A low temperature X-ray single-crystal diffraction and polarised infra-red study of epidote |
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| Authors: | G Diego Gatta Matteo Alvaro Geoffrey Bromiley |
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| Institution: | (1) Dipartimento di Scienze della Terra, Universit? degli Studi di Milano, Via Botticelli 23, 20133 Milan, Italy;(2) CNR-Istituto per la Dinamica dei Processi Ambientali, Milan, Italy;(3) Crystallography Laboratory, Department of Geosciences, Virginia Tech, Blacksburg, VA 24060, USA;(4) School of GeoSciences and CSEC, The University of Edinburgh, Edinburgh, UK |
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| Abstract: | The effects of low-temperature on the crystal structure of a natural epidote Ca1.925Fe0.745Al2.265Ti0.004Si3.037O12(OH), a = 8.8924(7), b = 5.6214(3), c = 10.1547(6)? and β = 115.396(8)° at room conditions, Sp. Gr. P21
/m] have been investigated with a series of structure refinements down to 100 K on the basis of X-ray single-crystal diffraction
data. The reflection conditions confirm that the space group is maintained within the T-range investigated. Structural refinements at all temperatures show the presence of Fe3+ at the octahedral M(3) site only %Fe(M3) = 70.6(4)% at 295 K]. Only one independent proton site was located and two possible
H-bonds occur, with O(10) as donor and O(4) and O(2) as acceptors. The H-bonding scheme is maintained down to 100 K and is
supported by single crystal room-T polarised FTIR data. FTIR Spectra over the region 4,000–2,500 cm−1 are dominated by the presence of a strongly pleochroic absorption feature which can be assigned to protonation of O(10)–O(4).
Previously unobserved splitting of this absorption features is consistent with a NNN influence due to the presence of Al and
Fe3+ on the nearby M(3) site. An additional relatively minor absorption feature in FTIR spectra can be tentatively assigned to
protonation of O(10)–O(2). Low-T does not affect significantly the tetrahedral and octahedral bond distances and angles, even when distances are corrected
for “rigid body motions”. A more significant effect is observed for the bond distances of the distorted Ca(1)- and Ca(2)-polyhedra,
especially when corrected for “non-correlated motion”. The main low-T effect is observed on the vibrational regime of the atomic sites, and in particular for the two Ca-sites. A significant reduction
of the magnitude of the thermal displacement ellipsoids, with a variation of U
eq
(defined as one-third of the trace of the orthogonalised U
ij
tensor) by ~40% is observed for the Ca-sites between 295 and 100 K. Within the same T-range, the U
eq
of the octahedral and oxygen sites decrease similarly by ~35%, whereas those of the tetrahedral cations by ~22%. |
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