Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 8, Issue 8, Pages 1777-1783Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.7b00316
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Funding
- European Research Council [291198]
- French Agence National de la Recherche (FEMTO-2DNA) [ANR-15-CE29-0010]
- Spanish MINECO [CTQ2014-58624-P]
- CNR/CNRS
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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 S-1/S-0 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 (1)pi(2)pi* 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 pyrirnidine nucleosides.
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