon-ambient behaviourdisplacive phase transition
Type
Research Article
Information
Mineralogical Magazine , Volume 78 , Issue 7 , December 2014 , pp. 1589 - 1611
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2014

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