Structure and selective visible photodissociation of the O3:Br2 and O3:BrCl complexes: An infrared matrix isolation and ab initio study Original Research Article

Complexes of ozone with chlorine, bromine and bromine chloride were reinvestigated in argon matrix by Fourier Transform Infrared spectroscopy. All three ozone submolecule fundamentals were observed and ν1 was enhanced in intensity relative to ν3. The asymmetric mixed isotopic ozone complexes exhibit a split ν3 band which indicates unequivalent terminal oxygens. Photolysis of the O3/BrCl system which was studied with the 870, 633 and 532 nm laser lines gives only ClBrO as a primary product indicating that the most stable complex between BrCl and O3 occurs through bonding of ozone with Br. Results show that at 633 nm, ClBrO transforms it into BrClO whereas at 870 nm, it is isomerized to BrOCl. Ab initio calculations undertaken on the structures of O3:Cl2 and O3:BrCl support experimental observations.