The characterisation of some high temperature molecules using matrix isolation

Abstract

The molecules studied were those obtained from heating samples of sodium phosphate, arsenic oxide, antimony oxide and phosphorus oxides. A survey is given of previous applications of matrix isolation to high temperature chemistry. The experimental apparatus used in this work is described and the method of analysing vibrational spectra is given. Isotopic substitution is shown to be a powerful aid to spectral interpretation and was extensively used. The application of isotopic substitution is discussed with reference to the molecule FeCl3. Sodium phosphate vapour was studied in order to identify the major vapour phase species and this resulted in the determination of the geometry of the molecule NaP03, which until now has remained unknown. The 180 isotope pattern is shown to distinguish between mono- and bidentate coordination of the cation and experiments carried out on 180 enriched material show that coordination of the cation is bidentate. This conclusion is confirmed by a force constant analysis.The vapour above heated antimony trioxide was studied to determine the major species present, and matrix isolated molecular Sb406 was obtained. For the first time vibrational data was obtained for molecular Sb106 and parallel studies on Asg06 were carried out for comparative purposes. A method of identification of molecules of this type, via isotopic substitution was developed and an approach to the location of inactive fundamentals is discussed.The oxides of phosphorus P406, and P4010 were studied as an extension to the studies on As406 and Sb406. The molecules P407, P108 and P1409 were also prepared, and the frequencies of some of their fundamentals were measured. The results obtained represent the most complete set of vibrational data so far available for these molecules. The use of mass spectroscopy in conjunction with matrix isolation is shown to be a powerful method for studying high temperature vapours.

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