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Photoionization of pyrrole from the \(B_2\) state: a computational study on the effects of Rydberg–valence mixing

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Abstract

Does the optically bright \(B_2(\pi \rightarrow \pi ^*)\) transition in pyrrole correspond to an inter-valence or to a mixed valence–Rydberg transition? State-of-the-art electronic structure methods provide inconclusive results and relegate the answer to future time-resolved photoelectron spectroscopy experiments. Here, benchmark calculations of photoionization cross sections, asymmetry parameters and molecular frame photoelectron angular distributions (MFPADs) have been performed with the aim of discerning between the two types of transitions. In particular, we show that MFPADs are very sensitive probes of the electronic wave function and that accurate experimental MFPADs could be used to identify the electronic character of the \(B_2\) state.

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Acknowledgements

This research has been supported by the Croatian Science Foundation under the Grant HRZZ IP-2016-06-1142.

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Authors and Affiliations

  1. Department of Physical Chemistry, Ruđer Bošković Institute, 10000, Zagreb, Croatia

    Aurora Ponzi, Marin Sapunar & Nađa Došlić

  2. Dipartimento di Scienze Chimiche, Università di Trieste, 34127, Trieste, Italy

    Piero Decleva

Authors
  1. Aurora Ponzi
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  2. Marin Sapunar
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  3. Nađa Došlić
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  4. Piero Decleva
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Correspondence to Aurora Ponzi.

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Published as part of the topical collection of articles from the 17th edition of the Central European Symposium on Theoretical Chemistry (CESTC 2019) in Austria.

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Ponzi, A., Sapunar, M., Došlić, N. et al. Photoionization of pyrrole from the \(B_2\) state: a computational study on the effects of Rydberg–valence mixing. Theor Chem Acc 139, 137 (2020). https://doi.org/10.1007/s00214-020-02649-1

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