Vector correlations in the 355 nm photolysis of thermal NO2

Abstract

Correlations between the NO₂ transition moment μ, the fragment velocities ν and the NO rotational angular momentum J have been made for four NO(v=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 μ are seen to be decreased in comparison with those at lower temperatures, and in particular the translational anisotropy factor β is reduced by a factor of ca. 2. A speed independent value of β=0.7 is shown to describe the fast O(³P) 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 v=0 show some deviations from phase space theory, particularly at high J.