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 ∼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. © 2009 Elsevier B.V. All rights reserved.
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|Titolo:||A CASSCF/CASPT2 approach to the decomposition of thiazole-substituted dioxetanone: Substitution effects and charge-transfer induced electron excitation|
|Rivista:||CHEMICAL PHYSICS LETTERS|
|Citazione:||Liu, F., Liu, Y., DE VICO, L., & Lindh, R. (2009). A CASSCF/CASPT2 approach to the decomposition of thiazole-substituted dioxetanone: Substitution effects and charge-transfer induced electron excitation. CHEMICAL PHYSICS LETTERS, 484(1-3), 69-75.|
|Appare nelle tipologie:||1.1 Articolo in rivista|
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