A CASSCF/CASPT2 approach to the decomposition of thiazole-substituted dioxetanone: Substitution effects and charge-transfer induced electron excitation
2009 (English)In: Chemical Physics Letters, ISSN 0009-2614, E-ISSN 1873-4448, Vol. 484, no 1-3, 69-75 p.Article in journal (Refereed) Published
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.
Place, publisher, year, edition, pages
2009. Vol. 484, no 1-3, 69-75 p.
IdentifiersURN: urn:nbn:se:uu:diva-143867DOI: 10.1016/j.cplett.2009.11.009OAI: oai:DiVA.org:uu-143867DiVA: diva2:392346