title: Excited state structures and decay dynamics of 1,3-dimethyluracils in solutions: resonance Raman and quantum mechanical calculation study.
abstract: The resonance Raman spectroscopic study of the excited state structural dynamics of 1,3-dimethyluracil (DMU), 5-bromo-1,3-dimethyluracil (5BrDMU), uracil, and thymine in water and acetonitrile were reported. Density functional theory calculations were carried out to help elucidate the ultraviolet electronic transitions associated with the A-, and B-band absorptions and the vibrational assignments of the resonance Raman spectra. The effect of the methylation at N1, N3 and C5 sites of pyrimidine ring on the structural dynamics of uracils in different solvents were explored on the basis of the resonance Raman intensity patterns. The relative resonance Raman intensities of DMU and 5BrDMU are computed at the B3LYP-TD level. Huge discrepancies between the experimental resonance Raman intensities and the B3LYP-TD predicted ones were observed. The underlying mechanism was briefly discussed. The decay channel through the S1((1)nπ*)/S2((1)ππ*) conical intersection and the S1((1)nπ*)/T1((3)ππ*) intersystem crossing were revealed by using the CASSCF(8,7)/6-31G(d) level of theory calculations.
authors: Department of Chemistry and Key Laboratory of Advanced Textiles Material and Manufacture Technology, MOE, Zhejiang Sci-Tech University , Hangzhou, Zhejiang Province, 310023, People's Republic of China.
authors: Ming-Juan
authors: MJ
authors: Li
authors: Ming-Xia
authors: MX
authors: Liu
authors: Yan-Ying
authors: YY
authors: Zhao
authors: Ke-Mei
authors: KM
authors: Pei
authors: Hui-Gang
authors: HG
authors: Wang
authors: Xuming
authors: X
authors: Zheng
authors: Wei Hai
authors: WH
authors: Fang
mesh_terms: D000097:Acetonitriles / Q000737:chemistry; D000432:Methanol / Q000737:chemistry; D008745:Methylation; D008958:Models, Molecular; D011789:Quantum Theory; D012996:Solutions; D012997:Solvents / Q000737:chemistry; D013059:Spectrum Analysis, Raman; D013941:Thymine / Q000737:chemistry*; D014466:Ultraviolet Rays; D014498:Uracil / Q000031:analogs & derivatives* / Q000737:chemistry*; D014732:Vibration; D014867:Water / Q000737:chemistry
chemical_list: D000097:Acetonitriles; D012996:Solutions; D012997:Solvents; D014867:Water; D014498:Uracil; C061430:5-bromo-1,3-dimethyluracil; C002451:1,3-dimethyluracil; D013941:Thymine; D000432:Methanol; C032159:acetonitrile