SEMICLASSICAL TREATMENT OF THE PHOTOFRAGMENTATION OF AZOMETHANE

We have studied the photofragmentation of azomethane by classical traj ectories plus surface hopping, run on ab initio potential energy surfa ces. Transition probabilities are evaluated with the help of a general diabatization technique. The radiationless transition from S-1 to S(0 )occurs within 0.5 ps and the fragmentation takes place almost exclus ively in the ground state. About 2/3 of the trajectories lead to almos t simultaneous breaking of both N-C bonds, while 1/3 go through format ion of the CH3NN. radical; however, the latter breaks apart with a sho rt delay of the order of 1 ps. (C) 1998 Elsevier Science B.V. All righ ts reserved.