Modeling thiolate-protected gold clusters with density-functional tight-binding

  • Ville MäkinenEmail author
  • Pekka Koskinen
  • Hannu Häkkinen
Regular Article
Part of the following topical collections:
  1. Topical issue: ISSPIC 16 - 16th International Symposium on Small Particles and Inorganic Clusters


Thiolate-protected gold clusters are complex systems, in which both the surface-covalent Au-S bond and electronic structure of the gold core play an important role for the stability. In this study, a charge-self-consistent density-functional tight-binding parametrization for these systems is validated by studying Au25(SMe)18 -, Au102(SMe)44 and Au144(SMe)60 clusters, where recent X-ray structure determinations and density-functional calculations have revealed the detailed atomic structures and electronic properties. We show that the cluster geometries obtained from the tight-binding structure relaxation preserve the Divide and Protect structure motif [H. Häkkinen, M. Walter, H. Grönbeck, J. Phys. Chem. B 110, 9927 (2006)], where the gold core is protected by a number of oligomeric Au x (SR) y units. Furthermore, the electron shell structure in the metal core, composed of Au(6s) electrons, is reproduced. We conclude that the density-functional tight-binding method describes these systems well and offers a possibility to explore their dynamical phenomena.


Density Functional Theory Density Functional Theory Calculation Mulliken Charge Gold Core Electron Shell Structure 
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Copyright information

© EDP Sciences, SIF, Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • Ville Mäkinen
    • 1
    Email author
  • Pekka Koskinen
    • 1
  • Hannu Häkkinen
    • 1
    • 2
  1. 1.NanoScience Center, Department of Physics, University of JyväskyläJyväskyläFinland
  2. 2.NanoScience Center, Department of Chemistry, University of JyväskyläJyväskyläFinland

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