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首页> 外文期刊>Bulletin of the Chemical Society of Japan >Physical Chemistry of the Lowest Excited Singlet State of trans-Stilbene in Solution as Studied by time-Resolved Raman Spectroscopy
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Physical Chemistry of the Lowest Excited Singlet State of trans-Stilbene in Solution as Studied by time-Resolved Raman Spectroscopy

机译：通过时间分辨拉曼光谱研究的溶液中反式芪的最低激发单态状态的物理化学

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摘要

Structrue and dynamics of the lowest excited singlet state of trans-stilbene (the S_1 state of tSB) in solution are discussed with an emphasis placed on the elucidation of the mechanism of the trans-cis photoisomerization. Structure of S_1 tSB in solution is first discussed based on the time-resolved Raman spectral data and their isotope substitution effects. Original data for an asymmetrically deuteriated tSB, tSB-d_5, are presented to confirm the ethylene-like structure of the central C-C linkage of S_1 tSB. Next, the time-, temperature-, and solvent-dependent band shape changes of the olefinic C=C stretch band are discussed in terms of the solvent induced dynamic polarization. It is shown that the dynamic polarization model accounts very well, not only for the observed band shape changes, but also for their relevance to the isomerization mechanism. A new microscopic view on the photoisomerization of tSB is thus presented. Picosecond energy dissipation process of S_1 tSB is then discussed in relation to the microscopic solvation structure in chloroform. Finally, the mechanism of a new bimolecular reaction between S_1 tSB and carbon tetrachloride is discussed on the basis of the diffusion-controlled reaction model.
机译：讨论了溶液中最低激发态的结构和动力学的溶液中的最低激发态（S_1的S_1状态），并强调阐述Trans-CIS光学异构化机理的阐明。首先基于时间分辨的拉曼光谱数据及其同位素替换效果首先讨论S_1 TSB的结构。提出了非对称氘代射TSB，TSB-D_5的原始数据以确认S_1 TSB的中央C-C连杆的乙烯状结构。接下来，根据溶剂诱导的动态极化讨论烯烃C = C拉伸带的时间，温度和溶剂依赖性带状变化。结果表明，动态偏振模型占井，不仅用于观察到的频带形状而变化，而且还用于其与异构化机制的相关性。因此提出了关于TSB的光学硅运动的新微观视图。然后讨论S_1 TSB的PICOSECOND耗散过程与氯仿中的微观溶剂化结构有关。最后，在扩散控制的反应模型的基础上讨论了S_1 TSB和四氯化碳之间新的双分子反应的机制。

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    Hiro-o Hamaguchi; Koichi Iwata;

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    Department of Chemistry and Research Centre for Spectrochemistry School of Science The University of Tokyo 7-3-1 hongo Bunkyo-ku Tokyo 113-0033;

    Department of Chemistry and Research Centre for Spectrochemistry School of Science The University of Tokyo 7-3-1 hongo Bunkyo-ku Tokyo 113-0033;

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  • 正文语种 eng
  • 中图分类 化学;化学工业;
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