Journal article
The allyl radical revisited: a theoretical study of the electronic spectrum
Department of Theoretical Chemistry, Chemical Center, Lund University, P.O. Box 124, Lund S-22100, Sweden
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 2B1 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.
Language: | English |
---|---|
Year: | 2003 |
Pages: | 689-698 |
ISSN: | 18734448 and 00092614 |
Types: | Journal article |
DOI: | 10.1016/j.cplett.2003.09.079 |