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Unimolecular Decomposition Mechanism of 1,2-Dioxetanedione: Concerted or Biradical? That is the Question!
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0002-8453-5664
2017 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 121, p. 1189-1194Article in journal (Refereed) Published
Abstract [en]

Determination of the ground- and excited-stateunimolecular decomposition mechanisms of 1,2-dioxetanedionegives a level of insight into bimolecular decomposition reactionsof this kind for which some experimental results are reported.Although a few studies have put some effort to describe abiradical mechanism of this decomposition, there is still no systematic study that proves an existence of a biradical character.In the present study, state-of-the-art high-level multistatemulticonfigurational reference second-order perturbation theorycalculations are performed to describe the reaction mechanismof 1,2-dioxetanedione in detail. The calculations indicate that thedecomposition of this four-membered ring peroxide containingtwo carbonyl carbon atoms occurs in concerted but notsimultaneous fashion, so-called “merged”, contrary to the caseof unimolecular 1,2-dioxetane and 1,2-dioxetanone decompositions where biradical reaction pathways have been calculated. Atthe TS of the ground-state surface, the system enters an entropic trapping region, where four singlet and four triplet manifoldsare degenerated, which can lead to the formation of triplet and singlet excited biradical species. However, these excited specieshave to overcome a second activation barrier for C−C bond cleavage for excited product formation, whereas the ground-stateenergy surface possesses only one TS. Thus our calculations indicate that the unimolecular decomposition of 1,2-dioxetanedioneshould not lead to efficient excited-state formation, in agreement with the lack of direct emission from the peroxyoxalate reaction.

Place, publisher, year, edition, pages
2017. Vol. 121, p. 1189-1194
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Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-215156DOI: 10.1021/acs.jpca.6b10365ISI: 000394482500004Scopus ID: 2-s2.0-85027058047OAI: oai:DiVA.org:kth-215156DiVA, id: diva2:1146680
Note

QC 20171004

Available from: 2017-10-03 Created: 2017-10-03 Last updated: 2017-10-04Bibliographically approved

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Farahani, Pooria

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