Vitreous and relevant crystalline polymorphs of P2O5 have been synthesised and characterised by X-ray diffraction and Raman scattering spectroscopy. On the basis of the crystallographic data of single crystals of the three varieties H-P2O5, O-P2O5 and O'-P2O5, the interpretation of vitreous P2O5 Raman spectrum was given taking into consideration the short and intermediate range order. It inferred that the intermediate range order in v-P2O5 can mainly be described in terms of a mixture of both high temperature modifications, with however predominance of O'-P2O5. This hypothesis has been substantiated by in situ Raman study of v-P2O5 recrystallisation.
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