Abstract
The vertical valence ionization potentials of cyclopropane, ethylene oxide and ethylene imine are calculated by a many-body Green's function method. For C3H6 the ordering of the ionization potentials is 2e′(σ), 1e″(π), 2a′1(σ), 1a″2(π), 1e′(σ). The assignment of the 2a′1 and the 1a″2 ionization potentials which has been controversial is thus clarified. The ordering is in agreement with the result obtained via Koopmans' theorem. For ethylene oxide and ethylene imine Koopmans' theorem fails in predicting the correct order of ionic states. For C2H4O the ordering of the ionization potentials is 2b 1(π), 4a 1, 1a 2(π), 2b 2,3a 1, 1b 1(π), 1b 2, 2a 1 and for C2H5N 6a′, 5a′, 3a″, 2a″, 4a′, 3a′, 1a″, 2a′. The agreement of the computed ionization potentials with the experimental values is very satisfactory.
This is a preview of subscription content, log in via an institution to check access.
References
Turner, D. W., Baker, C., Baker, A. D., Brundle, C. R.: Molecular photoelectron spectroscopy. London: Wiley-Interscience (1970)
Basch, H., Robin, M. B., Kuebler, N. A., Baker, C., Turner, D. W.: J. Chem. Phys. 51, 52 (1969)
Lindholm, E., Fridh, C., Åsbrink, L.: J. Chem. Soc. Faraday Disc. 54, 127 (1972)
Koopmans, T.: Physica 1, 104 (1933)
Evans, S., Joachim, P. J., Orchard, A. F., Turner, D. W.: Intern. J. Mass Spectrom. Ion Phys. 9, 41 (1972)
Richards, W. G., Walker, T. E. H., Hinkley, R. K.: A bibliography of ab initio molecular wave functions. Oxford: Clarendon Press 1971. Supplement by Richards, W. G., Walker, T. E. H., Farnell, L., Scott, P. R. Oxford: Clarendon Press 1974
Haselbach, E.: Chem. Phys. Letters 7, 428 (1970)
Lathan, W. A., Radom, L., Hariharan, P. C., Hehre, W. J., Pople, J. A.: Topics Current Chem. 40, 1 (1973)
Skancke, A.: J. Mol. Struct. 30, 95 (1976)
Cederbaum, L. S.: Theoret. Chim. Acta (Berl.) 31, 239 (1973); J. Phys. B8, 290 (1975)
Diercksen, G. H. F., Kraemer, W. P.: MUNICH, Molecular Program System, Reference Manual, Special Technical Report, Max-Planck-Institut für Physik und Astrophysik, to be published
Diercksen, G. H. F.: Theoret. Chim. Acta (Berl.) 33, 1 (1974)
Huzinaga, S.: J. Chem. Phys. 42, 1293 (1965)
Salez, C., Veillard, A.: Theoret. Chim. Acta (Berl.) 11, 441 (1968)
Bastiansen, O., Fritsch, F. N., Hedberg, K.: Acta Cryst. 17, 538 (1964)
Cunningham, G. L., Boyd, A. W., Meyers, R. J., Gwinn, W. D., Le Van, W.I.: J. Chem. Phys. 19, 676 (1951)
Bak, B., Skaarup, S.: J. Mol. Struct. 10, 385 (1971)
Cederbaum, L. S., Domcke, W.: J. Chem. Phys. 64, 603 (1976)
Chong, D. P., Herring, F. G., McWilliams, D.: J. Chem. Soc. Faraday Trans. II 70, 193 (1974)
Cederbaum, L. S.: J. Chem. Phys. 62, 2160 (1975)
Turner, T. E., Fiora, V. C., Kendrick, W. M.: J. Chem. Phys. 23, 1966 (1955)
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
von Niessen, W., Cederbaum, L.S. & Kraemer, W.P. The electronic structure of molecules by a many-body approach. Theoret. Chim. Acta 44, 85–93 (1977). https://doi.org/10.1007/BF00548031
Issue Date:
DOI: https://doi.org/10.1007/BF00548031