The allyl radical revisited: A theoretical study of the electronic spectrum

Research output: Contribution to journalLetter – Annual report year: 2003Researchpeer-review

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  • Author: Aquilante, Francesco

    Lund University, Sweden

  • Author: Kepp, Kasper Planeta

    Lund University

  • Author: Roos, Björn O.

    Lund University, Sweden

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In this Letter, we report the electronic spectrum of the allyl radical, obtained with multiconfigurational perturbation theory (MS-CASPT2). The assignment of the spectrum is in accordance with experiment to within 0.2 eV. We have computed the complete first Rydberg series and the beginning of the second Rydberg series. A new valence-excited B-2(1) state has been found which has hitherto been hidden by Rydberg transitions. A rationalisation of the electronic spectrum is provided in terms of resonance forms in ground and excited states. This model shows that while a multiconfigurational wavefunction is necessary to qualitatively model the system, the large ionic character of the valence electronic states makes an accurate treatment of the dynamical correlation necessary for a quantitative description of the spectrum. (C) 2003 Elsevier B.V. All rights reserved.
Original languageEnglish
JournalChemical Physics Letters
Issue number5-6
Pages (from-to)689-698
Publication statusPublished - 2003
Externally publishedYes
CitationsWeb of Science® Times Cited: No match on DOI
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ID: 59089045