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Multiple Decay Mechanisms and 2D-UV Spectroscopic Fingerprints of Singlet Excited Solvated Adenine-Uracil Monophosphate

The decay channels of singlet excited adenine uracil monophosphate (ApU) in water are studied with CASPT2//CASSCF:MM potential energy calculations and simulation of the 2D-UV spectroscopic fingerprints with the aim of elucidating the role of the different electronic states of the stacked conformer in the excited state dynamics. The adenine 1La state can decay without a barrier to a conical intersection with the ground state. In contrast, the adenine 1Lb and uracil S(U) states have minima that are separated from the intersections by sizeable barriers. Depending on the backbone conformation, the CT state can undergo inter-base hydrogen transfer and decay to the ground state through a conical intersection, or it can yield a long-lived minimum stabilized by a hydrogen bond between the two ribose rings. This suggests that the 1Lb, S(U) and CT states of the stacked conformer may all contribute to the experimental lifetimes of 18 and 240ps. We have also simulated the time evolution of the 2D-UV spectra and provide the specific fingerprint of each species in a recommended probe window between 25000 and 38000cm-1 in which decongested, clearly distinguishable spectra can be obtained. This is expected to allow the mechanistic scenarios to be discerned in the near future with the help of the corresponding experiments. Our results reveal the complexity of the photophysics of the relatively small ApU system, and the potential of 2D-UV spectroscopy to disentangle the photophysics of multichromophoric systems

We acknowledge the participation of the late Luis Serrano- Andrés in the first stage of this work. L.B. and A.V. acknowledge financial support from the Spanish Ministry of Economy (CTQ2011-26573, CTQ2015-69363-P) and the Generalitat de Catalunya (2014SGR-1202) and the use of computer time at the Consorci de Serveis Universitaris de Catalunya. Q.L. acknowledges the National Natural Science Foundation of China (21303007). M.G. acknowledges support by the European Research Council Advanced Grant STRATUS (ERC-2011-AdG No.291198) and the Agence Nationale de la Recherche for the 2015 project FEMTO-2DNA (Spectroscopie 2DUV: un nouvel outil pour l’étude de biomolécules, ANR-15-CE29-0010). D.R.-S. acknowledges support from the Generalitat Valenciana (GV2015-057) and the Spanish Ministry of Economy (project CTQ2014-58624-P and grant JCI-2012-13431). S.M gratefully acknowledges the support of the Chemical Sciences, Geosciences, and Biosciences division, office of Basic Energy Sciences, U.S. Department of Energy, and the National Science Foundation (grant CHE-1361516)

© Chemistry - A European Journal, 2016, vol. 22, núm. 2, p. 7497-7507

Wiley

Autor: Li, Quansong
Giussani, Angelo
Segarra-Martí, Javier
Nenov, Artur
Rivalta, Ivan
Voityuk, Alexander A.
Mukamel, Shaul
Roca-Sanjuán, Daniel
Garavelli, Marco
Blancafort San José, Lluís
Data: 23 maig 2016
Resum: The decay channels of singlet excited adenine uracil monophosphate (ApU) in water are studied with CASPT2//CASSCF:MM potential energy calculations and simulation of the 2D-UV spectroscopic fingerprints with the aim of elucidating the role of the different electronic states of the stacked conformer in the excited state dynamics. The adenine 1La state can decay without a barrier to a conical intersection with the ground state. In contrast, the adenine 1Lb and uracil S(U) states have minima that are separated from the intersections by sizeable barriers. Depending on the backbone conformation, the CT state can undergo inter-base hydrogen transfer and decay to the ground state through a conical intersection, or it can yield a long-lived minimum stabilized by a hydrogen bond between the two ribose rings. This suggests that the 1Lb, S(U) and CT states of the stacked conformer may all contribute to the experimental lifetimes of 18 and 240ps. We have also simulated the time evolution of the 2D-UV spectra and provide the specific fingerprint of each species in a recommended probe window between 25000 and 38000cm-1 in which decongested, clearly distinguishable spectra can be obtained. This is expected to allow the mechanistic scenarios to be discerned in the near future with the help of the corresponding experiments. Our results reveal the complexity of the photophysics of the relatively small ApU system, and the potential of 2D-UV spectroscopy to disentangle the photophysics of multichromophoric systems
We acknowledge the participation of the late Luis Serrano- Andrés in the first stage of this work. L.B. and A.V. acknowledge financial support from the Spanish Ministry of Economy (CTQ2011-26573, CTQ2015-69363-P) and the Generalitat de Catalunya (2014SGR-1202) and the use of computer time at the Consorci de Serveis Universitaris de Catalunya. Q.L. acknowledges the National Natural Science Foundation of China (21303007). M.G. acknowledges support by the European Research Council Advanced Grant STRATUS (ERC-2011-AdG No.291198) and the Agence Nationale de la Recherche for the 2015 project FEMTO-2DNA (Spectroscopie 2DUV: un nouvel outil pour l’étude de biomolécules, ANR-15-CE29-0010). D.R.-S. acknowledges support from the Generalitat Valenciana (GV2015-057) and the Spanish Ministry of Economy (project CTQ2014-58624-P and grant JCI-2012-13431). S.M gratefully acknowledges the support of the Chemical Sciences, Geosciences, and Biosciences division, office of Basic Energy Sciences, U.S. Department of Energy, and the National Science Foundation (grant CHE-1361516)
Format: application/pdf
ISSN: 0947-6539 (versió paper)
1521-3765 (versió electrònica)
Accés al document: http://hdl.handle.net/10256/13185
Llenguatge: eng
Editor: Wiley
Col·lecció: MICINN/PN 2012-2014/CTQ2011-26573
MINECO/PE 2015-2017/CTQ2015-69363-P
AGAUR/2014-2017/2014SGR1202
Reproducció digital del document publicat a: http://dx.doi.org/10.1002/chem.201505086
Articles publicats (D-Q)
És part de: © Chemistry - A European Journal, 2016, vol. 22, núm. 2, p. 7497-7507
Drets: Attribution-NonCommercial-NoDerivs 3.0 Spain
URI Drets: http://creativecommons.org/licenses/by-nc-nd/3.0/es/
Matèria: Química quàntica
Quantum chemistry
Electrònica molecular
Molecular electronics
Espectroscòpia molecular
Molecular spectroscopy
Espectrofotometria
Spectrophotometry
Títol: Multiple Decay Mechanisms and 2D-UV Spectroscopic Fingerprints of Singlet Excited Solvated Adenine-Uracil Monophosphate
Tipus: info:eu-repo/semantics/article
Repositori: DUGiDocs

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