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Binding energies, lifetimes and implications of bulk and interface solvated electrons in water

Nature Chemistry volume 2, pages 274–279 (2010)Cite this article

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Abstract

Solvated electrons in liquid water are one of the seemingly simplest, but most important, transients in chemistry and biology, but they have resisted disclosing important information about their energetics, binding motifs and dynamics. Here we report the first ultrafast liquid-jet photoelectron spectroscopy measurements of solvated electrons in liquid water. The results prove unequivocally the existence of solvated electrons bound at the water surface and of solvated electrons in the bulk solution, with vertical binding energies of 1.6 eV and 3.3 eV, respectively, and with lifetimes longer than 100 ps. The unexpectedly long lifetime of solvated electrons bound at the water surface is attributed to a free-energy barrier that separates surface and interior states. Beyond constituting important energetic and kinetic benchmark and reference data, the results also help to understand the mechanisms of a number of very efficient electron-transfer processes in nature.

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Figure 1: Schematic of the experimental setup and strategy to measure liquid-state photoelectron spectra.
Figure 2: Photoelectron spectra of surface- and bulk-solvated electrons.
Figure 3: Comparison of experimental binding energies.
Figure 4: Explanation for the long lifetimes of the surface-bound electrons.
Figure 5: The concept of resonant dissociative electron attachment.

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Acknowledgements

Discussions with D. Neumark and P. Jungwirth are acknowledged. This work was supported by the Deutsche Forschungsgemeinschaft within the programmes SPP1134, GK 782 and SFB 755, the CRC (Nano-Spectroscopy and X-Ray Imaging) in Göttingen and the University of Leipzig.

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Authors and Affiliations

  1. Institut für Physikalische Chemie der Universität Göttingen, Tammannstrasse 6, Göttingen, 37077, Germany

    Katrin R. Siefermann, Yaxing Liu, Oliver Link & Bernd Abel

  2. Ostwald-Institut für Physikalische und Theoretische Chemie der Universität Leipzig, Linné-Strasse 2, Leipzig, D-04103, Germany

    Evgeny Lugovoy & Bernd Abel

  3. MPI für Dynamik und Selbstorganisation, Bunsenstrasse 10, Göttingen, 37073, Germany

    Manfred Faubel & Udo Buck

  4. Helmholtz-Zentrum Berlin für Materialien und Energie, and BESSY, Albert-Einstein-Strasse 15, Berlin, 12489, Germany

    Bernd Winter

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Contributions

B.A., M.F. and B.W. designed the experiments. K.R.S., Y.L., E.L. and O.L. performed the experiments. K.R.S. and Y.L. analysed the data. K.R.S., Y.L., O.L. and E.L. contributed materials and/or analysis tools. B.A., B.W. and U.B. co-wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Bernd Abel.

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Siefermann, K., Liu, Y., Lugovoy, E. et al. Binding energies, lifetimes and implications of bulk and interface solvated electrons in water. Nature Chem 2, 274–279 (2010). https://doi.org/10.1038/nchem.580

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