Direct observation of the primary and secondary C-Br bond cleavages from the 1,2-dibromopropane photodissociation at 234 and 265 nm using the velocity map ion imaging technique.

Photodissociation dynamics of 1,2-dibromopropane has been investigated at 234 and 265 nm by using the velocity map ion imaging method. At both pump energies, a single Gaussian-shaped speed distribution is observed for the Br*((2)P(1/2)) fragment, whereas at least three velocity components are found to be existent for the Br((2)P(3/2)) product. The secondary C-Br bond cleavage of the bromopropyl radical which is energized from the ultrafast primary C-Br bond rupture should be responsible for the multicomponent translational energy distribution at the low kinetic energy region of Br((2)P(3/2)). The recoil anisotropy parameter (beta) of the fragment from the primary C-Br bond dissociation is measured to be 0.53 (0.49) and 1.26 (1.73) for Br((2)P(3/2)) and Br*((2)P(1/2)), respectively, at 234 (265) nm. The beta value of Br((2)P(3/2)) from the secondary C-Br bond dissociation event at 265 nm is found to be 0.87, reflecting the fact that the corresponding Br((2)P(3/2)) fragment carried the initial vector component of the bromopropyl radical produced from the primary bond dissociation event. Density functional theory has been used to calculate energetics involved both in the primary and in the secondary C-Br bond dissociation dynamics.