Theoretica chimica acta

, Volume 51, Issue 2, pp 145–162 | Cite as

Calculation of transition metal compounds using an extension of the CNDO formalism

I. Method of calculation and application to mono-, di- and tetranuclear compounds
  • Hans-Joachim Freund
  • Georg Hohlneicher
Original Investigations


An extended CNDO formalism for the treatment of large transition metal cluster systems is presented. After a detailed discussion of parametrization it is applied to a family of compounds, namely to Co(CO) 4 , Co2(CO)8, Co4(CO)12, Mn2(CO)10.

The results can be interpreted in the light of simple electron counting rules and additionally allow detailed insight in bonding capabilities of large metal cluster systems.

Bridged and unbridged clusters are compared and the results are extrapolated to surface systems. In the case of Co4(CO)12 two possible stereoisomers of symmetryC3v andT d are discussed.

Key words

Transition metal compounds Adsorbate systems Extended CNDO 


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  1. 1a.
    Braterman, P. S.: Structure and bonding, Vol. 10, pp. 57–86 (1972)Google Scholar
  2. 1b.
    Joergensen, C. K.: Structure and bonding, Vol. 1, pp. 3–31 (1966)Google Scholar
  3. 1c.
    Mingos, D. M. P.: Advan. Organomet. Chem.15, 1 (1977)Google Scholar
  4. 1d.
    Segal, G. A.: Modern theoretical chemistry, Vol. 7, 8, Part A, B: Electronic structure calculations. New York: Plenum Press 1977Google Scholar
  5. 1e.
    Roesch, N., in: Electrons in finite and infinite systems, Phariseau, P. ed. New York: Plenum Press 1976Google Scholar
  6. 2.
    Schaefer, H. F. III: Acc. Chem. Res.10, 287 (1977)Google Scholar
  7. 3a.
    Messmer, R. P., Tucker, E. W., Johnson, K. H.: Surf. Sci.42, 341 (1975)Google Scholar
  8. 3b.
    Messmer, R. al.: Phys. Rev. B13, 1396 (1976)Google Scholar
  9. 4a.
    Pople, J. A., Santry, D. P., Segal, G. A.: J. Chem. Phys.43, S 130 (1965)Google Scholar
  10. 4b.
    Pople, J. A., Segal, G. A.: J. Chem. Phys.43, S 136 (1965)Google Scholar
  11. 4c.
    Pople, J. A., Segal, G. A.: J. Chem. Phys.44, 3289 (1966)Google Scholar
  12. 4d.
    Santry, D. P., Segal, G. A.: J. Chem. Phys.47, S 158 (1967)Google Scholar
  13. 5.
    Pople, J. A., Beveridge, D.: Approximate molecular orbital theory. New York: McGraw HillGoogle Scholar
  14. 6a.
    Baetzold, R. C.: J. Chem. Phys.55, 4355 (1971)Google Scholar
  15. 6b.
    Baetzold, R. C.: J. Chem. Phys.55, 4363 (1971)Google Scholar
  16. 7.
    Clack, D. W., Hush, N. S., Yandle, J. R.: J. Chem. Phys.57, 3503 (1972)Google Scholar
  17. 8.
    Blyholder, G.: J. Chem. Phys.62, 3193 (1975)Google Scholar
  18. 9.
    Moore, C. E.: Atomic energy levels, Vol. 1–3, NBS Circ.Google Scholar
  19. 10.
    Anno, T., Teruya, H.: J. Chem. Phys.52, 2840 (1970)Google Scholar
  20. 11.
    Crossley, R. J. S.: Advan. Atom. Mol. Phys.52, 37 (1969)Google Scholar
  21. 12.
    Shadmi, Y.: J. Res. NBS A73, 173Google Scholar
  22. 13.
    Hotop, H., Lineberger, W. C.: J. Chem. Phys. Ref. Data4, 539 (1975)Google Scholar
  23. 14.
    Clementi, E., Raimondi, P. L.: J. Chem. Phys.38, 2649 (1963)Google Scholar
  24. 15.
    Pariser, R.: J. Chem. Phys.21, 528 (1953)Google Scholar
  25. 16.
    Demuynck, J., Veillard, A.: Theoret. Chim. Acta (Berl.)28, 241 (1973)Google Scholar
  26. 17.
    Osman, R., Ewig, C. S., van Wazer, J. R.: Chem. Phys. Letters39, 27 (1976)Google Scholar
  27. 18.
    Hillier, I. H., Saunders, Y. R.: Mol. Phys.22, 1025 (1971)Google Scholar
  28. 19.
    Turner, D. al.: Molecular photoelectron spectroscopy. Wiley Interscience 1970Google Scholar
  29. 20.
    Edgell, W. F., Lyford, J. IV: J. Chem. Phys.52, 4329 (1970)Google Scholar
  30. 21.
    Sumner, G. G., Klug, H. P., Alexander, L. E.: Acta Cryst.17, 732 (1964)Google Scholar
  31. 22.
    Wei, C.-H., Dahl, L. F.: J. Am. Chem. Soc.88, 1821 (1966)Google Scholar
  32. 23.
    Dahl, L. F., Rundle, R. E.: Acta Cryst.16, 419 (1963)Google Scholar
  33. 24.
    Gelius, U.: Phys. Scripta9, 133 (1974)Google Scholar
  34. 25.
    Ozin, G. A.: in Intern. Conf. Matrix Isol. Spectry., Gerischer, H. ed., p. 180. Berlin 1977Google Scholar
  35. 26.
    Freund, H. J.: Dissertation, Köln, 1978Google Scholar
  36. 27a.
    Adams, D. I., Zooper, M. A., Squire, A. J.: J. Chem. Soc. 71 (1971)Google Scholar
  37. 27b.
    Flitcroft, N., Huggins, D. K., Kaesz, H. D.: Inorg. Chem.3, 1123 (1964)Google Scholar
  38. 27c.
    Lindner, E., Behrens, H., Brikle, S. J.: J. Organomet. Chem.15, 165 (1968)Google Scholar
  39. 28a.
    Haas, H., Sheline, R. K.: J. Inorg. Nucl. Chem.29, 693 (1967)Google Scholar
  40. 28b.
    Lucken, E. A. al.: J. Chem. Soc. A148 (1967)Google Scholar

Copyright information

© Springer-Verlag 1979

Authors and Affiliations

  • Hans-Joachim Freund
    • 1
  • Georg Hohlneicher
    • 1
  1. 1.Lehrstuhl für Theoretische Chemie der Universität zu KölnKölnFederal Republic of Germany

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