Citation: XU Zong-Ping, ZHAO Yan-Ying, WANG Hui-Gang, ZHENG Xu-Ming. Resonance Raman Spectroscopy and Density Functional Theory Investigations on the Excited State Structural Dynamics of N-Methylpyrrole-2-carboxaldehyde and Its Solvent Effect[J]. Acta Physico-Chimica Sinica, ;2012, 28(01): 65-72. doi: 10.3866/PKU.WHXB20122865 shu

Resonance Raman Spectroscopy and Density Functional Theory Investigations on the Excited State Structural Dynamics of N-Methylpyrrole-2-carboxaldehyde and Its Solvent Effect

1.
Key Laboratory of Advanced Textiles Materials and Manufacture Technology, and Engineering Research Center for Eco-dyeing and Finishing of Textiles, Ministry of Education, Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, P. R. China

Received Date: 30 August 2011
Available Online: 7 November 2011
Fund Project: 国家重点基础研究发展规划(2007CB815203) (2007CB815203) 国家自然科学基金(21033002, 20803066) (21033002, 20803066)浙江省自然科学基金(Y4090161)资助项目 (Y4090161)

Resonance Raman spectra of N-Methylpyrrole-2-carboxaldehyde (NMPCA) were obtained and seven excitations covered the A- and B-band electronic absorptions. The electronic excitations and the Franck-Condon region structural dynamics of NMPCA were studied by resonance Raman spectroscopy and time-dependent density functional theory (TD-DFT) calculations. The A- and B-band electronic absorptions were assigned to π →π^* transitions on the basis of the TD-B3LYP/6-311 ++ G(d,p) level of theory. The resonance Raman spectra showed Raman intensity in the fundamentals, the overtones and the combination bands for about 11-13 vibrational modes (A-band excitation) or 7-11 vibrational modes (B-band excitation). These were predominately due to the C＝O stretch mode ν₇, the ring deformation+N₁－ C₆ stretch ν₁₇, the ring deformation mode ν₂₁ and the C₆－N₁－C₂/C₂－C₃－C₄ anti-symmetry stretch mode ν₁₄. This indicates that the Franck-Condon region S_π structural dynamics of NMPCA mainly occurs along the C＝O stretch, the ring deformation, and the N₁－C₆ stretch reaction coordinates. In a certain solvent and under different excitation wavelengths the relative intensity of the C＝O stretch mode ν₇ versus the C₆－N₁－C₂/C₂－C₃ －C₄ anti-symmetry stretch mode ν₁₄ shows an intense to weak to intense change as the excitation wavelengths decrease. This intensity variation directly reflects the S_n/S_π state-mixing or crossing of the potential energy surfaces in the Franck-Condon region. Solvents can efficiently tune the Franck- Condon region S_n/S_π state-mixing or crossing processes.
- N-Methylpyrrole-2-carboxaldehyde,
- Excited state structural dynamics,
- Resonance Raman spectrum,
- Solvent effect
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