Dissociative Excitation Transfer in the Reaction of O2(a(1)delta(g)) with OH-(H2O)1,2 Clusters
AIR FORCE RESEARCH LAB HANSCOM AFB MA SPACE VEHICLES DIRECTORATE
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Rate constants for the dissociation of OH-H20 and OH-H202 by transfer of electronic energy from 02a1Deltag were measured. Values of 1.8 X 10-11 and 2.2 X 10-11 cm3 molecule-1 s-1 respectively, at 300 K were derived and temperature dependencies were obtained from 300 to 500 K for OH-1H20 and from 300 to 400 K for OH-H202. Dissociative excitation transfer with OH-1H20 is slightly endothermic and the reaction appears to have a positive temperature dependence, but barely outside the uncertainty range. In contrast, the reaction of OH-H202 is exothermic and appears to have a negative temperature dependence. The rate constants are analyzed in terms of unimolecular rate theory, which suggests that the dissociation is prompt and is not affected by collisions with the helium buffer gas.
- Physical Chemistry
- Atomic and Molecular Physics and Spectroscopy