Abstract

This paper examined the heterogeneous photochemistry of OCIO in solution. The detailed photochemistry of this molecule is important as ozone destruction in the Antarctic has been linked to the photochemical dynamics of OCIO and related chlorine oxides. Recent gas phase spectroscopic studies show that excitation in the near ultraviolet of isolated OCIO leads to both photodissociation to form vibrationally excited CIO and O and to photoisomerization which ultimately leads to Cl and O₂. The former photoprocess is more efficient in the gas phase, but the relative quantum yields for these two reactive channel are still controversial. The latter process generates atomic chlorine, a product which can result in catalytic ozone depletion. The interactions between OCIO and polar molecules, e.g. H₂O, can dramatically effect the observed molecules. We have examined the spectroscopy and photochemistry of OCIO in solutions. Reactivity in a variety of polar aprotics, nonpolar hydrocarbons, alcohols and water have been examined. These studies reveal rich and complicated photodynamics.

© 1992 The Author(s)