The allyl radical revisited: A theoretical study of the electronic spectrum.
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/128645
- author
- Aquilante, Francesco LU ; Jensen, Kasper LU and Roos, Björn LU
- organization
- publishing date
- 2003
- 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
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
- id
- 07fae2e5-d459-4ca9-9ad1-f1225851ca0b (old id 128645)
- date added to LUP
- 2016-04-01 17:16:02
- date last changed
- 2023-01-05 06:25:47
@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}}, doi = {{10.1016/j.cplett.2003.09.079}}, volume = {{380}}, year = {{2003}}, }