Abstract
The C.I. method is applied to already published double-ζ SCF wave functions for OF2, NO −2 and CN−. All doubly excited configurations are considered. The second order approximation values presented for those cases are compared with the exact energy values in some minor cases. An attempt has been made to improve the rate of convergency of the process by transforming the canonical SCF occupied orbitals into localized ones and the virtual canonical orbitals into a particular type of localized orbitals. These latter show also an intuitively acceptable spatial conformation.
Zusammenfassung
Die CI Methode wird auf bereits bekannte Doppel-Zeta-SCF-Wellenfuntionen für die Systeme OF2, NO −2 und CN− angewandt. Dabei werden alle doppelt angeregten Konfigurationen berücksichtigt. Um die Konvergenz zu verbessern, werden versuchsweise die kanonischen und besetzten SCF-Orbitale in lokalisierte Orbitale und die virtuellen kanonischen Orbitale in einen besonderen Typ von lokalisierten Orbitalen transformiert. Die letzteren zeigen eine besonders geeignete räumliche Anpassung.
Résumé
Pour un calcul de intéraction de configurations, comprenant toutes le configurations à double excitation, on a employé des fonctions d'onde SCF sur une base doublée. Pour le calcul complet on a essayé des formules d'approximation, qu'on a pu vérifier avec le calcul exact sur des cas réduits.
Pour améliorer la vélocité de convergence du procés on a transformé les orbitales canoniques SCF en orbitales localisées et aprés on a construit, selon un procedé particulier, des orbitales virtuelles localisées qui montrent une conformation dans l'espace qui est intuitivement satisfaisante.
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Work supported by the Consiglio Nazionale delie Ricerche.
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Bonaccorsi, R., Petrongolo, C., Scrocco, E. et al. Configuration-interaction calculations for the ground state of OF2, NO −2 , CN−: Canonical orbitals and exclusive orbitals. Theoret. Chim. Acta 15, 332–343 (1969). https://doi.org/10.1007/BF00529846
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DOI: https://doi.org/10.1007/BF00529846