Ionic Bonding of Adsorbates on Surfaces: Theoretical Characterization and Observable Consequences

  • P. S. Bagus
  • G. Pacchioni
Part of the NATO ASI Series book series (NSSB, volume 283)


Three examples where the chemisorption bond is dominantly ionic are reviewed. One example is for a cationic adatom K/Cu(100), representative of alkali metals adsorbed on metals; the other two are for anionic adsorbed molecules, NO/Cu(100) and SCN/Ag(100). Several theoretical techniques for the evaluation of bond ionicity will be described and they will be applied in these three examples. Consequences of ionic bonds for adsorbate vibrational spectra, frequency and intensity, and for adsorbate geometry will be presented. It will be shown that ionic bonds do not have a directionality which gives a well defined energetic preference for particular geometric orientations of an adsorbate. As well as not being directional, ionic bonds may be reasonably strong; we speculate that the combination of these two features of ionic bonds may lead to situations of high surface reactivity.


Cluster Model Ionic Bond Electron Energy Loss Spectroscopy Ionic Character Occupied Orbital 
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  1. 1.
    I. Langmuir and K. H. Kingdon, Phys. Rev. 21, 381 (1923).CrossRefGoogle Scholar
  2. 2.
    H. P. Bonzel, Surf. Sci. Reports 8, 43 (1987).CrossRefGoogle Scholar
  3. 3.
    M. R. Deakin, T. T. Li, and O. R. Melroy, J. Electroanal. Chem. 243, 343 (1988).CrossRefGoogle Scholar
  4. 4.
    See, for example, the reviews and references therein:* (a) P. S. Bagus, in Elemental and Molecular Clusters, edited by G. Benedeck, T. P. Martin, and G. Pacchioni (Springer-Verlag, Heidelberg, 1988), p. 286CrossRefGoogle Scholar
  5. (b) P. S. Bagus, G. Pacchioni, and C. J. Nelin, in Studies in Physical and Theoretical Chemistry 62, edited by R. Carbo (Elsevier, Amsterdam, 1989) p.475.Google Scholar
  6. 5.
    P. S. Bagus and I. P. Batra, Surf. Sci. 206, L895 (1988).CrossRefGoogle Scholar
  7. 6.
    G. Pacchioni and P. S. Bagus, Phys. Rev. B, to be published.Google Scholar
  8. 7.
    P. S. Bagus, in Plasma Synthesis and Etching of Electronic Materials, edited by R. T. H. Chang and B. Abeles, Materials Research Society Symposia Proceedings Vol. 38 (Materials Research Society, Pittsburgh, 1985), p. 179;Google Scholar
  9. 7a.
    M. Seel and P. S. Bagus, Phys. Rev. B 28, 2023 (1983).CrossRefGoogle Scholar
  10. 8.
    Lars G. M. Pettersson and Paul S. Bagus, Phys Rev. Lett. 56, 500 (1986)CrossRefGoogle Scholar
  11. 9.
    P. S. Bagus, G. Pacchioni, and M. R. Philpott, J. Chem. Phys. 90, 4287 (1989).CrossRefGoogle Scholar
  12. 10.
    P. S. Bagus and F. Mas, Phys. Rev. B 42, 10852 (1990).CrossRefGoogle Scholar
  13. 11.
    P. S. Bagus, K. Hermann, and C. W. Bauschlicher, J. Chem. Phys. 81, 1966 (1984).CrossRefGoogle Scholar
  14. 12.
    P. S. Bagus, C. W. Bauschlicher Jr., C. J. Nelin, B. C. Laskowski and M. Seel, J. Chem. Phys. 81, 3594(1984).CrossRefGoogle Scholar
  15. 13.
    G. Pacchioni and P. S. Bagus, J. Chem. Phys. 93, 1209 (1990).CrossRefGoogle Scholar
  16. 14.
    P. S. Bagus, C. J. Nelin, W. Müller, M. R. Philpott, and H. Scki, Phys. Rev. Lett. 58, 559 (1987).CrossRefGoogle Scholar
  17. 15.
    G. Pacchioni, P. S. Bagus, C. J. Nelin and M. R. Philpott, I. J. Quantum Chem. 38, 675 (1990).CrossRefGoogle Scholar
  18. 16.
    G. Pacchioni, F. Mas, M. R. Philpott, and P. S. Bagus, J. Chem. Phys., in press.Google Scholar
