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The Structure and Reactions of Large Clusters Studies by The Rotational Coherence Method

旋转相干法研究大团簇的结构和反应

基本信息

批准号：
06044108
负责人：
KAJIMOTO Okitsugu
金额：
$ 5.25万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for international Scientific Research
财政年份：
1994
资助国家：
日本
起止时间：
1994 至 1995
项目状态：
已结题

项目摘要

Knowledge of structure of solvated cluster is essentially important to understand its intramolecular reaction in microscopic level. However, the difficulty of spectroscopic determination of big molecules like solvated clusters prevents us from relating intramolecular reactions of solvated clusters with their structure. The bigger a molecule is, the less advantageous is traditional high-resolution frequency spectroscopy to determine molecular structure. How the number and location of solvent molecules affect the rate of intramolecular charge transfer reaction is our main interest. We adopted rotational coherence spectroscopy as a tool to determine the structure of such clusters.Complexes between bianthryl and other solvent molecules have lower symmetry than the monomer. In addition, intramolecular charge transfer reaction involves large structural change causing the rotation of the principal axis. These facts prevent observing rotational coherence signals with time-correlated single-pho … More ton counting method, which measures the rotational level structure of electronically excited state. Therefore, the pump-probe method was applied to obtain structural information of evectronically ground state of water complex, which shows non-adiabatic transition to a charge transfer state via photoexcitation. After some efforts to obtain good stability of the amplification system of short pulse laser, we finally observed the rotational coherence signal of water complex with this method. Loss of the rotational coherence signal in electronically excited state and observation of the rotational coherence in the electronically ground state suggest a large structural change following intramolecular charge transfer. To perform this research, Prof.Kajimoto visited Oxford and Dr.Langford visited Kyoto.Other molecules cousing intramolecular charge transfer reaction even without clustering with polar solvent molecules, 4- (N,N-dimethylamino) ethylbenzoate (Oxford) and 4- (N,N-dimethylamino) -3,5-dimethylbenzonitrile (Kyoto) were also investigated. From the analysis of their structure, close relation between torsional potential and formation of charge transfer reaction is established. To perform this research, Prof.Simons visited Kyoto and Ms.Lee visited Oxford. Less

了解溶剂化团簇的结构对于在微观水平上理解其分子内反应是至关重要的。然而，像溶剂化团簇这样的大分子的光谱测定的困难使我们无法将溶剂化团簇的分子内反应与其结构联系起来。分子越大，传统的高分辨率频率光谱法测定分子结构的优势就越小。溶剂分子的数目和位置如何影响分子内电荷转移反应的速率是我们的主要兴趣。我们采用旋转相干光谱作为工具来确定这种团簇的结构。双苯基与其他溶剂分子之间的配合物的对称性低于单体。此外，分子内电荷转移反应涉及到引起主轴旋转的较大结构变化。这些事实阻碍了用时间相关单光子计数法观测电子激发态旋转能级结构的旋转相干信号。因此，采用泵探针法获得了水配合物电子基态的结构信息，该基态通过光激发向电荷转移态的非绝热跃迁。经过努力使短脉冲激光放大系统具有良好的稳定性，我们终于用这种方法观测到了水配合物的旋转相干信号。电子激发态旋转相干信号的丢失和电子基态旋转相干信号的观察表明，分子内电荷转移后结构发生了很大的变化。为了进行这项研究，kajimoto教授访问了牛津大学，langford博士访问了京都。此外，还研究了与极性溶剂分子4- （N，N-二甲氨基）乙基苯甲酸酯（Oxford）和4- （N，N-二甲氨基）-3,5-二甲基苯腈（Kyoto）发生分子内电荷转移反应的分子。通过对其结构的分析，确定了扭转势与电荷转移反应的形成有密切的关系。为了进行这项研究，simons教授访问了京都，lee女士访问了牛津。少