The Vacuum Ultraviolet (VUV) photodissociation of CO2 via the dominant O(1D) channel near 155 nm were studied using Velocity Map Imaging (VMI) technique. Speed dependent vector correlations (the correlations among the transition dipole moment μ of the parent molecule, the recoil velocity vector v and rotational angular momentum vector j of the photofragments) were extracted. This was made possible via the application of a set of equation first developed by Grubb et al. And in combination with a Monte Carlo style simulation program and necessary approximations, full vector correlation information were extracted from the anisotropic angular distributions of the images. Our results indicated a picture of photodissociation mainly via the excited 21A’ (A) state. The transition dipole moment lies in the bent molecular plane. It is not parallel, but pointing away from the dissociating C-O bond. In addition, speed dependent μ-v correlation showed a clear trend, with higher rotationally excited CO correlating to larger angle between μ and the recoil direction. Such clear trend was successfully explained with a mathematical model (first developed by Reisler and coworkers) considering non-axial recoil effect. Although 11A” (B) state is also energetically available, we do not believe it is involved in this case.

Deciphering the dynamics and vector correlations of vacuum ultraviolet (VUV) photodissociation of CO2 at 155 nm

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