  19. 17.
    P. S. Bagus, C. J. Nelin and Ph. Avouis, J. Vac. Sci. Technnl A 5, 701 (1987).CrossRefGoogle Scholar
  20. 18.
    H. Ibach and D. L. Mills, Electron Energy Loss Spectroscopy and Surface Vibrations (Academic, New York, 1982).Google Scholar
  21. 19.
    P. S. Bagus and M. Seel, Phys. Rev. B 23, 5464 (1981).CrossRefGoogle Scholar
  22. 20.
    P. S. Bagus and G. Pacchioni, Electrochimica Acta, in press.Google Scholar
  23. 21.
    R. Hoffmann, Rev. Mod. Phys. 60, 601 (1988).CrossRefGoogle Scholar
  24. 22.
    H. F. Schaefer, The Electronic Structure of Atoms and Molecules, (Addison-Wesley, Reading, 1972);Google Scholar
  25. 22a.
    H. F. Schaefer, Methods of Electronic Structure Theory, edited by H. F. Schaefer (Plenum, New York, 1977);Google Scholar
  26. 22a.
    H. F. Schaefer, and Applications of Electronic Structure Theorv, edited by H. F. Schaefer (Plenum, New York, 1979).Google Scholar
  27. 23.
    K. Hermann, P. S. Bagus, and C. J. Nelin, Phys. Rev. B 35, 9467 (1987).CrossRefGoogle Scholar
  28. 24.
    P. S. Bagus, C. J. Nelin, K. Hermann, and M. R. Philpott. Phys. Rev. B 36, 8169 (1987).CrossRefGoogle Scholar
  29. 25.
    J. L. Whitten and T. A. Pakkanen, Phys. Rev. B 21, 4357 (1980).CrossRefGoogle Scholar
  30. 26.
    C. Pisani, Phys. Rev. B 17, 3143 (1978).CrossRefGoogle Scholar
  31. 27.
    K. Hermann, P. S. Bagus, C. R. Brundle, and D. Menzel, Phys. Rev. B 24, 7025 (1981);CrossRefGoogle Scholar
  32. 27a.
    C. R. Brundle, P. S. Bagus, D. Menzel, and K. Hermann, Phys. Rev. B 24, 7041 (1981).CrossRefGoogle Scholar
  33. 28.
    I. Panas, J. Schule, P. E. M. Siegbahn, and U. Wahlgrcn, Chem. Phys. Lett. 149, 265 (1988); P. E. M. Siegbahn, L. G. M. Pettersson, and U. Wahlgren, J. Chem. Phys. 94, 4024(1991).Google Scholar
  34. 29.
    P. S. Bagus, K. Hermann and C. W. Bauschlicher Jr., J. Chem. Phys. 80, 4378 (1984).CrossRefGoogle Scholar
  35. 30.
    C. J. Nelin, P. S. Bagus, and M. R. Philpott, J. Chem. Phys. 87, 2170 (1987).CrossRefGoogle Scholar
  36. 31.
    C. W. Bauschlicher, P. S. Bagus, C. J. Nelin, and B. Roos, J. Chem. Phys 85, 354 (1986).CrossRefGoogle Scholar
  37. 32.
    C. W. Bauschlicher, P. S. Bagus, and H. F. Schaefer, IBM J. Res. and Dev. 22, 213 (1978).CrossRefGoogle Scholar
  38. 33.
    H. Ishida, Phys. Rev. B 38, 8006 (1988); ibid. 42, 10899 (1990).Google Scholar
  39. 34.
    P. O. Garland, Phys. Nor. 6, 201 (1972).Google Scholar
  40. 35.
    See the discussion in F. Mas and P. S. Bagus, J. Chem. Phys. 94, 1236 (1991) and references therein.CrossRefGoogle Scholar
  41. 36.
    C. E. Moore, Atomic Energy Levels, Natl. Bur. Stand. Circ. No. 467 (U. S. GPO, Washington, D. C., 1949).Google Scholar
  42. 37.
    K. P. Huber and G. Ilerzberg, Molecular Spectra and Molecular Structure IV. Constants of Diatomic Molecules (Van Nostrand-Rcinhold, New York, 1979).Google Scholar
  43. 38.
    J. F. Wendelken, Appl. Surf. Sci. 11/12, 172 (1982).CrossRefGoogle Scholar
  44. 39.
    P. S. Bagus and G. Pacchioni, Surf. Sci., 236, 233 (1990).CrossRefGoogle Scholar

Copyright information

© Plenum Press, New York 1992

Authors and Affiliations

  • P. S. Bagus
    • 1
  • G. Pacchioni
    • 2
  1. 1.IBM Research DivisionAlmaden Research CenterSan JoseUSA
  2. 2.Dip. di Chimica Inorganica e Metallorganica, Centro CNRUniversita’ degli Studi di MilanoMilanoItaly

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