Ultraviolet spectrum and chemical reactivity of the ClO dimer

The ClO dimer was prepared by photolysis (wavelength greater than 300 nm) of Cl2/Cl2O or Cl2/O3 mixtures or by photolysis of Cl2O alone. Temperatures were in the range 195-217 K, and experiments were carried out both in the gas phase and in the cryogenic solvents CF4, CO2, and N2O. Dimer cross sections in the range 190-400 nm are reported both in the gas phase and in the solvents. Results indicate that ClOOCl is the only dimer structure formed as a stable product. Upper limits of 1 x 10 to the -19th and 1 x 10 to the -20th cu cm/s are placed on the reactions of ClOOCl with O3 and with itself, respectively.