Two primary product channels in OClO photodissociation near 360 nm

In the near UV region, there are two product channels possible for the photodissociation of OClO—OCl+O and Cl+O2. We have performed a number of experiments which confirm that Cl atoms are a primary product of OClO photodissociation near 360 nm. We use (2+1) resonance-enhanced multiphoton ionization to detect the Cl(2P3/2 and 2P1/2) and OCl (X 2Π) products of the photolysis of jet-cooled OClO. The two product channels have action spectra which have the same peak positions as the OClO Ã←X̃ absorption spectrum, but which have different relative peak intensities, showing that the two product channels are dynamically different. Kinetic studies show that the Cl atom signal disappears at a rate consistent with the reaction Cl+OClO→2OCl, also indicating that Cl is a primary photodissociation product. A double-resonant excitation of OClO might take place, and could explain the disparate photodissociation results reported to date.