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A CASSCF/CASPT2 approach to the decomposition of thiazole-substituted dioxetanone: Substitution effects and charge-transfer induced electron excitation

Liu, Fengyi LU ; Liu, Yajun; De Vico, Luca and Lindh, Roland LU (2009) In Chemical Physics Letters 484(1-3). p.69-75
Abstract
The gas-phase decompositions of a thiazole-substituted dioxetanone, in both the natural and anionic forms, were investigated theoretically in a CASSCF/CASPT2 study. The neutral conjugated thiazole (with or without a hydroxyl group) substitution on the dioxetanone has no evident effect on the dissociation; however, a subsequent deprotonation - invoking charge-transfer excitations from the thiazole to the dioxetanone moiety - will dramatically change the reaction mechanism from stepwise to concerted, and reduce the activation barrier by similar to 8 kcal mol(-1). These findings are helpful for the better understanding of dioxetanone chemiluminescence and the charge-transfer induced electron excitation in chemi- and bioluminescence processes.... (More)
The gas-phase decompositions of a thiazole-substituted dioxetanone, in both the natural and anionic forms, were investigated theoretically in a CASSCF/CASPT2 study. The neutral conjugated thiazole (with or without a hydroxyl group) substitution on the dioxetanone has no evident effect on the dissociation; however, a subsequent deprotonation - invoking charge-transfer excitations from the thiazole to the dioxetanone moiety - will dramatically change the reaction mechanism from stepwise to concerted, and reduce the activation barrier by similar to 8 kcal mol(-1). These findings are helpful for the better understanding of dioxetanone chemiluminescence and the charge-transfer induced electron excitation in chemi- and bioluminescence processes. (C) 2009 Elsevier B.V. All rights reserved. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Chemical Physics Letters
volume
484
issue
1-3
pages
69 - 75
publisher
Elsevier
external identifiers
  • wos:000272179300015
  • scopus:71549157460
ISSN
0009-2614
DOI
10.1016/j.cplett.2009.11.009
language
English
LU publication?
yes
id
c17d4c5a-a18f-4349-a568-bb9f3eae5627 (old id 1517769)
date added to LUP
2010-01-08 11:06:44
date last changed
2017-08-27 04:39:57
@article{c17d4c5a-a18f-4349-a568-bb9f3eae5627,
  abstract     = {The gas-phase decompositions of a thiazole-substituted dioxetanone, in both the natural and anionic forms, were investigated theoretically in a CASSCF/CASPT2 study. The neutral conjugated thiazole (with or without a hydroxyl group) substitution on the dioxetanone has no evident effect on the dissociation; however, a subsequent deprotonation - invoking charge-transfer excitations from the thiazole to the dioxetanone moiety - will dramatically change the reaction mechanism from stepwise to concerted, and reduce the activation barrier by similar to 8 kcal mol(-1). These findings are helpful for the better understanding of dioxetanone chemiluminescence and the charge-transfer induced electron excitation in chemi- and bioluminescence processes. (C) 2009 Elsevier B.V. All rights reserved.},
  author       = {Liu, Fengyi and Liu, Yajun and De Vico, Luca and Lindh, Roland},
  issn         = {0009-2614},
  language     = {eng},
  number       = {1-3},
  pages        = {69--75},
  publisher    = {Elsevier},
  series       = {Chemical Physics Letters},
  title        = {A CASSCF/CASPT2 approach to the decomposition of thiazole-substituted dioxetanone: Substitution effects and charge-transfer induced electron excitation},
  url          = {http://dx.doi.org/10.1016/j.cplett.2009.11.009},
  volume       = {484},
  year         = {2009},
}