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Probing the Structural Evolution of the Hydrated Electron in Water Cluster Anions (H2O)n-, n ≤ 200, by Electronic Absorption Spectroscopy.

  • Author(s): Herburger, Andreas;
  • Barwa, Erik;
  • Ončák, Milan;
  • Heller, Jakob;
  • van der Linde, Christian;
  • Neumark, Daniel M;
  • Beyer, Martin K
  • et al.
Abstract

Electronic absorption spectra of water cluster anions (H2O)n-, n ≤ 200, at T = 80 K are obtained by photodissociation spectroscopy and compared with simulations from literature and experimental data for bulk hydrated electrons. Two almost isoenergetic electron binding motifs are seen for cluster sizes 20 ≤ n ≤ 40, which are assigned to surface and partially embedded isomers. With increasing cluster size, the surface isomer becomes less populated, and for n ≥ 50, the partially embedded isomer prevails. The absorption shifts to the blue, reaching a plateau at n ≈ 100. In this size range, the absorption spectrum is similar to that of the bulk hydrated electron but is slightly red-shifted; spectral moment analysis indicates that these clusters are reasonable model systems for hydrated electrons near the liquid-vacuum interface.

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