A theoretical study of photofragmentation and geminate recombination of ICN in solid Ar

Photodissociation of ICN in an Ar matrix is studied by molecular dynamics with quantum transitions (MDQT) with the motion of the nuclei treated classically and the electronic motion quantum mechanically. Four electronic surfaces and their corresponding couplings are included in the calculations. The coupling between electronic states at large I-CN internuclear distances is modeled using a diatomic in molecules (DIM) treatment of the mixing of the different spin-orbit states of iodine induced by the Ar atoms. For a total propagation time of 3 ps, no cage exit is found and 44% of the trajectories recombine to the ground electronic state. The principal mechanism for geminate recombination involves the reaction path (II0+)-I-3-->(II1)-I-1-->(1)Sigma(0+)(+). (C) 1998 American Institute of Physics.