Highly inverted vibrational level populations are found for ClO fragments resulting from the UV photodissociation of OClO(2A2 ν1>20) into ClO(X 2ΠΩ,v,J) and O(3PJ) fragments. These distributions depend significantly on the spin–orbit J state of the oxygen O(3PJ) partner atom. In contrast, the ClO rotational excitation is modest. Distinct rotational structure is visible in the O (3PJ) photofragment yield spectrum recorded from the highly excited OClO (2A2 ν1=21) vibronic band, which is indicative for hitherto unforeseen long dissociation lifetimes of very highly excited OClO. The data point towards an unexpected nearly-linear and highly asymmetric dissociation geometry. Carrying out near-threshold fragmentation experiments of OClO (2A20,0,0)→ClO (X 2Π3/2v=0,J)+O(3P2,1,0) the dissociation energy D0 of OClO has been accurately determined to 247.3±0.5 kJ/mol.

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