Multiple Decay Mechanisms and 2D-UV Spectroscopic Fingerprints of Singlet Excited Solvated Adenine-Uracil Monophosphate
dc.contributor.author
dc.date.accessioned
2016-11-22T08:18:55Z
dc.date.available
2016-11-22T08:18:55Z
dc.date.issued
2016-05-23
dc.identifier.issn
0947-6539
dc.identifier.uri
dc.description.abstract
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
dc.description.sponsorship
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)
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Wiley
dc.relation
info:eu-repo/grantAgreement/MICINN//CTQ2011-26573/ES/MODELIZACION QUIMICO CUANTICA DE FOTOQUIMICA Y TRANSFERENCIA ELECTRONICA: SISTEMAS GRANDES, EFECTOS COLECTIVOS Y CONTROL OPTICO/
info:eu-repo/grantAgreement/MINECO//CTQ2015-69363-P/ES/OMPUTACION DEL ESTADO EXCITADO: DE ESPECTROS MOLECULARES A SISTEMAS MULTICROMOFORICOS/
AGAUR/2014-2017/2014SGR1202
dc.relation.isformatof
Reproducció digital del document publicat a: http://dx.doi.org/10.1002/chem.201505086
dc.relation.ispartof
© Chemistry - A European Journal, 2016, vol. 22, núm. 2, p. 7497-7507
dc.relation.ispartofseries
Articles publicats (D-Q)
dc.rights
Attribution-NonCommercial-NoDerivs 3.0 Spain
dc.rights.uri
dc.subject
dc.title
Multiple Decay Mechanisms and 2D-UV Spectroscopic Fingerprints of Singlet Excited Solvated Adenine-Uracil Monophosphate
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.embargo.terms
Cap
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.contributor.funder
dc.relation.ProjectAcronym
dc.identifier.eissn
1521-3765