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Triplet versus singlet chemiexcitation mechanism in dioxetanone: a CASSCF/CASPT2 study
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry. Univ Valencia, Inst Ciencia Mol, POB 22085, Valencia 46071, Spain..ORCID iD: 0000-0001-8232-4989
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.ORCID iD: 0000-0002-0684-7689
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.ORCID iD: 0000-0001-7567-8295
Univ Valencia, Inst Ciencia Mol, POB 22085, Valencia 46071, Spain..
2017 (English)In: Theoretical Chemistry accounts, ISSN 1432-881X, E-ISSN 1432-2234, Vol. 136, no 6, 70Article in journal (Refereed) Published
Abstract [en]

Chemiluminescence is a fundamental process of chemistry consisting in the conversion of chemical energy stored in chemical bonds into light. It is used by nature and by man-made technology, being especially relevant in chemical analysis. The understanding of the phenomenon strongly relies in the study of peroxide models such as 1,2-dioxetanones. In the present contribution, the singlet S2 and the triplet T2 potential energy surfaces of the unimolecular decomposition of 1,2-dioxetanone have been mapped along the O-O and C-C bond coordinates on the grounds of the multiconfigurational CASPT2//CASSCF approach. Results confirm the energy degeneracy between T2, T1, S1, and S0 at the TS region, whereas S2 is unambiguously predicted at higher energies. Triplet-state population is also supported by the spin-orbit couplings between the singlet and triplet states partaking in the process. In particular, the first-principle calculations show that decomposition along the T2 state is a competitive process, having a small (similar to 3 kcal/mol) energy barrier from the ground-state TS structure. The present findings can explain the higher quantum yield of triplet-state population with respect to the excited singlet states recorded experimentally for the uni-molecular decomposition of 1,2-dioxetanone models.

Place, publisher, year, edition, pages
2017. Vol. 136, no 6, 70
Keyword [en]
Quantum chemistry, Excited states, CASSCF/CASPT2, Chemiluminescence, Dioxetanone decomposition, Triplet states
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-329733DOI: 10.1007/s00214-017-2095-xISI: 000404250000001OAI: oai:DiVA.org:uu-329733DiVA: diva2:1143164
Funder
Swedish Research Council, 2012-3910eSSENCE - An eScience Collaboration
Available from: 2017-09-20 Created: 2017-09-20 Last updated: 2017-12-28Bibliographically approved

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Francés-Monerris, AntonioFernández Galván, IgnacioLindh, Roland

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