Photodissociation of Benzoyl Chloride: A Velocity Map Imaging Study Using VUV Detection of Chlorine Atoms.

UV photodissociation of benzoyl chloride, Ph-CO-Cl, is associated with the loss of a chlorine atom. Here we excite benzoyl chloride to the S1, S2, and S3 excited states at 237, 253, 265, and 279.6 nm and detect the Cl photofragment by [1 + 1'] photoionization using 118.9 nm VUV radiation. The translational energy distribution of the Cl atom is measured by velocity map ion imaging. An isotropic image and a unimodal translational energy distribution are observed at all dissociation wavelengths, and a fraction of 18-20% of the excess energy is released into translation. The results indicate a dissociation that predominately proceeds from the vibrationally hot S0 ground state, although the observed translational energy release deviates significantly from a prior distribution. However, the impulsive model does also not represent the translational energy release. As a Cl/Cl* branching ratio of 9:1 or more is observed in one-color experiments at 235 nm, we conclude that direct dissociation from excited electronic states contributes only to a minor extent.