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Highest electron affinity as a predictor of cluster anion structures

Nature Materials volume 1, pages 49–53 (2002)Cite this article

Abstract

Small clusters have a range of unique physical and chemical phenomena that are strongly size dependent. However, analysis of these phenomena often assumes that thermodynamic equilibrium conditions prevail. We compare experimentally measured and ab initio computed photoelectron spectra of bare and deuterated silicon cluster anions produced in a plasma environment. We find that the isomers detected experimentally are usually not the ground-state isomers, but metastable ones, which indicates that cluster relaxation is strongly limited kinetically by a dwell time that is much shorter than the relaxation time. We show that, under these conditions, the highest electron affinity replaces the traditional lowest total energy as the appropriate criterion for predicting isomer structures. These findings demonstrate that a stringent examination of non-equilibrium effects can be crucial for a correct analysis of cluster properties.

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Figure 1: Photoelectron spectra (PES) of selected Si m D n - clusters ( m = 6, 8 and 10; n = 1 and 2).
Figure 2: Photoelectron spectra of several clusters obeying the highest vertical electron affinity (VEA) rule.
Figure 3: Photoelectron spectra of the two clusters disobeying the highest VEA rule.

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Acknowledgements

We acknowledge the support provided by the National Science Foundation, the US Department of Energy, the Minnesota Supercomputer Institute, the Deutsche Forschungsgemeinschaft and the Sonderforschungsbereich 513.

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Authors and Affiliations

  1. Department of Chemical Engineering and Materials Science, and Minnesota Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota, 55455, USA

    Leeor Kronik, Eunjung Ko & James R. Chelikowsky

  2. Department of Physics, University of Konstanz, Konstanz, D-78457, Germany

    Roland Fromherz & Gerd Ganteför

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Correspondence to James R. Chelikowsky.

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Kronik, L., Fromherz, R., Ko, E. et al. Highest electron affinity as a predictor of cluster anion structures. Nature Mater 1, 49–53 (2002). https://doi.org/10.1038/nmat704

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