The allyl radical revisited: a theoretical study of the electronic spectrum.
2003 (English)In: Chemical Physics Letters, ISSN 0009-2614, E-ISSN 1873-4448, Vol. 380, no 5-6, 689-698 p.Article in journal (Refereed) Published
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.
Place, publisher, year, edition, pages
2003. Vol. 380, no 5-6, 689-698 p.
Other Basic Medicine
IdentifiersURN: urn:nbn:se:uu:diva-145691DOI: 10.1016/j.cplett.2003.09.079ISI: 000186265500030OAI: oai:DiVA.org:uu-145691DiVA: diva2:396621