title: Short-time dynamics of 2-thiouracil in the light absorbing S2(ππ(∗)) state.
abstract: Ultrahigh quantum yields of intersystem crossing to the lowest triplet state T1 are observed for 2-thiouracils (2TU), which is in contrast to the natural uracils that predominantly exhibit ultrafast internal conversion to the ground state upon excitation to the singlet excited state. The intersystem crossing mechanism of 2TU has recently been investigated using second-order perturbation methods with a high-level complete-active space self-consistent field. Three competitive nonadiabatic pathways to the lowest triplet state T1 from the initially populated singlet excited state S2 were proposed. We investigate the initial decay dynamics of 2TU from the light absorbing excited states using resonance Raman spectroscopy, time-dependent wave-packet theory in the simple model, and complete-active space self-consistent field (CASSCF) and time dependent-Becke's three-parameter exchange and correlation functional with the Lee-Yang-Parr correlation functional (TD-B3LYP) calculations. The obtained short-time structural dynamics in easy-to-visualize internal coordinates were compared with the CASSCF(16,11) predicted key nonadiabatic decay routes. Our results indicate that the predominant decay pathway initiated at the Franck-Condon region is toward the S2/S1 conical intersection point and S2T3 intersystem crossing point, but not toward the S2T2 intersystem crossing point.
authors.affiliation: Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, People's Republic of China.
authors.forename: Jie
authors.initials: J
authors.lastname: Jiang
authors.affiliation: Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, People's Republic of China.
authors.forename: Teng-shuo
authors.initials: TS
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, People's Republic of China.
authors.forename: Jia-dan
authors.initials: JD
authors.lastname: Xue
authors.affiliation: Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, People's Republic of China.
authors.forename: Xuming
authors.initials: X
authors.lastname: Zheng
authors.affiliation: Chemistry College, Beijing Normal University, Beijing 100875, People's Republic of China.
authors.forename: Ganglong
authors.initials: G
authors.lastname: Cui
authors.affiliation: Chemistry College, Beijing Normal University, Beijing 100875, People's Republic of China.
authors.forename: Wei-hai
authors.initials: WH
authors.lastname: Fang
mesh_terms: D000097:Acetonitriles / Q000737:chemistry; D008958:Models, Molecular; D013889:Thiouracil / Q000737:chemistry*; D056928:X-Ray Absorption Spectroscopy
chemical_list: D000097:Acetonitriles; D013889:Thiouracil; C032159:acetonitrile