CHARGE FLOW AND SOLVENT DYNAMICS IN THE PHOTODISSOCIATION OF CLUSTER IONS - A NONADIABATIC MOLECULAR-DYNAMICS STUDY OF I-2(-)CENTER-DOT-AR-N

Experimental studies of photodissociation in I-2(-). Ar-n clusters hav e shown a rapid onset of caging for n > 10 and bimodal photofragment d istributions in both dissociation and recombination channels. We simul ate and interpret these results using a Hamiltonian that accounts for the strong perturbation of the solute electronic structure by the solv ent, The high-mass products in the recombination channel are identifie d with excited state recombination, The two classes of dissociation pr oducts are identified with ejection of either a neutral I atom or an I - ion from the cluster, with the latter mechanism driven by the negati ve polarizability of the excited electronic state. (C) 1997 Elsevier S cience B.V.