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A Raman spectroscopic study of the uranyl mineral rutherfordine – revisited

Frost, Ray L. & Cejka, Jiri (2009) A Raman spectroscopic study of the uranyl mineral rutherfordine – revisited. Journal of Raman Spectroscopy, 40(9), pp. 1096-1103.

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Abstract

The molecular structure of the uranyl mineral rutherfordine has been investigated by the measurement of the NIR and Raman spectra and complemented with infrared spectra including their interpretation. The spectra of the rutherfordine show the presence of both water and hydroxyl units in the structure as evidenced by IR bands at 3562 and 3465 cm-1 (OH) and 3343, 3185 and 2980 cm-1 (H2O). Raman spectra show the presence of four sharp bands at 3511, 3460, 3329 and 3151 cm-1. Corresponding molecular water bending vibrations were only observed in both Raman and infrared spectra of one of two studied rutherfordine samples. The second rutherfordine sample studied contained only hydroxyl ions in the equatorial uranyl plane and did not contain any molecular water. The infrared spectra of the (CO3)2- units in the antisymmetric stretching region show complexity with three sets of carbonate bands observed. This combined with the observation of multiple bands in the (CO3)2- bending region in both the Raman and IR spectra suggests that both monodentate and bidentate (CO3)2- units may be present in the structure. This cannot be exactly proved and inferred from the spectra; however, it is in accordance with the X-ray crystallographic studies. Complexity is also observed in the IR spectra of (UO2)2+ antisymmetric stretching region and is attributed to non-identical UO bonds. U-O bond lengths were calculated using wavenumbers of the 3 and 1 (UO2)2+ and compared with data from X-ray single crystal structure analysis of rutherfordine. Existence of solid solution having a general formula (UO2)(CO3)1-x(OH)2x.yH2O ( x, y  0) is supported in the crystal structure of rutherfordine samples studied.

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ID Code: 27423
Item Type: Journal Article
Additional Information: This paper is one of a large series of papers on the Raman Spectroscopy of the secondary minerals containing the uranyl ion
Keywords: rutherfordine, uranyl carbonate, molecular water, hydroxyls, infrared and Raman spectroscopy, U-O and O-H, O bond lengths
DOI: 10.1002/jrs.2174
ISSN: 0377-0486
Subjects: Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > PHYSICAL CHEMISTRY (INCL. STRUCTURAL) (030600)
Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > PHYSICAL CHEMISTRY (INCL. STRUCTURAL) (030600) > Structural Chemistry and Spectroscopy (030606)
Divisions: Past > QUT Faculties & Divisions > Faculty of Science and Technology
Past > Schools > School of Physical & Chemical Sciences
Copyright Owner: Copyright 2009 Wiley
Deposited On: 18 Sep 2009 09:56
Last Modified: 01 Mar 2012 00:07

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