Electron Solvation in Finite Systems: Femtosecond Dynamics of Iodide·(Water) n Anion Clusters

Author:

Lehr L.1,Zanni M. T.1,Frischkorn C.1,Weinkauf R.1,Neumark D. M.1

Affiliation:

1. Department of Chemistry, University of California, Berkeley, CA 94720, USA and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.

Abstract

Electron solvation dynamics in photoexcited anion clusters of I (D 2 O) n =4–6 and I (H 2 O) 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 (D 2 O) n with I (H 2 O) n indicates more rapid solvation in the H 2 O clusters.

Publisher

American Association for the Advancement of Science (AAAS)

Subject

Multidisciplinary

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