A general numerical method is given to extract angular correlations from photodissociation experiments with ion imaging detection. The angular correlations among the transition dipole moment of the parent molecule, μ, the photoproduct recoil velocity, v, and its angular momentum, j, are parametrized analytically using the semiclassical bipolar moment scheme due to Dixon. The method is a forward-convolution scheme which allows quantitative extraction of all measurable bipolar moments and can be applied in experiments with both linearly and circularly polarized probe light. It avoids the cylindrical symmetry limitations of the inverse Abel transform method, traditionally used for extracting photoproduct recoil anisotropy and speed distribution from imaging data. The method presented here also takes into account the possibility of multiple photodissociation channels. The features of the method are illustrated in a two-color 1+1′ REMPI-ion imaging study of the NO photoproduct trajectories resulting from the 650 nm photodissociation of 2-chloro-2-nitrosopropane (CNP). A comparison between experimental and synthetic images is presented for selected experimental geometries. The experimental images for CNP and the results from their fit confirm earlier TOF studies showing that the recoil speed distribution is bimodal with the low and high speed components having average values of approximately 500 and 910 m/s. These components have been previously assigned to dissociation from the S0 and T1 electronic states of the parent molecule, respectively. The experimental results from the current study also confirm that for the high-speed component the product NO velocity vector, v, is preferentially perpendicular to its angular momentum, j [β00(22)=−0.21], and that there is no significant correlation between v and the transition dipole moment μ of the CNP molecule [β02(20)=−0.02].

Circularly polarized 1+1′ REMPI with ion imaging detection was used to probe μ–v–j angular correlations of the NO (X 2Π1/2,3/2, v=0) photoproduct from linearly polarized 355 nm photodissociation of NO2 in a molecular beam. Rotational angular momentum orientation was measured for the NO product, with the sense and magnitude of the orientation depending upon the direction of the NO recoil velocity with respect to the polarization vector of the photolysis light. The rotational orientation is shown to originate from the directionality of the torque responsible for NO rotational motion. The experimentally observed sense of rotation in the plane of the NO2 parent molecule is consistent with an effective recoil impulse force applied to the N end of the NO product. A preliminary measure of the bipolar moment associated with this orientation for the j=21.5 and j=36.5 rotational levels gives a value of approximately β02(21)=0.2.

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