Ab initio study of the molecular structure and vibrational spectra of dichlorine hexoxide and its significance to stratospheric ozone depletion

Abstract

Abstract Five minimum energy structures have been identified for dichlorine hexoxide and ab initio calculations have been performed on these isomers at the 6–31G∗ and MP2/6–31G∗ levels. Among the five structures, the oxygen-bridged structure and a symmetrical dimer containing a ClCl bond were found to be stable. Normal mode analysis has been carried out on the stable conformers. The relative strength of the O3ClO and OClO2 bonds of the oxygen-bridged structure is discussed on the basis of their vibrational frequencies. In addition, the paper focuses attention on the great importance of the reaction 2OClO + 2O3 → Cl2O6 + 2O2. The implications of these results to the chemistry of stratospheric ozone depletion are delineated.