Natural states of interacting systems and their use for the calculation of intermolecular forces. II. Natural states in the asymptotic 1/R expansion |
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Authors: | F Maeder W Kutzelnigg |
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Institution: | Laboratoire de Chimie, Ecole Normale Supérieure de Jeunes Filles, 92 Montrouge, France;Ruhr-Universität Bochum, Lehrstuhl für Theoretische Chemie, 4630 Bochum, FRG |
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Abstract: | The asymptotic natural states i.e. the natural states of the subsystems in the various terms of the asymptotic expansion of the primitive wavefunction of the supersystem are defined. Integro-differential equations are derived that allow the direct calculation of these asymptotic natural states and from them, the terms C6, C8 etc. in the asymptotic 1/R expansion of the interaction energy. A pictorial interpretation of these states is given and the rapid convergence of the expansion in natural states is explained. The transferability of certain matrix elements is demonstrated and a virtually exact combination rule for the calculation of the Ck coefficients between different atoms from those for like atoms is obtained- The effects of intraatomic electron correlation on the Ck as well as the justification of a core-valence separation are discussed. |
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