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A CASPT2 study of the valence and lowest Rydberg electronic states of benzene and phenol.

Lorentzon, Johan LU ; Malmqvist, Per-Åke LU ; Fülscher, Markus LU and Roos, Björn O. LU (1995) In Theoretica Chimica Acta 91. p.91-108
Abstract
The valence excited states and the 3s, 3p, and 3d
(united atom) Rydberg states of benzene and phenol have been obtained by
the CASPT2 method, which computes a second-order perturbation
correction to complete active space self-consistent field (CASSCF)
energies. All non-zero dipole oscillator strengths are also computed, at
the CASSCF level. For benzene, 16 singlet and 16 triplet states with
excitation energies up to ca. 7.86 eV (63 400 cm–1) are
obtained. Of these, 12 singlet and three triplet energies are
experimentally known well enough to allow meaningful comparison. The
average error is around 0.1 eV. The highest of these singlet states (21... (More)
The valence excited states and the 3s, 3p, and 3d
(united atom) Rydberg states of benzene and phenol have been obtained by
the CASPT2 method, which computes a second-order perturbation
correction to complete active space self-consistent field (CASSCF)
energies. All non-zero dipole oscillator strengths are also computed, at
the CASSCF level. For benzene, 16 singlet and 16 triplet states with
excitation energies up to ca. 7.86 eV (63 400 cm–1) are
obtained. Of these, 12 singlet and three triplet energies are
experimentally known well enough to allow meaningful comparison. The
average error is around 0.1 eV. The highest of these singlet states (21 E2g)
is the highest valence ππ* state predicted by elementary π-electron
theory. Its energy is then considerably lower than has been suggested
from laser flash experiments, but in perfect agreement with a
reinterpretation of that experiment. For phenol, 27 singlet states are
obtained, in the range 4.53–7.84 eV (63 300 cm−1). Only the
lowest has a well-known experimental energy, which agrees with the
computed result within 0.03 eV. The ionization energy is in error by
0.05 eV. (Less)
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author
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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Theoretica Chimica Acta
volume
91
pages
18 pages
publisher
Springer
external identifiers
  • scopus:0003067046
ISSN
0040-5744
DOI
10.1007/BF01113865
language
English
LU publication?
yes
id
86f02167-7293-4289-b7d0-c191f7b607a5
date added to LUP
2022-05-26 12:36:18
date last changed
2023-04-05 16:43:39
@article{86f02167-7293-4289-b7d0-c191f7b607a5,
  abstract     = {{The valence excited states and the 3<i>s</i>, 3<i>p</i>, and 3<i>d</i> <br>
(united atom) Rydberg states of benzene and phenol have been obtained by<br>
 the CASPT2 method, which computes a second-order perturbation <br>
correction to complete active space self-consistent field (CASSCF) <br>
energies. All non-zero dipole oscillator strengths are also computed, at<br>
 the CASSCF level. For benzene, 16 singlet and 16 triplet states with <br>
excitation energies up to ca. 7.86 eV (63 400 cm<sup>–1</sup>) are <br>
obtained. Of these, 12 singlet and three triplet energies are <br>
experimentally known well enough to allow meaningful comparison. The <br>
average error is around 0.1 eV. The highest of these singlet states (2<sup>1</sup> E<sub>2g</sub>)<br>
 is the highest valence ππ* state predicted by elementary π-electron <br>
theory. Its energy is then considerably lower than has been suggested <br>
from laser flash experiments, but in perfect agreement with a <br>
reinterpretation of that experiment. For phenol, 27 singlet states are <br>
obtained, in the range 4.53–7.84 eV (63 300 cm<sup>−1</sup>). Only the <br>
lowest has a well-known experimental energy, which agrees with the <br>
computed result within 0.03 eV. The ionization energy is in error by <br>
0.05 eV.}},
  author       = {{Lorentzon, Johan and Malmqvist, Per-Åke and Fülscher, Markus and Roos, Björn O.}},
  issn         = {{0040-5744}},
  language     = {{eng}},
  pages        = {{91--108}},
  publisher    = {{Springer}},
  series       = {{Theoretica Chimica Acta}},
  title        = {{A CASPT2 study of the valence and lowest Rydberg electronic states of benzene and phenol.}},
  url          = {{http://dx.doi.org/10.1007/BF01113865}},
  doi          = {{10.1007/BF01113865}},
  volume       = {{91}},
  year         = {{1995}},
}