Competitive Reaction Pathways

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The Experimental Physical Chemistry Program supports Curt Wittig of the University of Southern California in his continuing studies of photoinduced reactions. He will focus on two sets of experiments: (a) reactions in the restricted geometries of dimers and (b) unimolecular reaction rates at threshold. In the former, he will use double resonance techniques for cluster size selection. Rotationally resolved states of clusters will be selected and their photochemistries interrogated. Wittig will study the hydrogen exchange reaction and inelastic scattering in HF-HCl, HCl-HF and HCl dimer and its deuterated analogs. The second set of studies will focus on nitrogen dioxide, HNCO, water and HF. An underlying theme of these studies is to challenge theoretical modeling by providing benchmark data. Thus, in some cases, existing models of the associated gas phase phase processes will need to be reconsidered. In other cases, systems are studied for which the dynamics are believed to be known for the associated gas phase processes. The cluster experiments to be carried out here will then display effects attributable to the restricted entrance channel, i.e., effects due to the geometry of the cluster. Such work starts to bridge the gap between the gaseous and condensed phases at a high level of precision, again with experimental benchmarks, albeit in a microcosm that is neither the condensed nor gas phase. Results from these investigations will thus have a very significant impact in advancing our knowledge and understanding in reaction dynamics.