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Photoprocesses of chlorine dioxide in the near-UV have become highly important for stratospheric photoprocesses at high latitudes, especially in Antarctica. Chlorine dioxide has been identified among other absorbers because of its specific absorption cross section in the near-UV. Possible contributions of chlorine dioxide photochemistry to polar ozone depletion have been discussed recently. The high-resolution He I photoelectron spectrum and the absolute (vacuum-UV) absorption cross section (6-25 eV) as well as the ionic fragmentation of chlorine dioxide (OCIO) are reported. The photoelectron spectrum is interpreted in terms of exchange splitting effects of the various singlet and triplet cation states as well as by comparison to chemically related molecules. The vacuum-UV absorption spectrum shows different Rydberg series converging to the cation states. These Rydberg series and their vibrational progressions are assigned by term value arguments, dipole selection rules, and comparison with the photoelectron spectrum. Photoionization mass spectrometry is used for measurements of the ionization and fragmentation threshold of OCIO. The major fragment is ClO[sup +] which occurs above 13.4 eV. Thermomechanical data such as heats of formation and bond dissociation energies are derived. No evidence for isomerization of OClO[sup +] is found, as observed for the electronically excited neutral molecule. 54 refs.,more » 6 figs., 7 tabs.« less |
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