DYNAMICS AND MODE SPECIFICITY IN OCLO PHOTODISSOCIATION

The photodissociation of OClO in a molecular beam was studied using photofragment translational energy spectroscopy at wavelengths between 350 and 475 nm. Although the dominant products are ClO(X2-PI) + (O(P))-P-3, we observe formation of (Cl(P))-P-2 + O2(3-SIGMA(g)-)and find strong evidence for a substantial yield of Cl(2P) + O2(1-DELTA(g)). The total yield reaches a maximum of 3.9 +/- 0.8% near 404 nm and decreases to <0.2% under the absorption peaks in the wavelength range 350-370 nm. The branching ratios display mode specificity: the yield of Cl + O2 from OClO with symmetric stretching excitation or symmetric stretching + bending is approximately 10 times greater than from states at nearly the same energy with asymmetric stretching excitation. The Cl + O2 results from concerted unimolecular decomposition with release of up to approximately 68 kcal/mol in relative translational energy.