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New Insights into the Photophysics of DNA Nucleobases

MPS-Authors

Prokhorenko,  V.
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

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Picchiotti,  A.
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
International Max Planck Research School for Ultrafast Imaging & Structural Dynamics (IMPRS-UFAST), Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

Dijkstra,  A.
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Department of Chemistry and Department of Physics, University of Toronto, 80 St. George Street, Toronto, Canada M5S 1H6;
The Hamburg Center for Ultrafast Imaging, Luruper Chaussee 149, 22761 Hamburg, Germany;

Miller,  R. J. D.
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

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Citation

Prokhorenko, V., Picchiotti, A., Pola, M., Dijkstra, A., & Miller, R. J. D. (2016). New Insights into the Photophysics of DNA Nucleobases. The Journal of Physical Chemistry Letters, 7(22), 4445-4450. doi:10.1021/acs.jpclett.6b02085.


Cite as: https://hdl.handle.net/21.11116/0000-0007-0FFF-B
Abstract
We report the results of an extended time-resolved study of DNA nucleobases in aqueous solutions conducted in the deep UV using broad-band femtosecond transient absorption and electronic two-dimensional spectroscopies. We found that the photodeactivation in all DNA nucleobases occurs in two steps: fast relaxation (500–700 fs) from the excited state ππ* to a “dark” state and its depopulation to the ground state within 1–2 ps. Our experimental observations and performed theoretical modeling allow us to conclude that this dark state can be associated with the nπ* electronic state, which is connected to the excited and ground states via conical intersections.