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Resonant excitation transfer of molecular vibrations and time-domain optical processes in liquids and proteins

液体和蛋白质中分子振动和时域光学过程的共振激发传递

基本信息

批准号：
13640500
负责人：
TORII Hajime
金额：
$ 2.5万
依托单位：
Shizuoka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2002
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13640500/
关键词：
Liquid Protein Molecular Vibration Resonant Excitation Transfer Time-Domein Optical Precess Transition Dipole Coupling Infrared and Reman Intensities

项目摘要

Analysis of vibrational modes with large vibrational interactions is important for structural chemistry of large-size molecular systems such as proteins and liquids. It is expected that deep insight is obtained by analyzing phenomena related to those modes. The following studies have been carried out in relation to this point. (1) To clarify the factors that determine the intensities of the signals of time-domain optical processes, the effects of molecular hyperpolarizabilities on the low-frequency Raman and optical Kerr effect intensities of molecular liquids are examined. (2) A theoretical method is developed for analyzing the effect of liquid dynamics on the noncoincidence effect of Raman bands that arises from resonant excitation transfer of molecular vibrations in liquids. By using this method, an analysis is carried out for a real liquid system as an example. The changes in the vibrational eigenstates of the liquid on the sub-picosecond time scale arising from its dynamics are clarified in detail. (3) The interactions between vibrational modes with large dipole derivatives and nonpolar solvents are analyzed to get deep insight into the mechanism of vibrational dephasing that competes with resonant excitation transfer of molecular vibrations in liquids. It is shown that rather strong electric field exists around some widely used nonpolar solvent molecules such as carbon tetrachloride, and it arises from electric quadrupoles on the heavy atoms such as chlorine. (4) The concentration dependence of the noncoincidence effect of the Raman bands of the liquid mixtures of methanol and carbon tetrachloride is analyzed. It is shown that microscopically anisotropic structural changes occur as methanol is diluted in carbon tetrachloride. (5) The changes in the optical properties arising from the interactions between protein backbone and the dye molecule contained in it are analyzed. The role of vibrational modes with large vibrational interactions is shown.

分析具有大振动相互作用的振动模式对蛋白质和液体等大尺寸分子系统的结构化学具有重要意义。通过分析与这些模式相关的现象，有望获得更深入的认识。关于这一点，进行了以下研究。(1)为了阐明决定时域光学过程信号强度的因素，研究了分子超极化率对分子液体的低频拉曼和光克尔效应强度的影响。(2)提出了一种分析液体动力学对液体中分子振动共振激发转移引起的拉曼带非符合效应影响的理论方法。用该方法对一个实际的液体系统进行了分析。详细阐明了液体动力学引起的亚皮秒时间尺度上的振动本征态变化。(3)分析了具有大偶极导数的振动模式与非极性溶剂之间的相互作用，深入了解了液体中分子振动与共振激发转移相竞争的振动减相机制。结果表明，在一些广泛使用的非极性溶剂分子（如四氯化碳）周围存在着相当强的电场，它是由重原子（如氯）上的电四极产生的。(4)分析了甲醇与四氯化碳液体混合物拉曼谱带非符合效应的浓度依赖性。结果表明，甲醇在四氯化碳中稀释后，发生了微观上的各向异性结构变化。(5)分析了蛋白质骨架与所含染料分子相互作用引起的光学性质的变化。表明了具有大振动相互作用的振动模态的作用。