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.
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 [10.1016/j.cplett.2009.11.009].
A CASSCF/CASPT2 approach to the decomposition of thiazole-substituted dioxetanone: Substitution effects and charge-transfer induced electron excitation
De Vico, Luca;
2009-01-01
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 ∼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.File | Dimensione | Formato | |
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https://hdl.handle.net/11365/1006576
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