Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 115, Issue 21, Pages 5247-5255Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp201327w
Keywords
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Funding
- Austrian Science Fund within the framework of the Special Research Program F41 (ViCoM)
- German Research Foundation [SPP 1315, GE 1676/1-1]
- Institute of Organic Chemistry and Biochemistry of the Academy of Sciences of the Czech Republic (AS CR) [Z40550506]
- Ministry of Education of the Czech Republic (Center for Biomolecules and Complex Molecular Systems) [LC512]
- Praemium Academiae of the AS CR
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Nonadiabatic dynamics simulations performed at the state-averaged CASSCF method are reported for uracil. Supporting calculations on stationary points and minima on the crossing seams have been performed at the MR-CISD and CASPT2 levels. The dominant mechanism is characterized by relaxation into the S(2) minimum of pi pi* character followed by the relaxation to the S(1) minimum of n pi* character. This mechanism contributes to the slower relaxation with a decay constant larger than 1.5 ps, in good agreement with the long time constants experimentally observed. A minor fraction of trajectories decay to the ground state with a time constant of about 0.7 Ps, which should be compared to the experimentally observed short constant. The major part of trajectories decaying with this time constant follows the pi pi* channel and hops to the ground state via an ethylenic conical intersection. A contribution of the relaxation proceeding via a ring-opening conical intersection was also observed. The existence of these two latter channels together with a reduced long time constant is responsible for a significantly shorter lifetime of uracil compared to that of thymine.
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