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Raman Spectroscopic Investigations of ZrSiO 4 :V 4+ , the Blue Zircon Vanadium Pigment
Author(s) -
Waal Danita de,
Heyns Anton M.,
Pretorius Gerard,
Clark Robin J. H.
Publication year - 1996
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/(sici)1097-4555(199609)27:9<657::aid-jrs10>3.0.co;2-g
Subject(s) - raman spectroscopy , zircon , vanadium , dopant , chemistry , crystallography , crystal (programming language) , crystal structure , infrared , infrared spectroscopy , bond length , analytical chemistry (journal) , materials science , inorganic chemistry , doping , optics , geology , organic chemistry , paleontology , physics , optoelectronics , computer science , programming language
Powdered and single‐crystal samples of the vanadium‐containing zircon pigment ZrSiO 4 :V 4+ were investigated by means of Raman spectroscopy, the spectra being recorded between 200 and 1100 cm −1 at ambient conditions. V–O vibrational bands could be identified by comparison with spectra of pure ZrSiO 4 . The possibility of V 4+ occupation of the interstitial 8d site with C 2 h symmetry was excluded on group theoretical grounds. V—O bond lengths for ZrSiO 4 :V 4+ were estimated to be between 172 and 175 pm from the Raman band wavenumbers; these bond lengths are much shorter than those (204 and 227.6 pm) expected for V 4+ on the Zr 4+ site, but similar to that for V 4+ on the Si 4+ site (175.8 pm). This would indicate substitution on the Si 4+ site, 4b, rather than the Zr 4+ site, 4a. This conclusion is supported by the influence of V 4+ and dopants such as Cr 4+ , Pr 4+ and others on the zircon crystal lattice. The changes in the strengths of Si—O bonds with the change of chromophore incorporated into the structure are reflected in the shifts in wavenumber of the Raman‐active zircon modes.