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Matrix isolation - I.R. studies: oxygen-fluorine discharges and the photolysis of cis-thionylimide Tchir, Peter Oryst

Abstract

Oxygen-fluorides: Attempts have been made at identifying O₃F₂ in the condensate of oxygen fluorine discharges using i.r. spectroscopy. O₂F₂, (O₂F)₂ , OF₂ , OF and O₃ have been observed and numerous overtones and combinations have been measured and assigned for the first time. No evidence could be found for the presence of an species suggesting that “O₃F₂” is actually a mixture of O₂F₂ and (O₂F)₂. The confirmation of the previously reported spectrum of solid O₂F₂ has been made and a careful analysis of the normal coordinate calculations has resulted in a preference for a force field for O₂F₂ with f [sub ∞]= 7.14 aJ/Ų in contrast to the previously reported calculations which found f [sub ∞]= 10.25 aJ/Ų. cis-HNSO: The spectra of cis-HNSO and its isotopic homologs containing ¹⁵N, D and ³⁴S have been obtained in Ar and N₂ matrices. A force field with 11 parameters (containing 3 interaction constants) has been calculated from the 29 observed frequencies. The u.v. and vacuum u.v. photolysis of cis-HNSO has been carried out in Ar matrices with the identification of 6 new species from their i.r. spectra. Complete spectra have been observed for cis-HOSN and trans-HSNO, four modes for trans-HNSO, two modes for SNO and one mode for cis-HSNO and NSO. Using isotopic substitution, assignments have been made in all cases and approximate force fieldshave been obtained for cis-HOSN, trans-HSNO and trans-HNSO using guessed structures. The following reaction scheme has been determined from kinetic studies.[See Thesis for Equations]

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