Cluster chemistry from the electronic perspective


Andrei Sanov, sanov@u.arizona.edu1, Richard Mabbs, mabbs@wustl.edu2, Terefe Habteyes, terefeg@yahoo.com1, Luis Velarde, lvelarde@email.arizona.edu1, and S. Eric Surber, surber@u.arizona.edu3. (1) Department of Chemistry, University of Arizona, Tucson, AZ 85721-0041, (2) Department of Chemistry, Washington University in St. Louis, Campus Box 1134, One Brookings Drive, St. Louis, MO 63130, (3) School of Chemical Science, University of Illinois, 600 S Matthews, urbana, IL 61801
Photoelectron imaging is used to study the electronic structure of molecular cluster anions and its transformations in the solvent and reaction-coordinate domains. Results for I•X (X = Ar, H2O, CH3I, CH3CN), [(CO2)n(H2O)m], (CS2)n and other cluster systems are presented along with several models facilitating the conceptual interpretation of the structural and dynamical information in the time- and solvent-domain photoelectron images. Solvent domain studies focus on electronic isomers, charge transfer to solvent, and signatures of excited anionic states. The effects of increasing solvation and covalent interactions on core-anion orbitals shed light on the cluster properties and reactivity. The decay dynamics of the excited states and competition of cluster fragmentation and both direct and indirect electron emission mechanisms are examined. Time-resolved photoelectron imaging allows tracking the evolution of the electronic structure from reactants to products.