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Issue 20, 2009
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Thymine relaxation after UV irradiation: the role of tautomerization and πσ* states

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Abstract

Ab initio calculations and femtosecond pump–probe ionization experiments were carried out to identify excited state relaxation processes in isolated thymine monomer and small thyminewater clusters. Three transient species with life times of ≤100 fs, 7 ps and >1 ns were observed in the experiments on gas phase thymine. The longer-lived transients were weak or absent in thyminewater clusters. Available theoretical results on thymine agree with the assignment of low-lying ππ* and nπ* excited states to the femtosecond and picosecond transients but the assignment of the third transient remains opaque. Our theoretical results seem to exclude the possibility of ground or excited state tautomerization as well as the involvement of states with πσ* character. Remaining explanations for the observed transients are: very fast intersystem crossing to the triplet manifold or the observation of transient signals from local minima on the potential energy surfaces.

Graphical abstract: Thymine relaxation after UV irradiation: the role of tautomerization and πσ* states

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Article information


Submitted
08 Sep 2008
Accepted
10 Feb 2009
First published
13 Mar 2009

Phys. Chem. Chem. Phys., 2009,11, 3927-3934
Article type
Paper

Thymine relaxation after UV irradiation: the role of tautomerization and πσ* states

J. González-Vázquez, L. González, E. Samoylova and T. Schultz, Phys. Chem. Chem. Phys., 2009, 11, 3927
DOI: 10.1039/B815602F

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