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Two-photon spectroscopy of dipole-forbidden transitions

I. Dipole-forbidden transitions and double excited configurations in the CNDO-CI methods

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Abstract

We have investigated the applicability of CNDO/S-type methods for the calculation of optical spectra of molecules with the special implication that the calculations should not only describe the intense, dipole-allowed transitions which dominate the one-photon absorption spectrum but also those transitions which are one-photon forbidden in first-order approximation. We show that such a method is well suited to predict dipole allowed and dipole forbidden transitions at a similar level of accuracy if double excited configurations are taken into account. In spite of the lack of perfect pairing in NDO methods there are still two types of states which exhibit a different sensitivity towards correlation effects. Therefore, the approximation by which we describe the R-dependence of the Coulomb repulsion gains much more importance than in cases where mainly dipole allowed transitions are of interest. These findings confirm results obtained earlier from theories for which the pairing theorem is valid. The calculated data show an excellent stability with respect to further increase of the number of configurations if at least about 200 energy selected configurations are taken into account.

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  1. Lehrstuhl für Theoretische Chemie der Universität zu Köln, D-5000, Köln, Federal Republic of Germany

    Bernhard Dick & Georg Hohlneicher

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Dick, B., Hohlneicher, G. Two-photon spectroscopy of dipole-forbidden transitions. Theoret. Chim. Acta 53, 221–251 (1979). https://doi.org/10.1007/BF00550279

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