Journal of Mathematical Chemistry

, Volume 46, Issue 3, pp 971–980 | Cite as

A parallel study of Ni@Si12 and Cu@Si12 nanoclusters

  • A. D. Zdetsis
  • E. N. Koukaras
  • C. S. Garoufalis
Original Paper


The Ni@Si12 and Cu@Si12 clusters are studied in parallel within the framework of the density functional theory using the hybrid functional of Becke-Lee, Parr and Yang (B3LYP), emphasizing the differences and similarities in structural and electronic properties. The dominant structures for both clusters are a distorted hexagonal structure of Cs symmetry and a distorted octahedral structure of D2d. For Ni@Si12 the two structures are practically isonergetic whereas for Cu@Si12 the energy difference of the D2d structure from the lowest Cs structure of hexagonal origin is about 0.7 eV, at the B3LYP/TZVP level of theory. Contrary to Cu@Si12 for which the well known Frank–Kasper (FK) structure of C5v symmetry is a real local minimum of the energy hyper-surface (although higher by more than 1.6 eV from the global minimum), for Ni@Si12 the FK structure is dynamically unstable. The HOMO-LUMO gaps, the binding energies per atom and the embedding energies for Cu@Si12 clusters are smaller by 0.5, 0.1 and 1.1 eV, respectively compared to the Ni@Si12 clusters. This is attributed to different type of bonding in the two clusters.


Metal encapsulated clusters Nanocluster Silicon Transition metal Ab initio calculations 


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  1. 1.
    Beck S.M.: J. Chem. Phys. 90, 6306 (1989)CrossRefGoogle Scholar
  2. 2.
    Beck S.M.: J. Chem. Phys. 87, 4233 (1987)CrossRefGoogle Scholar
  3. 3.
    Hiura H., Miyazaki T., Kanayama T.: Phys. Rev. Lett. 86, 1733 (2001)CrossRefGoogle Scholar
  4. 4.
    Xiao C., Hagelberg F.: Phys. Rev. B 66, 075425 (2002)CrossRefGoogle Scholar
  5. 5.
    Sen P., Mitas L.: Phys. Rev. B 68, 155404 (2003)CrossRefGoogle Scholar
  6. 6.
    Menon M., Andriotis A., Froudakis G.: Nano Lett. 2, 301 (2002)CrossRefGoogle Scholar
  7. 7.
    Singu A.K., Briere T.M., Kumar V., Kawazoe Y.: Phys. Rev. Lett. 91, 146802 (2003)CrossRefGoogle Scholar
  8. 8.
    Khanna S.N., Rao B.K., Jena P.: Phys. Rev. Lett. 89, 016803 (2002)CrossRefGoogle Scholar
  9. 9.
    Kumar V.: Eur. Phys. J. D 24, 227 (2003)CrossRefGoogle Scholar
  10. 10.
    Lu J., Nagase S.: Phys. Rev. Lett. 90, 115506 (2003)CrossRefGoogle Scholar
  11. 11.
    Mpourmpakis G., Froudakis G.E., Andriotis A.N., Menon M.: Phys. Rev. B 68, 125407 (2003)CrossRefGoogle Scholar
  12. 12.
    Kumar V.: Comp. Mat. Sci. 30, 260 (2004)CrossRefGoogle Scholar
  13. 13.
    Zdetsis A.D.: Phys. Rev. A 64, 023202 (2001)CrossRefGoogle Scholar
  14. 14.
    Zdetsis A.D.: Rev. Adv. Mat. Sci. (RAMS) 11, 56–78 (2006)Google Scholar
  15. 15.
    Garoufalis C.S., Zdetsis A.D., Grimme S.: Phys. Rev. Lett. 87, 276402 (2001)CrossRefGoogle Scholar
  16. 16.
    Becke A.D.: Phys. Rev. A 38, 3098 (1988)CrossRefGoogle Scholar
  17. 17.
    Perdew J.P.: Phys. Rev. B 33, 8822 (1986)CrossRefGoogle Scholar
  18. 18.
    Schäfer A., Horn H., Ahlrichs R.: J. Chem. Phys. 97, 2571 (1992)CrossRefGoogle Scholar
  19. 19.
    Eichkorn K., Treutler O., Häser H., Häser M., Ahlrichs R.: Chem. Phys. Lett. 240, 283 (1995)CrossRefGoogle Scholar
  20. 20.
    Stephens P.J., Devlin F.J., Chabalowski C.F., Frisch M.J.: J. Phys. Chem. 98, 11623 (1994)CrossRefGoogle Scholar
  21. 21.
    Schäfer A., Huber C., Ahlrichs R.: J. Chem. Phys. 100, 5829 (1994)CrossRefGoogle Scholar
  22. 22.
    Stephens P.J., Devlin F.J., Chabalowski C.F., Frisch M.J.: J. Phys. Chem. 98, 11623 (1994)CrossRefGoogle Scholar
  23. 23.
    Yanagisawa K., Tsuneda T., Hirao K.: J. Chem. Phys. 112, 545 (2000)CrossRefGoogle Scholar
  24. 24.
    Ahlrichs R., Bär M., Häser M., Horn H., Kölmel C.: Chem. Phys. Lett. 162, 165 (1989)CrossRefGoogle Scholar
  25. 25.
    Andriotis A.T., Mpourmpakis G., Froudakis G.E., Menon M.: New J. Phys. 4, 78 (2002)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2009

Authors and Affiliations

  • A. D. Zdetsis
    • 1
  • E. N. Koukaras
    • 1
  • C. S. Garoufalis
    • 1
  1. 1.Department of PhysicsUniversity of PatrasPatrasGreece

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