Photodissociation dynamics of allyl bromide at 234, 265, and 267 nm

The photodissociation dynamics of allyl bromide was investigated at 234, 265, and 267 nm. A two-dimensional photofragment ion velocity imaging technique coupled with a [2+1] resonance-enhanced multiphoton ionization scheme was utilized to obtain the angular and translational energy distributions of the nascent Br-* (P-2(1/2)) and Br (P-2(3/2)) atoms. The Br fragments show a bimodal translational energy distribution, while the Br-* fragments reveal one translational energy distribution. The vertical excited energies and the mixed electronic character of excited states were calculated at ab initio configuration interaction method. It is presumed that the high kinetic energy bromine atoms are attributed to the predissociation from (1)(pi pi(*)) or (1)(pi sigma(*)) state to the repulsive (1)(n sigma(*)) state, and to the direct dissociation from (3)(n sigma(*)) and (3)(pi sigma(*)) states, while the low kinetic energy bromine atoms stem from internal conversion from the lowest (3)(pi pi(*)) state to (3)(pi sigma(*)) state.