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Photoinduced Formation Mechanism of the Thymine-Thymine (6-4) Adduct
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.
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2013 (English)In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 117, no 7, 1999-2004 p.Article in journal (Refereed) Published
Abstract [en]

The photoinduced mechanism leading to the formation of the thymine-thymine (6-4) photolesion has been studied by using the CASPT2//CASSCF approach over a dinucleotide model in vacuo. Following light absorption, localization of the excitation on a single thymine leads to fast singlet-triplet crossing that populates the triplet 3(n pi*) state of thymine. This state, displaying an elongated C-4=O bond, triggers (6-4) dimer formation by reaction with the C-5=C-6 double bond of the adjacent thymine, followed by a second intersystem crossing, which acts as a gate between the excited state of the reactant and the ground state of the photoproduct. The requirement of localized excitation on just one thymine, whose main decay channel (by radiationless repopulation of its ground state) is nonphotochemical, can rationalize the experimentally observed low quantum yield of formation for the thymine-thymine (6-4) adduct.

Place, publisher, year, edition, pages
2013. Vol. 117, no 7, 1999-2004 p.
National Category
Natural Sciences
URN: urn:nbn:se:uu:diva-197655DOI: 10.1021/jp307200gISI: 000315432200002OAI: oai:DiVA.org:uu-197655DiVA: diva2:613905
Available from: 2013-04-02 Created: 2013-04-02 Last updated: 2013-04-02Bibliographically approved

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