Photoabsorption and photoionization of chlorine dioxide

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