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Ab Initio Calculations of Radiative Transition Probabilities in Diatomic Molecules

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Comparison of Ab Initio Quantum Chemistry with Experiment for Small Molecules

Abstract

Multiconfiguration self consistent field (MCSCF) and multiconfiguration reference configuration interaction (MCSCF-CI) techniques have been employed to calculate electric dipole moment and electronic transition moment functions of diatomic molecules and molecular ions. From these data radiative transition probabilities and lifetimes have been evaluated. It is demonstrated that the results are strongly dependent on electron correlation effects. Using highly correlated MCSCF-CI wavefunctions the radiative lifetimes are obtained with an accuracy of 10–15 percent, which is comparable to the uncertainties of the best experimental values. Often the calculated predictions appear to be more reliable than measured values. In some cases it has been found that empirical transition moment functions, which have been derived from measured relative intensities, exhibit an incorrect variation with the inter-nuclear distance.

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Author information

Authors and Affiliations

  1. Fachbereich Chemie, Universität Frankfurt/M, D-6000, Frankfurt, West Germany

    Hans-Joachim Werner (Visiting Fellow) & Pavel Rosmus (Visiting Fellow)

  2. Chemical Laboratory, University of Cambridge, Cambridge, CB2 1EW, England

    Hans-Joachim Werner (Visiting Fellow)

  3. JILA, Boulder, Colorado, 80309, USA

    Pavel Rosmus (Visiting Fellow)

  4. University of Colorado, Boulder, Colorado, 80309, USA

    Pavel Rosmus (Visiting Fellow)

Authors
  1. Hans-Joachim Werner
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  2. Pavel Rosmus
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Editors and Affiliations

  1. Quantum Theory Project, University of Florida, USA

    Rodney J. Bartlett

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© 1985 D. Reidel Publishing Company

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Werner, HJ., Rosmus, P. (1985). Ab Initio Calculations of Radiative Transition Probabilities in Diatomic Molecules. In: Bartlett, R.J. (eds) Comparison of Ab Initio Quantum Chemistry with Experiment for Small Molecules. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-5474-8_10

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  • DOI: https://doi.org/10.1007/978-94-009-5474-8_10

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-8917-3

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