Change search
ReferencesLink to record
Permanent link

Direct link
Theoretical study of the dark photochemistry of 1,3-butadiene via the chemiexcitation of Dewar dioxetane
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry. Univ Valencia, Inst Ciencia Mol, ES-46071 Valencia, Spain.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.ORCID iD: 0000-0002-1312-1202
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.
Univ Valencia, Inst Ciencia Mol, ES-46071 Valencia, Spain.
2015 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 17, no 28, 18653-18664 p.Article in journal (Refereed) Published
Abstract [en]

Excited-state chemistry is usually ascribed to photo-induced processes, such as fluorescence, phosphorescence, and photochemistry, or to bio-and chemiluminescence, in which light emission originates from a chemical reaction. A third class of excited-state chemistry is, however, possible. It corresponds to the photochemical phenomena produced by chemienergizing certain chemical groups without light - chemiexcitation. By studying Dewar dioxetane, which can be viewed as the combination of 1,2-dioxetane and 1,3-butadiene, we show here how the photo-isomerization channel of 1,3-butadiene can be reached at a later stage after the thermal decomposition of the dioxetane moiety. Multi-reference multiconfigurational quantum chemistry methods and accurate reaction-path computational strategies were used to determine the reaction coordinate of three successive processes: decomposition of the dioxetane moiety, non-adiabatic energy transfer from the ground to the excited state, and finally non-radiative decay of the 1,3-butadiene group. With the present study, we open a new area of research within computational photochemistry to study chemically-induced excited-state chemistry that is difficult to tackle experimentally due to the short-lived character of the species involved in the process. The findings shall be of relevance to unveil "dark'' photochemistry mechanisms, which might operate in biological systems under conditions of lack of light. These mechanisms might allow reactions that are typical of photo-induced phenomena.

Place, publisher, year, edition, pages
2015. Vol. 17, no 28, 18653-18664 p.
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-260743DOI: 10.1039/c5cp02269jISI: 000357808500049PubMedID: 26119390OAI: oai:DiVA.org:uu-260743DiVA: diva2:848320
Funder
Swedish Research CouncileSSENCE - An eScience CollaborationSwedish National Infrastructure for Computing (SNIC), SNIC-2013-1-51 SNIC-2013-1-267 SNIC 2013/1-138
Available from: 2015-08-24 Created: 2015-08-24 Last updated: 2016-10-27Bibliographically approved

Open Access in DiVA

fulltext(25808 kB)18 downloads
File information
File name FULLTEXT01.pdfFile size 25808 kBChecksum SHA-512
f24909f4bd6e06bf4cd683cf52c3991307dd9b940d82e3076d685070c411876d03db28307aac1650cee1ff66dc0ea0289bf4ab922126e3039e0e515459ab02bf
Type fulltextMimetype application/pdf

Other links

Publisher's full textPubMed

Search in DiVA

By author/editor
Farahani, PooriaLundberg, MarcusLindh, Roland
By organisation
Theoretical Chemistry
In the same journal
Physical Chemistry, Chemical Physics - PCCP
Theoretical Chemistry

Search outside of DiVA

GoogleGoogle Scholar
Total: 18 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 464 hits
ReferencesLink to record
Permanent link

Direct link