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A theoretical investigation of valence and Rydberg electronic states of acrolein

Aquilante, Francesco LU ; Barone, V and Roos, Björn LU (2003) In Journal of Chemical Physics 119(23). p.12323-12334
Abstract
The main features of the ultraviolet spectrum of acrolein have been studied by a multireference perturbative treatment and by a time dependent density functional approach. The valence and Rydberg transition energies have been calculated and the assignment of the experimental bands has been clarified. The different relaxation trends of the three lowest singlet and triplet excited states have been analyzed by unconstrained geometry optimizations. This has allowed, in particular, the characterization of a twisted 3(*) state, which is crucial for the interesting photophysics and photochemistry of the acrolein molecule and, more generally, of the ,-enones. Solvatochromic shifts in aqueous solution have been investigated using a combined... (More)
The main features of the ultraviolet spectrum of acrolein have been studied by a multireference perturbative treatment and by a time dependent density functional approach. The valence and Rydberg transition energies have been calculated and the assignment of the experimental bands has been clarified. The different relaxation trends of the three lowest singlet and triplet excited states have been analyzed by unconstrained geometry optimizations. This has allowed, in particular, the characterization of a twisted 3(*) state, which is crucial for the interesting photophysics and photochemistry of the acrolein molecule and, more generally, of the ,-enones. Solvatochromic shifts in aqueous solution have been investigated using a combined discrete/continuum approach based on the so called polarizable continuum model. The experimental trends are well reproduced by this approach and a closer degeneracy in the triplet manifold has been detected in solution with respect to gas phase. ©2003 American Institute of Physics. (Less)
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author
organization
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Contribution to journal
publication status
published
subject
in
Journal of Chemical Physics
volume
119
issue
23
pages
12323 - 12334
publisher
American Institute of Physics
external identifiers
  • wos:000186970000031
  • scopus:0347948266
ISSN
0021-9606
DOI
language
English
LU publication?
yes
id
17550021-cbe4-42fd-8c47-43740beb59cb (old id 128650)
date added to LUP
2007-07-17 09:04:39
date last changed
2018-05-29 09:23:53
@article{17550021-cbe4-42fd-8c47-43740beb59cb,
  abstract     = {The main features of the ultraviolet spectrum of acrolein have been studied by a multireference perturbative treatment and by a time dependent density functional approach. The valence and Rydberg transition energies have been calculated and the assignment of the experimental bands has been clarified. The different relaxation trends of the three lowest singlet and triplet excited states have been analyzed by unconstrained geometry optimizations. This has allowed, in particular, the characterization of a twisted 3(*) state, which is crucial for the interesting photophysics and photochemistry of the acrolein molecule and, more generally, of the ,-enones. Solvatochromic shifts in aqueous solution have been investigated using a combined discrete/continuum approach based on the so called polarizable continuum model. The experimental trends are well reproduced by this approach and a closer degeneracy in the triplet manifold has been detected in solution with respect to gas phase. ©2003 American Institute of Physics.},
  author       = {Aquilante, Francesco and Barone, V and Roos, Björn},
  issn         = {0021-9606},
  language     = {eng},
  number       = {23},
  pages        = {12323--12334},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {A theoretical investigation of valence and Rydberg electronic states of acrolein},
  url          = {http://dx.doi.org/},
  volume       = {119},
  year         = {2003},
}