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

Aquilante, Francesco LU ; Jensen, Kasper LU and Roos, Björn LU (2003) In Chemical Physics Letters 380(5-6). p.689-698
Abstract
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... (More)
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. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Chemical Physics Letters
volume
380
issue
5-6
pages
689 - 698
publisher
Elsevier
external identifiers
  • wos:000186265500030
  • scopus:0242289410
ISSN
0009-2614
DOI
10.1016/j.cplett.2003.09.079
language
English
LU publication?
yes
id
07fae2e5-d459-4ca9-9ad1-f1225851ca0b (old id 128645)
date added to LUP
2007-07-17 09:01:21
date last changed
2017-01-01 07:28:56
@article{07fae2e5-d459-4ca9-9ad1-f1225851ca0b,
  abstract     = {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.},
  author       = {Aquilante, Francesco and Jensen, Kasper and Roos, Björn},
  issn         = {0009-2614},
  language     = {eng},
  number       = {5-6},
  pages        = {689--698},
  publisher    = {Elsevier},
  series       = {Chemical Physics Letters},
  title        = {The allyl radical revisited: A theoretical study of the electronic spectrum.},
  url          = {http://dx.doi.org/10.1016/j.cplett.2003.09.079},
  volume       = {380},
  year         = {2003},
}