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(upsilon = 0, J) states which span the most populated rotational levels formed by 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 describe 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 distributions in upsilon = 0 show some deviations from phase space theory, particularly at high J.