1 Raman and infrared spectroscopy of selected vanadates

Raman and infrared spectroscopy has been used to study the structure of selected vanadates including pascoite, huemulite, barnesite, hewettite, metahewettite, hummerite. Pascoite, rauvite and huemulite are examples of simple salts involving the decavanadates anion (V10O28). Decavanadate consists of four distinct VO6 units which are reflected in Raman bands at the higher wavenumbers. The Raman spectra of these minerals are characterised by two intense bands at 991 and 965 cm. For pascoite Raman bands are observed at 991, 965, 958 and 905 cm and originate from four distinct VO6 sites. The other minerals namely barnesite, hewettite, metahewettite and hummerite have similar layered structures to the decavanadates but are based upon (V5O14) units. Barnesite is characterised by a single Raman band at 1010 cm, whilst hummerite has Raman bands at 999 and 962 cm. The absence of four distinct bands indicates the overlap of the vibrational modes from two of the VO6 sites. Metarossite is characterised by a strong band at 953 cm. These bands are assigned to ν1 symmetric stretching modes of (V6O16) units and terminal VO3 units. In the infrared spectra of these minerals, bands are observed in the 837 to 860 and in the 803 to 833 cm region. In some of the Raman spectra bands are observed for pascoite, hummerite and metahewettite in similar positions. These bands are assigned to ν3 antisymmetric stretching of (V10O28) units or (V5O14) units. Because of the complexity of the spectra in the low wavenumber region assignation of bands is difficult. Bands are observed in the 404 to 458 cm region and are assigned to the ν2 bending modes of (V10O28) units or (V5O14) units. Raman bands are observed in the 530 to 620 cm region and are assigned to the ν4 bending modes of (V10O28) units or (V5O14) units. The Raman spectra of the vanadates in the low wavenumber region are complex with multiple overlapping bands which are probably due to VO subunits and MO bonds.