Electronic structure of metal clusters

  • G. K. Wertheim


Photoemission spectra of valence electrons in metal clusters, together with threshold ionization potential measurements, provide a coherent picture of the development of the electronic structure from the isolated atom to the large metallic cluster. An insulator-metal transition occurs at an intermediate cluster size, which serves to define the boundary between small and large clusters. Although the outer electrons may be delocalized over the entire cluster, a small cluster remains insulating until the density of states near the Fermi level exceeds 1/kT. In large clusters, with increasing cluster size, the band structure approaches that of the bulk metal. However, the bands remain significantly narrowed even in a 1000-atom cluster, giving an indication of the importance of long-range order.

The core-electron binding-energy shifts of supported metal clusters depend on changes in the band structure in the initial state, as well as on various final-state effects, including changes in core hole screening and the coulomb energy of the final-state charge. For cluster supported on amorphous carbon, this macroscopic coulomb shift is often dominant, as evidenced by the parallel shifts of the core-electron binding energy and the Fermi edge. Auger data confirm that final-state effects dominate in cluster of Sn and some other metals. Surface atom core-level shifts provide a valuable guide to the contributions of initial-state changes in band structure to cluster core-electron binding energy shifts, especially for Au and Pt. The available data indicate that the shift observed in supported, metallic clusters arise largely from the charge left on the cluster by photoemission. As the metal-insulator transition is approached from above, metallic screening is suppressed and the shift is determined by the local environment.


