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Chemiexcitation without the Peroxide Bond?: Replacing oxygen with other heteroatoms
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.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.ORCID iD: 0000-0001-9418-6579
2019 (English)In: ChemPhotoChem, ISSN 2367-0932, Vol. 3, no 9, p. 957-967Article in journal (Refereed) Published
Abstract [en]

Chemiexcitation is the population of electronic excited states from the electronic ground state via radiationless non-adiabatic transitions upon thermal activation. The subsequent emission of the excess of energy in the form of light is called chemiluminescence or bioluminescence when occurring in living organisms. Key intermediates in these reactions have been shown to contain a high-energy (often cyclic) peroxide which decomposes. The simplest molecules, 1,2-dioxetane and 1,2-dioxetanone, have thus been used extensively both theoretically and experimentally as model systems to understand the underlying mechanisms of chemiexcitation. An outstanding question remains whether the peroxide bond is a necessity and whether equivalent processes could happen in other simple molecules not containing an OO bond. In the present work, the decomposition reactions of four analogs of 1,2-dioxetane not containing a peroxide bond, the 1,2-oxazetidine anion, the 1,2-diazetidine anion, (neutral) 1,2-oxazetidine and 1,2-dithietane, have been studied theoretically using ab initio multicongurational methods. In particular, the reaction energy barriers and spin-orbit coupling strengths were calculated; the electronic degeneracy was studied and compared to the case of 1,2-dioxetane to assess the potentiality of chemiexcitation in the analog molecules.

Place, publisher, year, edition, pages
2019. Vol. 3, no 9, p. 957-967
Keywords [en]
chemiexcitation, chemiluminescence, 1.2-dioxetane, ab initio calculations, computational photochemistry
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-372040DOI: 10.1002/cptc.201800232ISI: 000487014600032OAI: oai:DiVA.org:uu-372040DiVA, id: diva2:1275206
Funder
Swedish Research Council, 2016-03398Swedish National Infrastructure for Computing (SNIC)Available from: 2019-01-04 Created: 2019-01-04 Last updated: 2019-10-31Bibliographically approved

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Fernández Galván, IgnacioVacher, Morgane

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