Ultraviolet Photolysis of the ClO Dimer
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Abstract
Photodissociation of the ClO dimer (ClOOCl) is studied in the ultraviolet regime (250 and 308 nm) under collision-free conditions. The primary photolysis products are probed by photoionization mass spectrometry. At both photolysis wavelengths, exclusively the formation of 2Cl + O2 is observed, corresponding to a primary quantum yield γCl near unity. Considering the error limit of the experimental results one obtains γCl ≥ 0.98 at 250 nm and γCl ≥ 0.90 at 308 nm, respectively. At both photolysis wavelengths the pathway yielding ClO is not observed, corresponding to γClO ≤ 0.02 at 250 nm and γClO ≤ 0.10 at 308 nm. Sensitivity studies of these results with respect to ozone depletion in the stratosphere regarding photochemically induced ozone loss are discussed using model simulations. These simulations suggest that a change of γCl from 1.0 to 0.9 leads to a reduction of polar ozone loss of ∼5%.
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