Photofragment translational spectroscopy was used to identify the primary and secondary reaction pathways in 193 nm photodissociation of chlorine azide ͑ClN 3 ͒ under collision-free conditions. Both the molecular elimination ͑NCl+ N 2 ͒ and the radical bond rupture channel ͑Cl+ N 3 ͒ were investigated and compared with earlier results at 248 nm. The radical channel strongly dominates, just as at 248 nm. At 193 nm, the ClN 3 ͑C 1 AЉ͒ state is excited, rather than the B 1 AЈ state that is

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... at 248 nm, resulting in different photofragment angular distributions. The chlorine translational energy distribution probing the dynamics of the radical bond rupture channel shows three distinct peaks, with the two fastest peaks occurring at the same translational energies as the two peaks seen at 248 nm that were previously assigned to linear and "high energy" N 3 . Hence, nearly all the additional photon energy relative to 248 nm appears as N 3 internal excitation rather than as translational energy, resulting in considerably more spontaneous dissociation of N 3 to N 2 +N.