title: Ultrafast Excited-State Dynamics of 6-Azauracil Studied by Femtosecond Transient Absorption Spectroscopy.
abstract: The excited-state dynamics of 6-azauracil in different solvents have been studied using femtosecond transient absorption spectroscopy. The molecule is populated to the S2 state with a pump pulse at 264 nm. Broad-band white light continuum which covers from 320 to 600 nm is used as the probe. With a global fitting analysis of the measured transient spectra, three decay time constants, i.e., <0.3, 5.2 ± 0.1, and >1000 ps, are directly obtained in the solvent of acetonitrile. These newly observed lifetime constants are important in clarifying its decay dynamics as well as in providing a criterion for the ultrafast dynamics simulations in 6-azauracil using quantum chemical theories. In combination with previous theoretical works, the main decay channel is proposed: the initially populated S2 decays to S1 through internal conversion in <0.3 ps, followed by an intersystem crossing from S1 to T1 in 5.2 ± 0.1 ps. The >1000 ps component is due to the decay of the T1 state. A comparison of the excited-state dynamics in different solvents reveals that the decay from S1 to T1 shows a clear dependence on the polarity of the solvents. With higher polarity, the S1 excited state decays faster. This observation is in line with the prediction by Etinski et al. [ Phys. Chem. Chem. Phys. 2010 , 12 , 15665 - 15671 ], where a blue-shift of the T1 state potential energy surface leading to an increase of the intersystem crossing rate was proposed. With the new information obtained in the present measurement, a clearer picture of the decay dynamics of 6-azauracil on the S2 excited state is provided.
authors.affiliation: State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences , Wuhan 430071, P. R. China.
authors.forename: XinZhong
authors.initials: X
authors.lastname: Hua
authors.affiliation: State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences , Wuhan 430071, P. R. China.
authors.forename: LinQiang
authors.initials: L
authors.lastname: Hua
authors.affiliation: State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences , Wuhan 430071, P. R. China.
authors.forename: XiaoJun
authors.initials: X
authors.lastname: Liu
mesh_terms: D011789:Quantum Theory; D013057:Spectrum Analysis; D013997:Time Factors; D014498:Uracil / Q000031:analogs & derivatives* / Q000737:chemistry
chemical_list: D014498:Uracil; C100248:azauracil