PHOTODISSOCIATION, RECOMBINATION, AND ELECTRON-TRANSFER IN CLUSTER IONS - A NONADIABATIC MOLECULAR-DYNAMICS STUDY OF I-2(-)(CO2)(N)

we simulate and interpret the photodissociation and recombination of I -2(-) embedded in CO2 clusters using a Hamiltonian that accounts for t he strong perturbation of the solute electronic structure by the solve nt. The calculated product distributions agree well with the experimen tal results of Lineberger and co-workers. Excited-state dynamics are m ore involved than anticipated from the isolated solute potential curve s. For example, dissociation does not occur from the A' state, and per manent recombination occurs only on the X state, despite the fact that the A state of I-2(-) is weakly bound. we discuss the role of the clu ster environment in bringing about recombination and electronic relaxa tion in terms of a qualitative model inspired by the theory of electro n transfer in solution.