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

作者：Liu Fengyi^*; Liu Yajun; De Vico Luca; Lindh Roland

来源：Chemical Physics Letters, 2009, 484(1-3): 69-75.

DOI：10.1016/j.cplett.2009.11.009

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.

• 出版日期2009-12-8
• 单位北京师范大学