Structure and selective visible photodissociation of the O-3:Br-2 and O-3:BrCl complexes: An infrared matrix isolation and ab initio study

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 nu(1) was enhanced in intensity relative nu(3). The asymmetric mixed isotopic ozone complexes exhibit a split nu(3) band which indicates unequivalent terminal oxygens. Photolysis of the O-3/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 O-3, 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 O-3:Cl-2 and O-3:BrCl support experimental observations.