Excited State Structures and Decay Dynamics of 1,3-Dimethyluracils in Solutions: Resonance Raman and Quantum Mechanical Calculation Study

详细信息    查看全文

• 作者：Ming-Juan Li ; Ming-Xia Liu ; Yan-Ying Zhao ; Ke-Mei Pei ; Hui-Gang Wang ; Xuming Zheng ; Wei Hai Fang
• 刊名：Journal of Physical Chemistry B
• 出版年：2013
• 出版时间：October 3, 2013
• 年：2013
• 卷：117
• 期：39
• 页码：11660-11669
• 全文大小：436K
• 年卷期：v.117,no.39(October 3, 2013)
• ISSN：1520-5207

文摘

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(¹n蟺*)/S₂(¹蟺蟺*) conical intersection and the S₁(¹n蟺*)/T₁(³蟺蟺*) intersystem crossing were revealed by using the CASSCF(8,7)/6-31G(d) level of theory calculations.