A MATRIX-ISOLATION STUDY OF THE WATER COMPLEXES OF CL2, CLOCL, OCLO, AND HOCL AND THEIR PHOTOCHEMISTRY

The IR spectra and photochemistry of the binary water complexes of Cl2, ClOCl, HOCl, and OClO, isolated in argon matrices, have been studied. Water acts as a lone pair done toward Cl2, ClOCl, and ClO2, probably with the water oxygen next to a chlorine atom in all three cases. Irradiation of the water-chlorine complex with near-UV radiation produces a complex between HOCl and HCl, with HCl as proton donor and HOCl as acceptor. The photoproduct of the ClOCl water complex is (HCl)2-O2. H2O-ClO2 gives H2O-ClOO upon UV irradiation. Complex formation does not change the photochemistry of matrix isolated OClO. HOCl forms a hydrogen bond to the water oxygen, we were unable to decompose the HOCl-water complex.