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Electrons in Finite-Sized Water Cavities: Hydration Dynamics Observed in Real Time

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Science  22 Oct 2004:
Vol. 306, Issue 5696, pp. 672-675
DOI: 10.1126/science.1102827

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Abstract

We directly observed the hydration dynamics of an excess electron in the finite-sized water clusters of Embedded Image with n = 15, 20, 25, 30, and 35. We initiated the solvent motion by exciting the hydrated electron in the cluster. By resolving the binding energy of the excess electron in real time with femtosecond resolution, we captured the ultrafast dynamics of the electron in the presolvated (“wet”) and hydrated states and obtained, as a function of cluster size, the subsequent relaxation times. The solvation time (300 femtoseconds) after the internal conversion [140 femtoseconds for Embedded Image] was similar to that of bulk water, indicating the dominant role of the local water structure in the dynamics of hydration. In contrast, the relaxation in other nuclear coordinates was on a much longer time scale (2 to 10 picoseconds) and depended critically on cluster size.

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