Ultraviolet Photolysis Studies on XeO4 in Noble‐Gas and F2 Matrices and the Formation and Characterization of a New XeVIII Oxide, (η2‐O2)XeO3

AbstractThe photolytic behavior of the thermochemically unstable xenon(VIII) oxide XeO4 was investigated by UV irradiation in noble‐gas and F2 matrices. Photolysis of Xe16O4 or Xe18O4 in noble‐gas matrices at 365 nm yielded XeO3 and a new xenon(VIII) oxide, namely, (η2‐O2)XeO3, which, along with XeO4, was characterized by matrix‐isolation IR spectroscopy and quantum‐chemical calculations. Calculations of the UV spectrum showed that the photodecomposition is induced by an n→σ* transition, but the nature of the excitation differs when different light sources are used. There is strong evidence for the formation of mobile 1D excited O atoms in the case of excitation at 365 nm, which led to the formation of (η2‐O2)XeO3 by reaction with XeO4. Matrix‐isolation IR spectroscopy in Ne and Ar matrices afforded the natural‐abundance xenon isotopic pattern for the ν3(T2) stretching mode of Xe16O4, and 18O enrichment provided the 16O/18O isotopic shifts of XeO4 and (η2‐O2)XeO3.

Ultraviolet Photolysis Studies on XeO₄ in Noble‐Gas and F₂ Matrices and the Formation and Characterization of a New Xe^VIII Oxide, (η²‐O₂)XeO₃ Journal Articles