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

这个项目的目的是通过旋转相干光谱来确定溶剂化团簇的结构，并在所确定的团簇结构的基础上，了解团簇反应的精确动力学。在本项目期间，对以下课题进行了深入的研究。大分子溶剂化团簇结构测定方法的发展旋转相干谱(RCS)比普通高分辨光谱更适合于测定溶剂化团簇等大分子的结构。RCS通过观察星团在时间域中的自转周期，直接确定星团的自转常数。我们建立了一个由Ti：Al_2O_3ps激光器和分子束装置组成的RCS系统。对9，9‘-联苯并(BA)的RCS的观察表明，RCS信号反映了每个扭曲振动能级…的平均旋转角更多的是L在其强度和连贯时间上。9，9‘-联菲络合物的结构用烧孔光谱获得了BA络合物的详细光谱，并测定了它们的内旋转势。在He络合物中，微小的微扰使简并的扭曲能级略有分裂，而在Ar和H_2O络合物中，势的形状发生了很大的变化，双势垒势中的一个势垒消失了。这些络合物的RCS不能用检测激发态相干性的时间相关单光子计数方法得到。另一方面，同时检测基态和激发态相干性的时间分辨荧光耗尽法提供了BA-Ne、BA-Ar和BA-H_2O络合物的转动常数信息。在经验原子相互作用势的基础上进行结构优化，确定了这些配合物的结构。首次在超音速射流条件下合成并研究了4-(9-蒽基)苯胺(AA)的内旋和电荷转移反应，其行为与典型的电荷转移化合物4-(9-蒽基)-N，N-二甲基苯胺(ADMA)基本相同。确定了内旋转势，提出了一种新的CT特征电子态的存在。较少

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