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Theoretical study of the electronic structure of diazomethane

I. The dissociation process CH2N2→CH2 + N2 in point group C 2v Symmetry

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Abstract

Ab initio calculations of the dissociation process CH2N2 → CH2 + N2 are presented. Calculations were made on the ground 1 A 1 state as well as on the first few excited states (3 B 1, 1 B 1, 1 A 1*) necessary to the description of the dissociation mechanism in point group C 2v symmetry. The variation of energy was determined as a function of the parameters R CH-R NN and θ HCH at several R CN values. Most results were obtained by using a basis set of Gaussian lobe functions contracted to “double-zeta” accuracy. A few calculations were made with the addition of polarization functions on all centers. The equilibrium geometry of the ground state, determined from coupled quadratic equations in the molecular parameters, is in satisfactory agreement with experimental values. The dissociation paths on the potential energy surfaces were determined. The locus of intersection points of the two 1 A 1 states is described; the avoided crossing of the two potential surfaces was determined from CI calculations based on an “intermediate” Hamiltonian. The geometric and electronic rearrangements due to dissociation as well as the bonding characteristics of the orbitals are discussed.

The dissociation energy of the molecule (D 00 (CH2N2)) is calculated to be 0.91 eV.

Finally, the term energy of the 1 A 1 state of CH2 is predicted to be 0.49 eV.

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References

  1. See e.g.: Allinger, N. L., Cava, M. P., De Jongh, D. C., Johnson, C. R., Lebel, N. A., Stevens, C. L.: Organic chemistry. New York, N.Y.: Worth Publishers 1971

