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Density functional study of low-lying isomers of SiO4, GeO4 and CO4, and their relation to tetrahedral solid phases

  • I. CabriaEmail author
  • M. J. López
  • J. A. Alonso
  • N. H. March
Regular Article
  • 144 Downloads

Abstract

In silica (SiO2) and in most silicates, atomic associations exist with composition SiO4 and a structure with four O atoms in tetrahedral coordination around the Si atom. A similar feature is observed in germania (GeO2) and some solids containing Ge instead of Si, although the number of phases containing GeO4 tetrahedra is smaller. In contrast, and in spite of the fact that C is in the same column of the periodic table as Si and Ge, CO2 is a molecular solid, and crystalline and amorphous phases of CO2 showing CO4 tetrahedra are only obtained under extremely high pressures. We have investigated the relation between free SiO4, GeO4 and CO4 clusters and the tetrahedral associations found in the solids mentioned above. The lowest energy structure of those three free clusters is planar, but they have near-tetrahedral and distorted-tetrahedral isomers. The promotion energy from the planar structure to the distorted tetrahedral is low in SiO4, large in CO4, and intermediate in GeO4. This correlates with the facility to form tetrahedral associations in the solids.

Keywords

Clusters and Nanostructures 

References

  1. 1.
    J. Chen, Z. Liu, T. Yu, Z. Chen, J. Sun, L. Weng, B. Tu, D. Zhao, Chem. Lett. 32, 474 (2003)CrossRefGoogle Scholar
  2. 2.
    X. Zou, T. Conradsson, M. Klingstedt, M.S. Dadachov, M. O′Keeffe, Nature 437, 716 (2005)ADSCrossRefGoogle Scholar
  3. 3.
    G.D. Ilyushin, L.N. Demyanets, Russ. J. Inorg. Chem. 51, 306 (2006)CrossRefGoogle Scholar
  4. 4.
    J.H. Zhang, C.L. Hu, X. Xu, F. Kong, J.G. Mao, Inorg. Chem. 50, 1973 (2011)CrossRefGoogle Scholar
  5. 5.
    S. Saito, T. Ono, Jpn J. Appl. Phys. 50, 021503 (2011)ADSCrossRefGoogle Scholar
  6. 6.
    V. Iota, C.S. Yoo, H. Cynn, Science 283, 1510 (1999)ADSCrossRefGoogle Scholar
  7. 7.
    C.S. Yoo, H. Cynn, F. Gygi, G. Galli, V. Iota, M. Nicol, S. Carlson, D. Häusermann, C. Mailhiot, Phys. Rev. Lett. 83, 5527 (1999)ADSCrossRefGoogle Scholar
  8. 8.
    M. Santoro, F.A. Gorelli, R. Bini, G. Ruocco, S. Scandolo, W.A. Crichton, Science 441, 857 (2006)Google Scholar
  9. 9.
    F. Cacace, G. de Petris, M. Rosi, A. Troiani, Angew. Chem. Int. Ed. 42, 2985 (2003)CrossRefGoogle Scholar
  10. 10.
    L.Y. Yeung, M. Okumura, J.T. Paci, G.C. Schatz, J. Zhang, T.K. Minton, J. Am. Chem. Soc. 131, 13940 (2009)CrossRefGoogle Scholar
  11. 11.
    B.M. Elliott, A.I. Boldyrev, J. Phys. Chem. A 109, 3722 (2005)CrossRefGoogle Scholar
  12. 12.
    Y. Kowada, H. Adachi, M. Tatsumisago, T. Minami, J. Non-Cryst. Solids 150, 318 (1992)ADSCrossRefGoogle Scholar
  13. 13.
    A.Y. Kuznetsov, A.B. Sobolev, A.N. Varaksin, O.A. Kedahave, J. Struct. Chem. 38, 878 (1997)CrossRefGoogle Scholar
  14. 14.
    G. Forte, G.G.N. Angilella, V. Pittalà, N.H. March, R. Pucci, Phys. Lett. A 376, 476 (2012)ADSCrossRefGoogle Scholar
  15. 15.
    W. van der Lugt, J. Phys.: Condens. Matter 8, 6115 (1996)ADSCrossRefGoogle Scholar
  16. 16.
    L.M. Molina, J.A. Alonso, M.J. Stott, J. Chem. Phys. 111, 7053 (1999)ADSCrossRefGoogle Scholar
  17. 17.
    J.A. Alonso, Structure and Properties of Atomic Nanoclusters, 2nd edn. (Imperial College Press, London, 2011)Google Scholar
  18. 18.
    J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77, 3865 (1996)ADSCrossRefGoogle Scholar
  19. 19.
    C. Amovilli, N.H. March, F. Bogár, T. Gál, Phys. Lett. A 373, 3158 (2009)ADSzbMATHCrossRefGoogle Scholar
  20. 20.
    http://wiki.fysik.dtu.dk/dacapo, updated March 16th 2012
  21. 21.
    D. Vanderbilt, Phys. Rev. B 41, 7892 (1990)ADSCrossRefGoogle Scholar
  22. 22.
    C.S. Jamieson, A.M. Mebel, R.I. Kaiser, Chem. Phys. Lett. 440, 105 (2007)ADSCrossRefGoogle Scholar
  23. 23.
    N.H. March, Proc. Camb. Philos. Soc. 48, 665 (1952)ADSzbMATHCrossRefGoogle Scholar
  24. 24.
    J.F. Mucci, N.H. March, J. Chem. Phys. 71, 5270 (1979)ADSCrossRefGoogle Scholar
  25. 25.
    N.H. March, Electron Density Theory of Atoms and Molecules (Academic Press, London, 1992)Google Scholar
  26. 26.
    N.H. March, R.G. Parr, Proc. Natl. Acad. Sci. USA 77, 6285 (1980)ADSCrossRefGoogle Scholar

Copyright information

© EDP Sciences, SIF, Springer-Verlag Berlin Heidelberg 2012

Authors and Affiliations

  • I. Cabria
    • 1
    Email author
  • M. J. López
    • 1
  • J. A. Alonso
    • 1
  • N. H. March
    • 1
    • 2
    • 3
  1. 1.Departamento de Física Teórica, Atómica y ÓpticaUniversidad de ValladolidValladolidSpain
  2. 2.Department of PhysicsUniversity of AntwerpAntwerpBelgium
  3. 3.Oxford UniversityOxfordEngland

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