<em>N</em>-甲基吡咯-2-甲醛激发态结构动力学及其溶剂效应的共振拉曼光谱和密度泛函理论研究

引用本文: 许宗平, 赵彦英, 王惠钢, 郑旭明. N-甲基吡咯-2-甲醛激发态结构动力学及其溶剂效应的共振拉曼光谱和密度泛函理论研究[J]. 物理化学学报, 2012, 28(01): 65-72. doi: 10.3866/PKU.WHXB20122865 shu

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

N-甲基吡咯-2-甲醛激发态结构动力学及其溶剂效应的共振拉曼光谱和密度泛函理论研究

基金项目:
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)

摘要: 获取了覆盖N-甲基吡咯-2-甲醛(NMPCA)A-带和B-带电子吸收共7 个激发波长的共振拉曼光谱, 并结合含时密度泛函理论(TD-DFT)方法研究了的A-带和B-带电子激发和Franck-Condon 区域结构动力学.TD-B3LYP/6-311++G(d,p)计算表明: A-带和B-带电子吸收的跃迁主体为π→π^*. 共振拉曼光谱可以指认为,11-13 振动模式(A-带激发)或者7-11 振动模式(B-带激发)的基频、倍频和组合频, 其中C＝O伸缩振动(ν₇)、环的变形振动+N₁－C₆伸缩振动(ν₁₇)、环的变形振动(ν₂₁)和C₆－N₁－C₂/C₂－C₃－C₄不对称伸缩振动(ν₁₄)占据了绝大部分. 这表明NMPCA的S_π激发态结构动力学主要沿C＝O伸缩振动、环的变形振动和环上N₁－C₆伸缩振动等反应坐标展开. 在同一溶剂的共振拉曼光谱中随激发波长由长变短, ν₇与ν₁₄的强度比呈现出由强变弱再变强的现象, 这种变化规律被认为与Franck-Condon 区域S_n/S_π态混合或势能面交叉有关. 溶剂对S_n/S_π态混合或势能面交叉具有调控作用.

关键词:

English

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: 29 December 2011
Fund Project:
国家重点基础研究发展规划(2007CB815203)

国家自然科学基金(21033002, 20803066)

浙江省自然科学基金(Y4090161)资助项目

Abstract: 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.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

N-甲基吡咯-2-甲醛激发态结构动力学及其溶剂效应的共振拉曼光谱和密度泛函理论研究

English

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

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

N-甲基吡咯-2-甲醛激发态结构动力学及其溶剂效应的共振拉曼光谱和密度泛函理论研究

English

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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs