15min:

ANNE B. MCCOY, Department of Chemistry, The Ohio State University, Columbus, OH 43210; AMANDA S CASE, JOSHUA P. MARTIN AND W. CARL LINEBERGER, JILA and Department of Chemistry and Biochemistry University of Colorado, Boulder, CO 80309.

The photofragmentation dynamics of ICN^- in isolation and in complexes with argon or CO₂ are investigated through a combination of experimental and theoretical studies. Experimentally, we probe the excited state dynamics of ICN^- following excitation to the lowest energy state that correlates to I^- + CN products. In the absence of solvating atoms or molecules, most of the excess charge localizes on I^-, although ~ 3% of the products have the charge localized on the CN^-. The introduction of a single CO₂ or argon atom changes the branching ratio between the three possible product channels (I^- , CN^- or ICN^-). Interestingly when one argon atom is introduced roughly 5% of the products undergo cage recombination to form ICN^-, providing an example of single atom caging. When CO₂ is introduced, cage recombination is only seen in larger complexes, but a significant fraction of the photoproducts obtained following excitation of ICN^- CO₂ have the charge localized on the CN. These results will be discussed and analyzed using potential surfaces evaluated at the MR-SOCISD level of theory.