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Theoretica chimica acta

, Volume 51, Issue 3, pp 207–217 | Cite as

Ab initio Calculations of the potential energy surface of the reaction of singlet methylene with the hydrogen molecule

  • Herbert Kollmar
  • Volker Staemmler
Original Investigations

Abstract

The potential energy surface for the insertion of singlet methylene into H2 has been computed on theab initio SCF level as well as with inclusion of electron correlation by means of the CEPA method. The results are compared with those of previous semiempirical,ab initio SCF and CI calculations. The system is a prototype of a reaction where an allowed and a symmetry-forbidden path can compete. The electron correlation energy was found to be very different for different regions of the surface, but did not have much influence on the optimum reaction path. From the computed heat of the reaction, the heat of formation of singlet methylene was estimated to be 101.5 kcal/mol. According to the calculations the reaction does not need any activation energy.

Key words

Methylene, reaction of singlet ∼ with H2 

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References

  1. 1.
    Chanmugam, J., Burton, M.: J. Am. Chem. Soc.78, 509 (1956)Google Scholar
  2. 2.
    Skell, P. S., Woodworth, R. C.: J. Am. Chem. Soc.78, 4496 (1956)Google Scholar
  3. 3.
    Kirmse, W.: Carbene Chemistry, Second ed., p. 209 ff. New York: Academic Press 1971Google Scholar
  4. 4.
    Dobson, R. C., Hayes, D. M., Hoffmann, R.: J. Am. Chem. Soc.93, 6188 (1971)Google Scholar
  5. 5.
    Bodor, N., Dewar, M. J. S., Wasson, J. S.: J. Am. Chem. Soc.94, 9095 (1972)Google Scholar
  6. 6.
    Kollmar, H.: Tetrahedron28, 5893 (1972)Google Scholar
  7. 7.
    Cremaschi, P., Simonetta, M.: J. Chem. Soc. Faraday Trans. II,70, 1801 (1974)Google Scholar
  8. 8.
    Zurawski, B.: private communicationGoogle Scholar
  9. 9.
    Bauschlicher, Jr., C. W., Haber, K., Schaefer III, H. F., Bender, C. F.: J. Am. Chem. Soc.99, 3610 (1977)Google Scholar
  10. 10.
    Woodward, R. B., Hoffmann, R.: J. Am. Chem. Soc.87, 395, 2046, 2511 (1965)Google Scholar
  11. 11.
    Bauschlicher, Jr., C. W., Schaefer III, H. F., Bender, C. F.: J. Am. Chem. Soc.98, 1653 (1976)Google Scholar
  12. 12.
    Murrell, J. N., Pedley, J. B., Durmaz, S.: J. Chem. Soc. Faraday Trans. II,69, 1370 (1973)Google Scholar
  13. 13.
    Huzinaga, S.: J. Chem. Phys.42, 1293 (1965)Google Scholar
  14. 14.
    Huzinaga, S.: Approximate atomic functions I. Preprint, University of Alberta 1971Google Scholar
  15. 15.
    Driessler, F., Ahlrichs, R.: Chem. Phys. Letters23, 571 (1973)Google Scholar
  16. 16.
    Ahlrichs, R.: Theoret. Chim. Acta (Berl.)33, 157 (1974)Google Scholar
  17. 17.
    Meyer, W.: Intern. J. Quantum Chem.S5, 341 (1971)Google Scholar
  18. 18.
    Meyer, W.: J. Chem. Phys.58, 1017 (1973)Google Scholar
  19. 19.
    Ahlrichs, R., Lischka, H., Staemmler, V., Kutzelnigg, W.: J. Chem. Phys.62, 1225 (1975)Google Scholar
  20. 20.
    Ahlrichs, R., Driessler, F., Lischka, H., Staemmler, V., Kutzelnigg, W.: J. Chem. Phys.62, 1235 (1975)Google Scholar
  21. 21.
    Ahlrichs, R., Lischka, H., Zurawski, B., Kutzelnigg, W.: J. Chem. Phys.63, 4685 (1975)Google Scholar
  22. 22.
    Herzberg, G., Johns, J. W. C.: Proc. Roy. Soc. (London)A295, 107 (1966)Google Scholar
  23. 23.
    Bartell, L. S., Kuchitsu, K., DeNui, R. J.: J. Chem. Phys.35, 1211 (1961)Google Scholar
  24. 24.
    Zurawski, B., Kutzelnigg, W.: J. Am. Chem. Soc.100, 2654 (1978)Google Scholar
  25. 25.
    Dewar, M. J. S., Kollmar, H., Li, W. K.: J. Chem. Educ.52, 305 (1975)Google Scholar
  26. 26.
    Lengel, R. K., Zare, R. N.: private communicationGoogle Scholar
  27. 27.
    JANAF thermochemical tables, 2nd Ed., National Bureau of Standards, NSRDS-NBS 37, 1971Google Scholar
  28. 28.
    Mills, I. M.: Spectrochim. Acta16, 35 (1960)Google Scholar
  29. 29.
    JANAF thermochemical tables, 1975 Supplement, J. Phys. Chem. Ref. Data4, 1 (1975)Google Scholar
  30. 30.
    Staemmler, V.: Theoret. Chim. Acta (Berl.)31, 49 (1973)Google Scholar

Copyright information

© Springer-Verlag 1979

Authors and Affiliations

  • Herbert Kollmar
    • 1
  • Volker Staemmler
    • 1
  1. 1.Lehrstuhl für Theoretische Chemie der Ruhr-Universität BochumBochumFederal Republic of Germany

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