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Konsequenzen des Koopmansschen Theorems in den Restricted Hartree Fock Methoden für open-shell-Systeme

Consequences of Koopmans' theorem in the restricted Hartree Fock methods for open shell systems

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Abstract

The application of Koopmans' theorem to open shell systems shows — compared with closed shell systems — an important difference: a mixture of one-electron-states of theN-electron system is needed for the quantum mechanical description of the (N – 1)-electron system. The ionization potentials are obtained as eigenvalues of a special matrix. Equations for the elements of thisI-matrix were derived which are applicable to systems having a doublet ground state. The derivation was carried out for the procedures developed by Roothaan, Kruglyak, McWeeny, Longuet-Higgins, and Pople and Nesbet using the density matrix formalism. First numerical calculations suggest that the effects which are taken into account in the exact form of Koopmans' theorem are important.

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  1. Sektion Chemie der Humboldt-Universität zu Berlin, Bunsenstr. 1, DDR-108, Berlin, DDR

    Joachim Sauer & Christoph Jung

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  1. Joachim Sauer
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  2. Christoph Jung
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Sauer, J., Jung, C. Konsequenzen des Koopmansschen Theorems in den Restricted Hartree Fock Methoden für open-shell-Systeme. Theoret. Chim. Acta 40, 129–141 (1975). https://doi.org/10.1007/BF01135884

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  • DOI: https://doi.org/10.1007/BF01135884

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