Raman spectroscopy of uranopilite of different origin - implications for molecular structure
Frost, Ray L., Cejka, Jiri, Weier, Matt L., Martens, Wayde N., & Ayoko, Godwin A. (2007) Raman spectroscopy of uranopilite of different origin - implications for molecular structure. Journal of Raman Spectroscopy, 38(4), pp. 398-409.
Uranopilite, [(UO2)6(SO4)O2(OH)6(H2O)6](H2O)8, the composition of which may vary, can be understood as a complex hydrated uranyl oxy hydroxy sulfate. The structure of uranopilite of different localities has been studied by Raman spectroscopy at 298 and 77 K. A single intense band at 1009 cm-1 assigned to the ￮1 (SO4)2- symmetric stretching mode shifts to higher wavenumbers at 77 K. Three low intensity bands are observed at 1143, 1117 and 1097 cm-1. These bands are attributed to the (SO4)2- ν3 antisymmetric stretching modes. Multiple bands provide evidence that the symmetry of the sulphate anion in the uranopilite structure is lowered. Three bands are observed at 843 to 816 cm-1 in both 298 and 77 K spectra and are attributed to the ν1 symmetric stretching modes of the (UO2)2+ units. Multiple bands prove the symmetry reduction of the UO2 ion. Multiple OH stretching modes prove a complex arrangement of OH groupings and hydrogen bonding in the crystal structure. A series of infrared bands not observed in the Raman spectra are found at 1559, 1540, 1526 and 1511 cm-1 attributed to ￤ UOH bending modes. U-O bond lengths in uranyl and O-H…O bond lengths are calculated and compared with X-ray single crystal structure analysis. Raman spectra of uranopilites of different origin show subtle differences in spectra proving the spectra are origin and sample dependent. Hydrogen-bonding network and its arrangement in the crystal structure play an important role in the origin and stability of uranopilite.
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|Item Type:||Journal Article|
|Keywords:||Keywords, uranopilite, johannite, zippeite, uranyl sulphate minerals, dehydroxylation, dehydration, infrared and Raman spectroscopy|
|Subjects:||Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > PHYSICAL CHEMISTRY (INCL. STRUCTURAL) (030600) > Structural Chemistry and Spectroscopy (030606)
Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > PHYSICAL CHEMISTRY (INCL. STRUCTURAL) (030600) > Structural Chemistry and Spectroscopy (030606)
Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > PHYSICAL CHEMISTRY (INCL. STRUCTURAL) (030600) > Colloid and Surface Chemistry (030603)
|Divisions:||Past > QUT Faculties & Divisions > Faculty of Science and Technology
Past > Schools > School of Physical & Chemical Sciences
|Copyright Owner:||Copyright 2007 John Wiley & Sons|
|Copyright Statement:||The definite version is available on publication at www3.interscience.wiley.com|
|Deposited On:||10 May 2007 00:00|
|Last Modified:||18 Jan 2016 04:18|
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