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20-Nanogold Au20(Td) and Low-Energy Hollow Cages: Void Reactivity

  • E. S. Kryachko
  • F. Remacle
Chapter
Part of the Progress in Theoretical Chemistry and Physics book series (PTCP, volume 22)

Abstract

Five 20-nanogold low-energy hollow cages are identified at the density functional level by performing a computational search on the corresponding potential energy surfaces in the different charge states. Their structures and stabilities are investigated and compared with the tetrahedral ground-state and space-filled cluster Au20(T d ). Special attention is devoted to the bifunctional reactivity of the studied Au20 hollow cages: the outer, exo-reactivity and the inner, void reactivity. The void reactivity results in endohedrality, i.e. in the existence of @-fullerenes of gold. We analyze the general features of the voids of the reported 20-nanogold fullerenes. The values of ionization potentials and electronaffinities, the molecular electrostatic potential and HOMO and LUMO patterns are invoked for this purpose and compared with those of C60 that has a similar void size. This is on the one hand. On the other, as already known in the literature, the space-filled Au20(T d ) reveals a perfect confinement for some guest atoms. The mechanism of the formation of void of Au20(T d ) that enables to trap a guest is illustrated by using a guest gold atom which is repelled by the so called ‘interior’ atoms of Au20(T d ). The computed repulsion energy provides a rough estimate of the energy needed to form a void inside this cluster.

Keywords

Charge State Outer Space Gold Cluster Gold Atom Molecular Electrostatic Potential 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Notes

Acknowledgements

This work was partially supported by the AIP ‘Clusters and Nanowires’ Project of the Belgian Federal Government and the EC FET proactive NanoICT Project ‘MOLOC’. One of the authors, E. S. K., gratefully thanks FNRS (Belgium) and the FRFC project 2.4.594.10.F for supporting his stay at the University of Liège and the Organizing Committee of the QSCP-XV, in particular the Chair Philip E. Hoggan, for the kind invitation, the generous hospitality, and the excellent organization. E. S. K. also thanks Benjamin Soulé de Bas, Mike J. Ford, Alessandro Fortunelli, Uzi Landman, Pekka Pyykkö, Gernot Frenking, and the reviewer for the valuable suggestions and comments.

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© Springer Science+Business Media B.V. 2012

Authors and Affiliations

  • E. S. Kryachko
    • 1
    • 2
  • F. Remacle
    • 2
  1. 1.Bogolyubov Institute for Theoretical PhysicsKiev-143Ukraine
  2. 2.Department of Chemistry, Bat. B6cUniversity of LiègeLiègeBelgium

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