    Google Scholar 

  2. Snyder, L. C., Basch, H.: J. Am. Chem. Soc. 91, 2189 (1969)

    Google Scholar 

  3. Hart, B. T.: Aust. J. Chem. 26, 461, 477 (1973)

    Google Scholar 

  4. Leroy, G., Sana, M.: Theoret. Chim. Acta (Berl.) 33, 329 (1974)

    Google Scholar 

  5. Lievin, J., Verhaegen, G.: to be published

  6. Woodward, R. B., Hoffmann, R.: The conservation of orbital symmetry. Weinheim: Verlag Chemie 1970

    Google Scholar 

  7. Chu, S. Y., Siu, A. K. Q., Hayes, E. F.: J. Am. Chem. Soc. 94, 2969 (1972)

    Google Scholar 

  8. Herzberg, G.: Spectra of diatomic molecules. Princeton, New Jersey: Van Nostrand 1950

    Google Scholar 

  9. Hehre, W. J., Stewart, R. F., Pople, J. A.: J. Chem. Phys. 51, 2657 (1969)

    Google Scholar 

  10. Clementi, E.: J. Chem. Phys. 46, 4737 (1967)

    Google Scholar 

  11. Burden, F. R., Hart, B. T.: Aust. J. Chem. 26, 1395 (1973)

    Google Scholar 

  12. Ditchfield, R., Hehre, W. J., Pople, J. A.: J. Chem. Phys. 54, 724 (1971)

    Google Scholar 

  13. Whitten, J. L.: J. Chem. Phys. 44, 359 (1966)

    Google Scholar 

  14. Huzinaga, S.: J. Chem. Phys. 42, 1293 (1965)

    Google Scholar 

  15. Whitten, J. L.: J. Chem. Phys. 39, 349 (1963)

    Google Scholar 

  16. Whitten, J. L.: Hackmeyer, M.: J. Chem. Phys. 51, 5584 (1969)

    Google Scholar 

  17. Whitten, J. L.: J. Chem. Phys. 56, 5458 (1972)

    Google Scholar 

  18. Basch, H., Robin, M. B., Kuebler, N. A.: J. Chem. Phys. 47, 1201 (1967)

    Google Scholar 

  19. Williamson, H.: C.A.C.M. 15, 100 (1972)

    Google Scholar 

  20. Liu, H. P. D., Verhaegen, G.: J. Chem. Phys. 53, 735 (1970); Int. J. Quantum Chem. 5, 103 (1971)

    Google Scholar 

  21. Mulliken, R. S.: J. Chem. Phys. 23, 1833 (1955)

    Google Scholar 

  22. Verhaegen, G., Moser, C. M.: J. Phys. B: Atom. Mol. Phys. 3, 478 (1970)

    Google Scholar 

  23. Desclaux, J. P., Moser, C. M., Verhaegen, G.: J. Phys. B: Atom. Molec. Phys. 4, 296 (1971)

    Google Scholar 

  24. Moore, C. B., Pimentel, G. C.: J.Chem. Phys. 40, 329, 342 (1964)

    Google Scholar 

  25. Cox, A. P., Thomas, L. F., Sheridan, J.: Nature (London) 181, 1000 (1958)

    Google Scholar 

  26. Wasserman, E., Hutton, R. S., Kuck, V. J., Jager, W. A.: J. Chem. Phys. 55, 2593 (1971)

    Google Scholar 

  27. Herzberg, G., Johns, J. W. C.: J. Chem. Phys. 54, 2276 (1971)

    Google Scholar 

  28. Salem, L., Leforestier, C., Segal, G., Wetmore, R.: J. Am. Chem. Soc. 97, 479 (1975)

    Google Scholar 

  29. Selected constants. Spectroscopic data relative to diatomic molecule, Rosen, B. Ed. Oxford: Pergamon Press 1970

  30. O'Neil, S., Schaeffer III, H. F., Bender, C. F.: J. Chem. Phys. 55, 162 (1971)

    Google Scholar 

  31. Laufer, A. H., Okabe, H.: J. Am. Chem. Soc. 93, 4137 (1971)

    Google Scholar 

  32. Paulett, G. S., Ettinger, R.: J. Chem. Phys. 39, 825, 3534 (1963)

    Google Scholar 

  33. Setser, D. W., Rabinovitch, B. S.: Can. J. Chem. 40, 1425 (1962)

    Google Scholar 

  34. Braun, W., Bass, A. M., Pilling, M.: J. Chem. Phys. 52, 5131 (1970)

    Google Scholar 

  35. For definition of method see: Hehre, W. J., Ditchfield, R., Radom, R., Pople, J. A.: J. Am. Chem. Soc. 92, 4796 (1970)

    Google Scholar 

  36. Hay, P. J., Hunt, W. J., Goddard III, W. A.: Chem. Phys. Letters 13, 30 (1972)

    Google Scholar 

  37. Staemmler, V.: Theoret. Chim. Acta (Berl.) 31, 49 (1973)

    Google Scholar 

  38. Handy, N. C.: Communication at the Seminar on Computational Methods in Molecular Physics, Strasbourg, September 1975

  39. Halberstadt, M. L., McNesby, J. R.: J. Am. Chem. Phys. 89, 4317 (1967); Carr Jr., R. W., Eder, T. W., Toper, M. G.: J. Chem. Phys. 53, 5716 (1970)

    Google Scholar 

  40. Frey, H. M.: J. Chem. Soc. Chem. Commun. 1024 (1972); Frey, H. M., Kennedy, G. J.: Chem. Commun. 6, 233 (1975)

  41. Harrison, J. F.: Accounts Chem. Res. 7, 378 (1974)

    Google Scholar 

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  1. Laboratoire de Chimie Physique Moléculaire, Université Libre de Bruxelles, Faculté des Sciences, Avenue F.D. Roosevelt, 50, B-1050, Brussels, Belgium

    Jacques Lievin & Georges Verhaegen

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  1. Jacques Lievin
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  2. Georges Verhaegen
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Lievin, J., Verhaegen, G. Theoretical study of the electronic structure of diazomethane. Theoret. Chim. Acta 42, 47–65 (1976). https://doi.org/10.1007/BF00548290

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  • DOI: https://doi.org/10.1007/BF00548290

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