A CASSCF/CASPT2 approach to the decomposition of thiazole-substituted dioxetanone: Substitution effects and charge-transfer induced electron excitation
(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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https://lup.lub.lu.se/record/1517769
- author
- Liu, Fengyi LU ; Liu, Yajun ; De Vico, Luca and Lindh, Roland LU
- organization
- publishing date
- 2009
- 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
- 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
- c17d4c5a-a18f-4349-a568-bb9f3eae5627 (old id 1517769)
- date added to LUP
- 2016-04-01 13:36:05
- date last changed
- 2023-01-03 23:40:39
@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}},
doi = {{10.1016/j.cplett.2009.11.009}},
volume = {{484}},
year = {{2009}},
}