Theoretical study of the chemiluminescent decomposition of dioxetanone.
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/1392218
- author
- Liu, Fengyi LU ; Liu, Yajun ; De Vico, Luca LU and Lindh, Roland LU
- organization
- publishing date
- 2009
- 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
- 2023-02-13 21:13:27
@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}},
}