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Pauli Repulsion Effects in Scattering from and Catalysis by Surfaces

  • E. J. Baerends
Part of the NATO ASI Series book series (NSSB, volume 283)

Abstract

The physical origin of the repulsion between adsorbates and a substrate crystal at short distances is discussed. This steric repulsion [3] or frozen orbital repulsion [4] is shown to consist of a generally attractive classical Coulomb interaction of the superimposed charge distributions and a repulsive contribution (Pauli repulsion) due to a kinetic energy increase caused by the antisymmetry requirement The non-pairwise additivity of the Pauli repulsion is shown to be important for scattering of ions at hyperthermal energies (in the order of 50 eV) from a surface. At a metallic surface relief of Pauli repulsion with the conduction electrons may easily occur because of the finite density of states at the Fermi energy. The finite-cluster representation of this effect by configuration changes (i.e. cluster excitations) is discussed for CO on Cu adsorption. The enhancement of the selectivity of the ethylene epoxidation by the presence of subsurface O below the catalytic Ag surface provides another example of the importance of the relief of Pauli repulsion.

Keywords

Fermi Energy Antibonding Orbital Hollow Site Cluster Orbital Lone Pair Orbital 
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.

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References

  1. 1.
    P.J. van den Hoek, A.W. Kleyn, E.J. Baerends, Comments At. Mol. Physics 23 (1989) 93.Google Scholar
  2. 2.
    P.J. van den Hoek, A.D. Tenner, A.W. Kleyn, E.J. Baerends, Phys. Rev. B 34 (1986) 5030.CrossRefGoogle Scholar
  3. 3.
    D. Post, E.J. Baerends, J. Chem. Phys. 78 (1983) 5663.CrossRefGoogle Scholar
  4. 4.
    P.S. Bagus, C.J. Nelin, C.W. Bauschlicher, Phys. Rev. B 28 (1983) 5423.CrossRefGoogle Scholar
  5. 5.
    A. Gavezzotti, G.F. Tantardini, M. Simonetta, Chem. Phys. 105 (1986) 333.CrossRefGoogle Scholar
  6. 6.
    G. Pacchioni, P.S. Bagus, J. Chem. Phys. 93 (1990) 1209.CrossRefGoogle Scholar
  7. 7.
    P.J. van den Hoek, E.J. Baerends, R.A. van Santen, J. Phys. Chem. 93 (1989) 6469.CrossRefGoogle Scholar
  8. 8.
    M.J. Feinberg, K. Ruedenberg, J. Chem. Phys. 54 (1971) 1495.CrossRefGoogle Scholar
  9. 9.
    A. Rozendaal, E.J. Baerends, Chem. Phys. 95 (1985) 57.CrossRefGoogle Scholar
  10. 10.
    A.D. Tenner, K.T. Gillen, T.C.M. Horn, J. Los, A.W. Kleyn, Surf. Sci. 172 (1986) 90.CrossRefGoogle Scholar
  11. 11.
    A.D. Tenner, R.P. Saxon, K.T. Gillen, D.E. Harrison, T.C.M. Horn, A.W. Kleyn, Surf. Sci. 172 (1986) 121.CrossRefGoogle Scholar
  12. 12.
    cf. Fig. 2 in: B.I. Lundquist, O. Gunnarsson, H. Hjelmberg, J.K. Norskov, Surf. Sci. 89 (1979) 196.CrossRefGoogle Scholar
  13. 13.
    cf. P.S. Bagus, G. Pacchioni, this volume.Google Scholar
  14. 14.
    M.A. Buijse, EJ. Baerends, J. Chem. Phys. 93 (1990) 4129.CrossRefGoogle Scholar
  15. 15.
    D. Post, E.J. Baerends, Surf. Sci. 116 (1982) 177.CrossRefGoogle Scholar
  16. 16.
    K. Hermann, P.S. Bagus, C.J. Nelin, J. Chem. Phys. 35 (1987) 9467.Google Scholar
  17. 17.
    T.H. Upton, W.A. Goddard, Phys. Rev. Lett. 42 (1979) 472.CrossRefGoogle Scholar
  18. 18.
    I. Panas, J. Schüle, P.E.M. Siegbahn, U. Wahlgrèn, Chem. Phys. Lett. 149 (1988) 265.CrossRefGoogle Scholar
  19. 19.
    J. Schule, P.E.M. Siegbahn, U. Wahlgren, J. Chem. Phys. 89 (1988) 6982.CrossRefGoogle Scholar
  20. 20.
    R.A. van Santen, H.P.C.E. Kuipers, Advances in Catalysis, Vol. 35 (1987) 265.CrossRefGoogle Scholar
  21. 21.
    R. Hoffmann, J.Y. Saillard, J. Am. Chem. Soc. 106 (1984) 2006.CrossRefGoogle Scholar
  22. 22.
    I. Panas, P.E.M. Siegbahn, J. Chem. Phys. 92 (1990) 4625.CrossRefGoogle Scholar
  23. 23.
    P.E.M. Siegbahn, L.G.M. Pettersson, U. Wahlgren, J. Chem. Phys. 94 (1991) 4024.CrossRefGoogle Scholar

Copyright information

© Plenum Press, New York 1992

Authors and Affiliations

  • E. J. Baerends
    • 1
  1. 1.Scheikundig LaboratoriumVrije UniversiteitAmsterdamThe Netherlands

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