Resolving ultrafast photoinduced deactivations in water-solvated pyrimidine nucleosides
File(s)JPCL_Rev_14-03 .pdf (3.22 MB)
Accepted version
Author(s)
Pepino, Ana Julieta
Segarra-Marti, Javier
Nenov, Artur
Improta, Roberto
Garavelli, Marco
Type
Journal Article
Abstract
For the first time, ultrafast deactivations of photoexcited water-solvated pyrimidine nucleosides are mapped employing hybrid QM(CASPT2)/MM(AMBER) optimizations that account for explicit solvation, sugar effects, and dynamically correlated potential energy surfaces. Low-energy S1/S0 ring-puckering and ring-opening conical intersections (CIs) are suggested to drive the ballistic coherent subpicosecond (<200 fs) decays observed in each pyrimidine, the energetics controlling this processes correlating with the lifetimes observed. A second bright 1π2π* state, promoting excited-state population branching and leading toward a third CI with the ground state, is proposed to be involved in the slower ultrafast decay component observed in Thd/Cyd. The transient spectroscopic signals of the competitive deactivation channels are computed for the first time. A general unified scheme for ultrafast deactivations, spanning the sub- to few-picosecond time domain, is eventually delivered, with computed data that matches the experiments and elucidates the intrinsic photoprotection mechanism in solvated pyrimidine nucleosides.
Date Issued
2017-03-27
Date Acceptance
2017-03-27
Citation
Journal of Physical Chemistry Letters, 2017, 8 (8), pp.1777-1783
ISSN
1948-7185
Publisher
American Chemical Society
Start Page
1777
End Page
1783
Journal / Book Title
Journal of Physical Chemistry Letters
Volume
8
Issue
8
Copyright Statement
© 2017 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry Letters, after peer review and technical editing by the publisher. To access the final edited and published work see https://dx.doi.org/10.1021/acs.jpclett.7b00316
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000400042200012&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Subjects
Science & Technology
Physical Sciences
Technology
Chemistry, Physical
Nanoscience & Nanotechnology
Materials Science, Multidisciplinary
Physics, Atomic, Molecular & Chemical
Chemistry
Science & Technology - Other Topics
Materials Science
Physics
EXCITED-STATE DYNAMICS
FLUORESCENCE UP-CONVERSION
NUCLEIC-ACIDS
PHOTOELECTRON-SPECTROSCOPY
ABSORPTION-SPECTROSCOPY
TRANSIENT ABSORPTION
MOLECULAR-DYNAMICS
DECAY MECHANISMS
AQUEOUS-SOLUTION
DNA BASES
Publication Status
Published