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

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Science  23 Apr 1999:
Vol. 284, Issue 5414, pp. 635-638
DOI: 10.1126/science.284.5414.635

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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 excitedn = 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.

  • * These authors contributed equally to this work.

  • Permanent address: Institut für Physikalische und Theoretische Chemie, Technischen Universität München, D-85748 Garching, Germany.

  • To whom correspondence should be addressed. E-mail: dan{at}radon.cchem.berkeley.edu

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