title: Electron solvation in finite systems: femtosecond dynamics of iodide. (Water)n anion clusters
abstract: Electron solvation dynamics in photoexcited anion clusters of I-(D2O)n=4-6 and I-(H2O)4-6 were probed by using femtosecond photoelectron spectroscopy (FPES). An ultrafast pump pulse excited the anion to the cluster analog of the charge-transfer-to-solvent state seen for I- in aqueous solution. Evolution of this state was monitored by time-resolved photoelectron spectroscopy using an ultrafast probe pulse. The excited n = 4 clusters showed simple population decay, but in the n = 5 and 6 clusters the solvent molecules rearranged to stabilize and localize the excess electron, showing characteristics associated with electron solvation dynamics in bulk water. Comparison of the FPES of I-(D2O)n with I-(H2O)n indicates more rapid solvation in the H2O clusters.
authors.affiliation: Department of Chemistry, University of California, Berkeley, CA 94720, USA and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
authors.initials: L
authors.lastname: Lehr
authors.initials: MT
authors.lastname: Zanni
authors.initials: C
authors.lastname: Frischkorn
authors.initials: R
authors.lastname: Weinkauf
authors.initials: DM
authors.lastname: Neumark