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A comparison of variational and non-variational internally contracted multiconfiguration-reference configuration interaction calculations

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Summary

The internally contracted multiconfiguration-reference configuration interaction (CMRCI) method and several non-variational variants of this method (averaged coupled pair approximation (ACPF), quasidegenerate variational perturbation theory (QD-VPT), linearized coupled pair many electron theory (LCPMET)) have been employed to compute potential energy functions and other properties for a number of diatomic molecules (F2, O2, N2, CN, CO) using large basis sets and full valence CASSCF reference wavefunctions. In most cases the variational CMRCI wavefunctions yield more accurate spectroscopic constants than any of the employed non-variational methods. Several basis sets are compared for the N2 molecule. It is found that atomic natural orbital (ANO) contractions led to significant errors in the computedr e , ω e , andD e values.

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Authors and Affiliations

  1. Fakultät für Chemie, Universität Bielefeld, D-4800, Bielefeld, Federal Republic of Germany

    Hans-Joachim Werner

  2. School of Chemistry and Molecular Sciences, University of Sussex, BN1 9QJ, Falmer, Brighton, UK

    Peter J. Knowles

Authors
  1. Hans-Joachim Werner
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  2. Peter J. Knowles
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Werner, HJ., Knowles, P.J. A comparison of variational and non-variational internally contracted multiconfiguration-reference configuration interaction calculations. Theoret. Chim. Acta 78, 175–187 (1990). https://doi.org/10.1007/BF01112867

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  • DOI: https://doi.org/10.1007/BF01112867

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