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An Approach to the microscopic features of liquid phase reactions using solvation clusters of known structure

使用已知结构的溶剂化团簇研究液相反应微观特征的方法

基本信息

批准号：
03403002
负责人：
KAJIMOTO Okitsugu
金额：
$ 19.78万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (A)
财政年份：
1991
资助国家：
日本
起止时间：
1991 至 1993
项目状态：
已结题

项目摘要

The aim of this project is to determine the structure of solvation clusters by means of the rotational coherence spectroscopy and, based on the determined structure of the clusters, to understand the precise dynamics of cluster reactions. The following subjects have been intensively studied during the period of this project.1. The development of the method for determining the structure of large solvation clustersFor the determination of the structure of large molecules like solvation clusters, the rotational coherence spectroscopy (RCS) is much more suitable than the ordinary high-resolution spectroscopy. RCS directly determines the rotational constants of a cluster by observing the rotational period in the time domain. We constructed an RCS system consisting of a Ti : Al_2O_3 ps laser and a molecular beam apparatus.The RCS of 9,9'-bianthryl (BA)The observation of RCS of 9,9'-bianthryl revealed that the RCS signal reflected the average rotational angle of each twisting vibrational leve … More l in its intensity and the coherence time.3. The structure of 9,9'-bianthryl complexesBy using the hole-burning spectroscopy, the detailed spectra of BA complexes were obtained and the potentials for the internal rotation were determined for the complexes. In a He complexe the small perturbation slightly splits the degenerate twisting levels whereas in Ar and H_2O complexes the shape of the potential is drastically changed ; one well of the double well potential disappears.The RCS of these complexes could not be obtained with the time-correlated single photon counting method which detected the coherence of the excited state. On the other hand the time-resolved fluorescence depletion method which detects both the ground and excited state coherence provided information of the rotational constants of BA-Ne, BA-Ar, and BA-H_2O complexes. With the aid of structure optimization based on the empirical atom-atom interaction potentials, the structure of these complexes were determined.4. The internal rotation and the charge-transfer reaction of 4- (9-anthryl) aniline (AA)An compound, 4- (9-anthryl) aniline(AA), whose behavior is essentially the same for the typical charge-transfer compounds 4- (9-anthryl) -N,N-dimethylaniline (ADMA), was first synthesized and studied under supersonic jet conditions. The potential for the internal rotation was determined and the presence of a new electronic state of CT character was proposed. Less

该项目的目的是通过旋转相干光谱确定溶剂化团簇的结构，并基于所确定的团簇结构，理解团簇反应的精确动力学。在本项目期间，对以下主题进行了深入研究。大分子溶剂化团簇结构测定方法的发展对于溶剂化团簇这类大分子的结构测定，旋转相干光谱（RCS）比普通的高分辨光谱更适合。RCS通过观测星系团在时域内的转动周期，直接确定星系团的转动常数。用Ti：Al_2O_3皮秒激光器和分子束装置组成RCS系统，测量了9，9 ′-联蒽（BA）的RCS，发现其RCS信号反映了BA分子各扭振能级的平均转角。 ...更多信息 l的强度和相干时间。9，9 ′-联蒽配合物的结构用烧孔光谱法获得了BA配合物的详细光谱，并确定了配合物的内旋转势。在He原子中，微扰使简并扭曲能级轻微分裂，而在Ar和H_2O原子中，势的形状发生了剧烈的变化，双势阱中的一个势阱消失了，用时间相关的单光子计数方法检测激发态的相干性，不能得到这些复合物的RCS。另一方面，时间分辨荧光耗尽法同时检测了基态和激发态的相干性，提供了BA-Ne、BA-Ar和BA-H_2 O配合物的转动常数信息。借助经验的原子-原子相互作用势进行结构优化，确定了配合物的结构. 4-（9-蒽基）苯胺（AA）的内旋转和荷移反应首次合成了一种与典型的荷移化合物4-（9-蒽基）-N，N-二甲基苯胺（ADMA）性质基本相同的化合物4-（9-蒽基）苯胺（AA），并在超音速射流条件下进行了研究。确定了内旋转的可能性，并提出了一种新的CT特征电子态的存在。少