Vector correlations in the 355 nm photolysis of thermal NO2

Correlations between the NO2 transition moment mu, the fragment velocities nu and the NO rotational angular momentum J have been made for four NO(upsi lon = 0, J) states which span the most populated rotational levels formed b y photolysis at 355 nm of a sample of NO2 at 298 K. Correlations involving mu are seen to be decreased in comparison with those at lower temperatures, and in particular the translational anisotropy factor beta is reduced by a factor of ca. 2. A speed independent value of beta = 0.7 is shown to descr ibe the fast O(P-3) atoms formed under these conditions and can be used in the analysis of the Doppler profiles measured in studies of their reactions with H2S by means of the "photoloc'' technique. Measured rotational distri butions in upsilon = 0 show some deviations from phase space theory, partic ularly at high J.