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Theoretical study of the chemiluminescent decomposition of dioxetanone.

Liu, Fengyi LU ; Liu, Yajun ; De Vico, Luca LU and Lindh, Roland LU (2009) In Journal of the American Chemical Society 131(17). p.6181-6188
Abstract
The unimolecular chemiluminescent decomposition of unsubstituted dioxetanone was studied at the complete active space self-consistent field level of theory combined with the multistate second-order multiconfigurational perturbation theory energy correction. The calculations revealed interesting features. Two transition states, two conical intersections, and one intermediate stable biradical structure along the lowest energy reaction path were identified. It was noted that the conical intersections are found at or in very close proximity to the transition states. The first and second transition states correspond to O-O and C-C cleavages, respectively. In particular, a planar structure is supported by the (1)(sigma,sigma*) state during the... (More)
The unimolecular chemiluminescent decomposition of unsubstituted dioxetanone was studied at the complete active space self-consistent field level of theory combined with the multistate second-order multiconfigurational perturbation theory energy correction. The calculations revealed interesting features. Two transition states, two conical intersections, and one intermediate stable biradical structure along the lowest energy reaction path were identified. It was noted that the conical intersections are found at or in very close proximity to the transition states. The first and second transition states correspond to O-O and C-C cleavages, respectively. In particular, a planar structure is supported by the (1)(sigma,sigma*) state during the O-O dissociation up to the first transition state and conical intersection. At this point the (1)(sigma,sigma*) state dissociation path bifurcates, corresponding to a torsion of the O-C-C-O angle. Simultaneously, the (1)(n,sigma*) state becomes lower in energy while still favoring a planar structure. As the lowest-energy reaction path proceeds toward the second transition state and conical intersection, the (1)(n,sigma*), (3)(n,sigma*), and (1)(sigma,sigma*) states are close in energy. This work suggests that the vibrational distribution at the first conical intersection and the interactions among the states as the reaction proceeds between the two transition states are the origin of the population of the chemiluminescent (n,sigma*) states. (Less)
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author
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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of the American Chemical Society
volume
131
issue
17
pages
6181 - 6188
publisher
The American Chemical Society (ACS)
external identifiers
  • wos:000265755800043
  • pmid:19358608
  • scopus:70249103205
  • pmid:19358608
ISSN
1520-5126
DOI
10.1021/ja808511t
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
3bf1ebd9-4380-4a9e-b42e-eeb65c0dd743 (old id 1392218)
date added to LUP
2016-04-01 14:09:47
date last changed
2021-10-10 04:35:57
@article{3bf1ebd9-4380-4a9e-b42e-eeb65c0dd743,
  abstract     = {The unimolecular chemiluminescent decomposition of unsubstituted dioxetanone was studied at the complete active space self-consistent field level of theory combined with the multistate second-order multiconfigurational perturbation theory energy correction. The calculations revealed interesting features. Two transition states, two conical intersections, and one intermediate stable biradical structure along the lowest energy reaction path were identified. It was noted that the conical intersections are found at or in very close proximity to the transition states. The first and second transition states correspond to O-O and C-C cleavages, respectively. In particular, a planar structure is supported by the (1)(sigma,sigma*) state during the O-O dissociation up to the first transition state and conical intersection. At this point the (1)(sigma,sigma*) state dissociation path bifurcates, corresponding to a torsion of the O-C-C-O angle. Simultaneously, the (1)(n,sigma*) state becomes lower in energy while still favoring a planar structure. As the lowest-energy reaction path proceeds toward the second transition state and conical intersection, the (1)(n,sigma*), (3)(n,sigma*), and (1)(sigma,sigma*) states are close in energy. This work suggests that the vibrational distribution at the first conical intersection and the interactions among the states as the reaction proceeds between the two transition states are the origin of the population of the chemiluminescent (n,sigma*) states.},
  author       = {Liu, Fengyi and Liu, Yajun and De Vico, Luca and Lindh, Roland},
  issn         = {1520-5126},
  language     = {eng},
  number       = {17},
  pages        = {6181--6188},
  publisher    = {The American Chemical Society (ACS)},
  series       = {Journal of the American Chemical Society},
  title        = {Theoretical study of the chemiluminescent decomposition of dioxetanone.},
  url          = {http://dx.doi.org/10.1021/ja808511t},
  doi          = {10.1021/ja808511t},
  volume       = {131},
  year         = {2009},
}