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Theoretical study of the lowest B-1(U) states of trans-stilbene

Gagliardi, L; Orlandi, G; Molina, Vicent LU ; Malmqvist, Per-Åke LU and Roos, Björn LU (2002) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 106(32). p.7355-7361
Abstract
The results of a theoretical study of the ground state, 1(1)A(g), and of the lowest B-1(u) states of trans-stilbene are presented. The vertical and adiabatic excitation energies of the lowest B-1(u) states have been computed using multiconfigurational SCF theory, followed by second-order perturbation. theory. It is shown that the two lowest excited states are separated by a small energy gap in the Franck-Condon region. They are the 1(1)B(u), characterized by the HOMO-->LUMO single excitation substantially localized on the ethylenic moiety, and the 2(1)B(u), formed by a combination,of one electron excitations localized mainly on the benzene rings. The most intense transition is found to be the lowest in energy when the interaction... (More)
The results of a theoretical study of the ground state, 1(1)A(g), and of the lowest B-1(u) states of trans-stilbene are presented. The vertical and adiabatic excitation energies of the lowest B-1(u) states have been computed using multiconfigurational SCF theory, followed by second-order perturbation. theory. It is shown that the two lowest excited states are separated by a small energy gap in the Franck-Condon region. They are the 1(1)B(u), characterized by the HOMO-->LUMO single excitation substantially localized on the ethylenic moiety, and the 2(1)B(u), formed by a combination,of one electron excitations localized mainly on the benzene rings. The most intense transition is found to be the lowest in energy when the interaction between different states is included at the level of second-order perturbation theory. The vibronic structure of emission and absorption spectra of the two lowest B-1(u) states have been determined within the Franck-Condon approximation. The spectrum calculated for the 1(1)B(u) state agrees with the experimental spectrum, while the low intensity band computed for the 2(1)B(u) state has no experimental counterpart. It is concluded that this band is buried in the strong 1(1)B(u) absorption and therefore not observed. (Less)
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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
volume
106
issue
32
pages
7355 - 7361
publisher
The American Chemical Society
external identifiers
  • wos:000177353700014
  • scopus:0037104731
ISSN
1520-5215
DOI
10.1021/jp0256138
language
English
LU publication?
yes
id
1aea4e3a-e02a-4d3d-b2e9-3d442c89b61d (old id 331641)
date added to LUP
2007-08-20 13:17:40
date last changed
2017-11-05 04:26:51
@article{1aea4e3a-e02a-4d3d-b2e9-3d442c89b61d,
  abstract     = {The results of a theoretical study of the ground state, 1(1)A(g), and of the lowest B-1(u) states of trans-stilbene are presented. The vertical and adiabatic excitation energies of the lowest B-1(u) states have been computed using multiconfigurational SCF theory, followed by second-order perturbation. theory. It is shown that the two lowest excited states are separated by a small energy gap in the Franck-Condon region. They are the 1(1)B(u), characterized by the HOMO-->LUMO single excitation substantially localized on the ethylenic moiety, and the 2(1)B(u), formed by a combination,of one electron excitations localized mainly on the benzene rings. The most intense transition is found to be the lowest in energy when the interaction between different states is included at the level of second-order perturbation theory. The vibronic structure of emission and absorption spectra of the two lowest B-1(u) states have been determined within the Franck-Condon approximation. The spectrum calculated for the 1(1)B(u) state agrees with the experimental spectrum, while the low intensity band computed for the 2(1)B(u) state has no experimental counterpart. It is concluded that this band is buried in the strong 1(1)B(u) absorption and therefore not observed.},
  author       = {Gagliardi, L and Orlandi, G and Molina, Vicent and Malmqvist, Per-Åke and Roos, Björn},
  issn         = {1520-5215},
  language     = {eng},
  number       = {32},
  pages        = {7355--7361},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory},
  title        = {Theoretical study of the lowest B-1(U) states of trans-stilbene},
  url          = {http://dx.doi.org/10.1021/jp0256138},
  volume       = {106},
  year         = {2002},
}