title: Ultraviolet photolysis studies on XeO4 in noble-gas and F2 matrices and the formation and characterization of a new Xe(VIII) oxide, (η(2) -O2 )XeO3.
abstract: The photolytic behavior of the thermochemically unstable xenon(VIII) oxide XeO4 was investigated by UV irradiation in noble-gas and F2 matrices. Photolysis of Xe(16) O4 or Xe(18) O4 in noble-gas matrices at 365 nm yielded XeO3 and a new xenon(VIII) oxide, namely, (η(2) -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 (1) D excited O atoms in the case of excitation at 365 nm, which led to the formation of (η(2) -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 Xe(16) O4 , and (18) O enrichment provided the (16) O/(18) O isotopic shifts of XeO4 and (η(2) -O2 )XeO3 .
authors.affiliation: Albert-Ludwigs Universität Freiburg, Institut für Anorganische und Analytische Chemie, Albertstrasse 21, 79104 Freiburg (Germany).
authors.forename: Thomas
authors.initials: T
authors.lastname: Vent-Schmidt
authors.affiliation: McMaster University, Department of Chemistry, 1280 Main Street West, Hamilton, Ontario L8S 4M1 (Canada).
authors.forename: James T
authors.initials: JT
authors.lastname: Goettel
authors.affiliation: Albert-Ludwigs Universität Freiburg, Institut für Anorganische und Analytische Chemie, Albertstrasse 21, 79104 Freiburg (Germany). schrobil@mcmaster.ca.|McMaster University, Department of Chemistry, 1280 Main Street West, Hamilton, Ontario L8S 4M1 (Canada). schrobil@mcmaster.ca.
authors.forename: Gary J
authors.initials: GJ
authors.lastname: Schrobilgen
authors.affiliation: Freie Universität Berlin, Institut für Chemie und Biochemie, Fabeckstrasse 34-36, 14195 Berlin (Germany). s.riedel@fu-berlin.de.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Riedel
keywords: IR spectroscopy; isotope effects; matrix isolation; photochemistry; xenon