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Theoretical investigation of the electronic spectrum of pyrazine

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Abstract

The description of Rydberg states by the complete active space self-consistent field (CASSCF) electronic structure method is known to be a difficult topic. In particular, two problems are frequently encountered: (a) the simultaneous presence of valence and Rydberg excited states in the same energy region can potentially lead to artificial valence–Rydberg mixing in the electronic wave functions. (b) Rydberg states have a tendency to be difficult to converge. We have implemented an approach for the consistent description of both valence and Rydberg excited states within the CASSCF electronic structure model. By employing the multiconfigurational second- and third-order perturbation theory (CASPT2/3) methods based on CASSCF reference wave functions, the procedure is verified by comparison with spectroscopic results for the example molecule pyrazine. Vertical excitation energies and other properties have been calculated for various electronic states. Basis sets and active spaces were selected to provide accurate results. Two combinations of aug-cc-pVTZ level basis sets complemented by Rydberg functions have been employed to calculate estimates for the properties of 19 singlet excited states of pyrazine. While many of the assignments made in previous studies could be confirmed, there are also several new aspects emerging from the present investigation.

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Acknowledgments

Á.V. acknowledges the OTKA Grant No. T67923 and the computational resources provided by the John-von-Neumann Institute, Research Centre Jülich (Project ID ehu01). Thanks go also to Wolfgang Domcke (TU München) and to the Leibniz Supercomputing Centre in München for providing computational resources on the Linux Cluster. We also thank Kenneth Ruud (U Tromsø) for stimulating discussions. G.J.H. and Á.V. acknowledge the DFG Grant (Project ID SU244/7-1) for partly supporting this study. C.W. would like to thank the Centre for Theoretical and Computational Chemistry (CTCC) at the University of Tromsø and the Research Council of Norway (Grant Nr. 177558/V30) for continued support.

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Authors and Affiliations

  1. Theoretical Chemistry (CTCC), Chemistry Department, University of Tromsø, 9037, Tromsø, Norway

    Clemens Woywod

  2. Department of Theoretical Physics, University of Debrecen, PO Box 5, 4010, Debrecen, Hungary

    Attila Papp & Ágnes Vibók

  3. Department of Information Technology, University of Debrecen, PO Box 12, 4010, Debrecen, Hungary

    Gábor J. Halász

Authors
  1. Clemens Woywod
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  2. Attila Papp
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  3. Gábor J. Halász
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  4. Ágnes Vibók
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Corresponding author

Correspondence to Clemens Woywod.

Additional information

Dedicated to Professor Sandor Suhai on the occasion of his 65th birthday and published as part of the Suhai Festschrift Issue.

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Woywod, C., Papp, A., Halász, G.J. et al. Theoretical investigation of the electronic spectrum of pyrazine. Theor Chem Acc 125, 521–533 (2010). https://doi.org/10.1007/s00214-009-0678-x

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  • DOI: https://doi.org/10.1007/s00214-009-0678-x

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