Electron Solvation in Finite Systems: Femtosecond Dynamics of Iodide.[.sub.n] Anion Clusters

Electron solvation dynamics in photoexcited anion clusters of [I.sup.-][([D.sub.2]O).sub.n=4-6] and [I.sup.-][(H[.sub.2]O).sub.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 st...

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Bibliographic Details
Published in:Science (American Association for the Advancement of Science) 1999-04, Vol.284 (5414), p.635
Main Authors: Lehr, L, Zanni, M. T, Frischkorn, C, Weinkauf, R, Neumark, D. M
Format: Article
Language:English
Subjects:
Anions
Photoelectron spectroscopy
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Summary:Electron solvation dynamics in photoexcited anion clusters of [I.sup.-][([D.sub.2]O).sub.n=4-6] and [I.sup.-][(H[.sub.2]O).sub.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.sup.-] 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 dusters the so[vent 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.sup.-][([D.sub.2]O).sub.n] with [I.sup.-][([H.sub.2]O).sub.n] indicates more rapid solvation in the [H.sub.2]O clusters.
ISSN:0036-8075
1095-9203
DOI:10.1126/science.284.5414.635