Abstract
The nascent vibrational distribution of ClO(X2Π) radicals produced in the ozone destruction reaction Cl + O3 → ClO + O2 has been measured, using vacuum-ultraviolet laser-induced fluorescence of the ClO(C2Σ-−X2Π) transition. The nascent vibrational distribution of the ClO radicals is shown to be strongly inverted, with the relative ratio (v=0):(v=1):(v=2):(v=3):(v=4):(v=5) = 0.8:1:1.3:2.4:2.9:2.7. The slope of the surprisal plots for the vibrational distribution of the product ClO is found to be (−8 ± 2). Vibrational relaxation processes for the ClO radicals in the X2Σ state by collisions are also studied. The upper limit values of the vibrational relaxation rate constants for ClO (v=1→0) by collisions with N2 and Ar molecules are estimated to be both 5 × 10-14 cm3 molecule-1 s-1.
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