79.60 36.40 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Martins, J.L., Buttet J., Car, R.: Phys. Rev. Lett. 53, 655 (1984).ADSCrossRefGoogle Scholar
  2. 2.
    Raghavachari, K., Logovinsky, V.: Phys. Rev. Lett. 55, 2853 (1985).ADSCrossRefGoogle Scholar
  3. see also Blaisten-Barojas, E., Levesque, D.: Phys. Rev. B. 34, 3910 (1986).ADSCrossRefGoogle Scholar
  4. 3.
    Kubo, R., Kawabata, A., Kobayashi, S.: Ann. Rev. Mater. Sci. 14, 49 (1984).ADSCrossRefGoogle Scholar
  5. 4.
    Casula, F., Andreoni, W., Maschke, K.: J. Phys. C. 19, 5155 (1986).ADSCrossRefGoogle Scholar
  6. 5.
    Hamilton, J.F., Logel, P.C.: Thin Solid Films 16, 49 (1973).ADSCrossRefGoogle Scholar
  7. Hamilton, J.F., Logel, P.C.: 23, 89 (1974).Google Scholar
  8. 6.
    DiCenzo, S.B., Wertheim, G.K.: Comments Solid State Phys. 11, 203 (1985).Google Scholar
  9. 7.
    Wertheim, G.K., DiCenzo, S.B.: Phys. Rev. B 37, 844 (1988).ADSCrossRefGoogle Scholar
  10. 8.
    Rohlfing, E.A., Cox, D.M., Kaldor, A.: Chem. Phys. Lett. 99, 161 (1983).ADSCrossRefGoogle Scholar
  11. 9.
    Powers, D., Hansen, S.G., Geusic, M.E., Michalopolous, D.L., Smalley, R.E.: J. Chem. Phys. 78, 2866 (1983).ADSCrossRefGoogle Scholar
  12. 10.
    Knight, W.D., Clemenger, K., deHeer, W.A., Saunders, W.A., Chou, M.Y., Cohen, M.L.: Phys. Rev. Lett. 52, 2141 (1984).ADSCrossRefGoogle Scholar
  13. 11.
    Ekardt, W.: Phys. Rev. B. 29, 1558 (1984).ADSCrossRefGoogle Scholar
  14. 12.
    Beck, D.E.: Solid State Commun. 49, 381 (1984).ADSCrossRefGoogle Scholar
  15. 13.
    Smith, J.M.: AIAA J. 3, 648 (1965).CrossRefGoogle Scholar
  16. 14.
    Wood, D.M.: Phys. Rev. Lett. 46, 749 (1981).ADSCrossRefGoogle Scholar
  17. 15.
    Plieth, W.J.: Surf. Sci. 156, 530 (1985).ADSCrossRefGoogle Scholar
  18. 16.
    Unwin, R., Bradshaw, A.M.: Chem. Phys. Lett. 58, 58 (1978).ADSCrossRefGoogle Scholar
  19. Takasu, Y., Unwin, R., Tesche, B., Bradshaw, A.M., Grunze, A.M.: Surf. Sci. 77, 219 (1978).ADSCrossRefGoogle Scholar
  20. 17.
    Egelhoff, W.F., Tibbetts, G.G.: Solid State Commun. 29, 53 (1979).ADSCrossRefGoogle Scholar
  21. Egelhoff, W.F., Tibbetts, G.G.: Phys. Rev. B 19, 5028 (1979).ADSCrossRefGoogle Scholar
  22. 18.
    Oberli, L., Monot, R, Mathieu, H.J., Landolt, D, Buttet, J.: Surf. Sci. 106, 301 (1981).ADSCrossRefGoogle Scholar
  23. 19.
    Lee, S.T., Apai, G., Mason, M.G., Benbow, R., Hurych, Z.: Phys. Rev. B 23, 505 (1981).ADSCrossRefGoogle Scholar
  24. 20.
    Mason, M.G.: Phys. Rev. B 27, 748 (1983), and references therein.ADSCrossRefGoogle Scholar
  25. 21.
    Colbert, J., Zangwill, A., Strongin, M., Krummacher, S.: Phys. Rev. B 27, 1378 (1983).ADSCrossRefGoogle Scholar
  26. 22.
    Cyrot-Lackmann, F.: Adv. Phys. 16, 393 (1967).ADSCrossRefGoogle Scholar
  27. Cyrot-Lackmann, F.: J. Phys. Chem. Solids 29, 235 (1968).CrossRefGoogle Scholar
  28. 23.
    DiCenzo, S.B., Berry, S., Hartford, E.: Phys. Rev. B 38, 8465 (1988).ADSCrossRefGoogle Scholar
  29. 24.
    Smalley, R.E.: Bull. Am. Phys. Soc. 33, 642 (1988).Google Scholar
  30. 25.
    Citrin, P.H., Wertheim, G.K., Baer, Y.: Phys. Rev. Lett. 41, 1425 (1978).ADSCrossRefGoogle Scholar
  31. Citrin, P.H., Wertheim, G.K., Baer, Y.: Phys. Rev. B 27, 3160 (1983).ADSCrossRefGoogle Scholar
  32. 26.
    Wertheim, G.K., DiCenzo, S.B, Youngquist, S.E.: Phys. Rev. Lett. 51, 3210 (1983).ADSCrossRefGoogle Scholar
  33. 27.
    Wertheim, G.K., DiCenzo, S.B., Buchanan, D.N.E.: Phys. Rev. B 33, 5384 (1986).ADSCrossRefGoogle Scholar
  34. 28.
    Wertheim, G.K., DiCenzo, S.B., Buchanan, D.N.E., Bennett, P.A.: Solid State Commun. 53, 377 (1985).ADSCrossRefGoogle Scholar
  35. 29.
    Cini, M.: Surf. Sci. 62, 148 (1977).ADSCrossRefGoogle Scholar
  36. 30.
    Castellani, N.J., Leroy, D.B., Lambrecht, W.: Chem. Phys. 95, 459 (1985).CrossRefGoogle Scholar
  37. 31.
    Parmigiani, F., Kay, E., Bagus, P.S., Neun, C.J.: J. Electron Spectrosc. Relat. Phenom. 36, 257 (1985).CrossRefGoogle Scholar
  38. 32.
    DiCenzo, S.B., Wertheim, G.K.: J. Electron Spectrosc. Relat. Phenom. 43, c7 (1987).CrossRefGoogle Scholar
  39. 33.
    Wagner, CD.: Faraday Discuss. Chem. Soc. 60, 291 (1975).CrossRefGoogle Scholar
  40. 34.
    Wertheim, G.K.: Phys. Rev. B 36, 9559 (1987).ADSCrossRefGoogle Scholar
  41. 35.
    Cheung, T.T.P.: Chem. Phys. Lett. 110, 219 (1984).ADSCrossRefGoogle Scholar
  42. 36.
    Cheung, T.T.P.: Surf. Sci. 127, L129 (1983).ADSCrossRefGoogle Scholar
  43. Cheung, T.T.P.: Surf. Sci. 140, 151 (1984).ADSCrossRefGoogle Scholar
  44. 37.
    Kohiki, S., Ikeda, S.: Phys. Rev. B. 34, 3786 (1986).ADSCrossRefGoogle Scholar

Copyright information

© Springer-Verlag 1989

Authors and Affiliations

  • G. K. Wertheim
    • 1
  1. 1.AT&T Bell LaboratoriesMurray HillUSA

Personalised recommendations