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Semi-empirical all valence electrons SCF-MO-CNDO theory

III. Orbital energies and ionization potentials

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Abstract

Orbital energy levels, calculated by the semi-empirical SCF-MO-CNDO theory developed previously, are compared with experimental ionization potentials assuming that Koopmans' theorem is valid. Most of the energy levels are in much better agreement with experiment than those calculated from either the Pople-Segal CNDO/2 theory or the Extended Hückel Theory. The results are used to assign observed ionization potentials to specific molecular orbitals for molecules for which this assignment has not been determined experimentally.

Zusammenfassung

Mit unserer SCF-MO-CNDO-Methode berechnete Orbitalenergien werden mit experimentellen Ionisationspotentialen verglichen. Die übereinstimmung ist besser als bei der erweiterten Hückeloder der CNDO2-Methode von Pople und Segal.

Résumé

Les niveaux d'énergie orbitale calculés à l'aide de la théorie semiempirique SCF-MO-CNDO, sont comparés avec les potentiaux experimentaux d'ionisation en admettant la validité de le théorème de Koopmans. La plupart des niveaux d'énergie sont en meilleur accord avec l'expérience que lesquels calculés selon la méthode Pople-Segal CNDO/2 ou la méthode d'Hückel extensé. Puis on a coordonné les résultats avec des orbitales moléculaires.

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Author notes

  1. J. M. Sichel

    Present address: Department of Chemistry, University of Bristol, Bristol 8, England

Authors and Affiliations

  1. Quantum Chemistry Laboratory, Department of Chemistry, McGill University, Montreal 2, Canada

    J. M. Sichel & M. A. Whitehead

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  1. J. M. Sichel
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  2. M. A. Whitehead
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Part 1 in Theoret. chim. Acta (Berl.) 7, 32 (1967).

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Sichel, J.M., Whitehead, M.A. Semi-empirical all valence electrons SCF-MO-CNDO theory. Theoret. Chim. Acta 11, 239–253 (1968). https://doi.org/10.1007/BF00528342

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