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

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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.


  • Fengyi Liu
  • Yajun Liu
  • Luca De Vico
  • Roland Lindh
Research areas and keywords

Subject classification (UKÄ) – MANDATORY

  • Theoretical Chemistry
Original languageEnglish
Pages (from-to)69-75
JournalChemical Physics Letters
Issue number1-3
Publication statusPublished - 2009
Publication categoryResearch

Bibliographic note

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)