Issue 13, 2011
From the journal:

Physical Chemistry Chemical Physics

Photodynamical simulations of cytosine: characterization of the ultrafast bi-exponential UV deactivation†

Mario Barbatti,*ab   Adélia J. A. Aquino,ac   Jaroslaw J. Szymczak,‡a   Dana Nachtigallovád  and  Hans Lischka*a  

* Corresponding authors

a Institute for Theoretical Chemistry, University of Vienna, Waehringerstrasse 17, A 1090 Vienna, Austria
E-mail: Mario Barbatti-barbatti@kofo.mpg.de, Hans Lischka-hans.lischka@univie.ac.at

b Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470 Mülheim an der Ruhr, Germany

c Institute of Soil Research, University of Natural Resources and Applied Life Sciences Vienna, Peter-Jordan-Straße 82, A-1190 Vienna, Austria

d Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nam. 2, CZ-16610 Prague 6, Czech Republic

Abstract

Deactivation of UV-excited cytosine is investigated by non-adiabatic dynamics simulations, optimization of conical intersections, and determination of reaction paths. Quantum chemical calculations are performed up to the MR-CISD level. Dynamics simulations were performed at multiconfigurational level with the surface hopping method including four electronic states. The results show the activation of four distinct reaction pathways at two different subpicosecond time scales and involving three different conical intersections. Most trajectories relax to a minimum of the S1 state and deactivate with a time constant of 0.69 ps mainly through a semi-planar conical intersection along the nOπ* surface. A minor fraction deactivate along ππ* regions of the S1 surface. Sixteen percent of trajectories do not relax to the minimum and deactivate with a time constant of only 13 fs.

Graphical abstract: Photodynamical simulations of cytosine: characterization of the ultrafast bi-exponential UV deactivation

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Article information

DOI
https://doi.org/10.1039/C0CP01327G
Article type
Paper
Submitted
27 Jul 2010
Accepted
27 Jan 2011
First published
24 Feb 2011

Phys. Chem. Chem. Phys., 2011,13, 6145-6155

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Photodynamical simulations of cytosine: characterization of the ultrafast bi-exponential UV deactivation

M. Barbatti, A. J. A. Aquino, J. J. Szymczak, D. Nachtigallová and H. Lischka, Phys. Chem. Chem. Phys., 2011, 13, 6145 DOI: 10.1039/C0CP01327G

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