Parent bending effects on nonadiabatic transition dynamics: Isotopomer-resolved imaging of photodissociation of CF3Br at two source temperatures.

Nonadiabatic transition between electronic states plays a critical role in the photodissociation of the CX3Y (X = H and F; Y = Cl, Br, and I) system, and the transition probability was considered to be closely related to the X-C-Y bending motion. Hereby the effect of F-C-Br bending vibration on the nonadiabatic transition dynamics is studied by time-sliced ion velocity imaging of Br(2P1/2,3/2) isotopomers produced from the photodissociation of title molecules at two source temperatures, 298 K and 473 K, respectively. At the photolysis wavelength 234 nm, the anisotropy parameter (β) of the Br(2P3/2) products decreases from 1.3 at 298 K to 0.9 at 473 K, while the β of Br(2P1/2) remains at almost 2 at two temperatures, indicating the significant effect of bending excitation on the ground channel. Two nonadiabatic dissociation pathways are suggested in the Br(2P3/2) channel. One of them is the parallel excitation from the ground state to the 3 Q 0 state in C3V symmetry, and then transition to the 1 Q 1 state via conical intersection, and the other is the perpendicular excitation to the 3A' state in Cs symmetry and then decomposition along this state in the presence of the avoided crossing between 3A' and 4A' states. Closely related to the F-C-Br bending vibration of CF3Br is the latter transition.