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Theoretical characterization of the lowest-energy absorption band of pyrrole

Roos, Björn LU ; Malmqvist, Per-Åke LU ; Molina, Vicent LU ; Serrano-Andres, L and Merchan, M (2002) In Journal of Chemical Physics 116(17). p.7526-7536
Abstract
The lowest-energy band of the electronic spectrum of pyrrole has been studied with vibrational resolution by using multiconfigurational second-order perturbation theory (CASPT2) and its multistate extension (MS-CASPT2) in conjunction with large atomic natural orbital-type basis sets including Rydberg functions. The obtained results provide a consistent picture of the recorded spectrum in the energy region 5.5-6.5 eV and confirm that the bulk of the intensity of the band arises from a pipi(*) intravalence transition, in contradiction to recent theoretical claims. Computed band origins for the 3s,3p Rydberg electronic transitions are in agreement with the available experimental data, although new assignments are suggested. As illustrated in... (More)
The lowest-energy band of the electronic spectrum of pyrrole has been studied with vibrational resolution by using multiconfigurational second-order perturbation theory (CASPT2) and its multistate extension (MS-CASPT2) in conjunction with large atomic natural orbital-type basis sets including Rydberg functions. The obtained results provide a consistent picture of the recorded spectrum in the energy region 5.5-6.5 eV and confirm that the bulk of the intensity of the band arises from a pipi(*) intravalence transition, in contradiction to recent theoretical claims. Computed band origins for the 3s,3p Rydberg electronic transitions are in agreement with the available experimental data, although new assignments are suggested. As illustrated in the paper, the proper treatment of the valence-Rydberg mixing is particularly challenging for ab initio methodologies and can be seen as the main source of deviation among the recent theoretical results as regards the position of the low-lying valence excited states of pyrrole. (C) 2002 American Institute of Physics. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Physics
volume
116
issue
17
pages
7526 - 7536
publisher
American Institute of Physics
external identifiers
  • wos:000175068800019
  • scopus:0036573687
ISSN
0021-9606
DOI
10.1063/1.1465406
language
English
LU publication?
yes
id
300494fc-aa91-4d26-b738-149060e18afb (old id 340282)
date added to LUP
2007-11-12 12:22:37
date last changed
2017-08-27 03:49:36
@article{300494fc-aa91-4d26-b738-149060e18afb,
  abstract     = {The lowest-energy band of the electronic spectrum of pyrrole has been studied with vibrational resolution by using multiconfigurational second-order perturbation theory (CASPT2) and its multistate extension (MS-CASPT2) in conjunction with large atomic natural orbital-type basis sets including Rydberg functions. The obtained results provide a consistent picture of the recorded spectrum in the energy region 5.5-6.5 eV and confirm that the bulk of the intensity of the band arises from a pipi(*) intravalence transition, in contradiction to recent theoretical claims. Computed band origins for the 3s,3p Rydberg electronic transitions are in agreement with the available experimental data, although new assignments are suggested. As illustrated in the paper, the proper treatment of the valence-Rydberg mixing is particularly challenging for ab initio methodologies and can be seen as the main source of deviation among the recent theoretical results as regards the position of the low-lying valence excited states of pyrrole. (C) 2002 American Institute of Physics.},
  author       = {Roos, Björn and Malmqvist, Per-Åke and Molina, Vicent and Serrano-Andres, L and Merchan, M},
  issn         = {0021-9606},
  language     = {eng},
  number       = {17},
  pages        = {7526--7536},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Theoretical characterization of the lowest-energy absorption band of pyrrole},
  url          = {http://dx.doi.org/10.1063/1.1465406},
  volume       = {116},
  year         = {2002},
}