Studies on vibrationally excited triplet states

本课题的目的是研究分离分子（气相）和凝聚相中振动激发三重态的性质。孤立分子我们已经建造了一个在孤立分子条件下（气相）研究激发态分子的装置。该装置由准分子激光泵浦染料激光器作为光源、具有超音速射流源的真空室系统和用于发射和MPI测量的检测系统组成。我们已经获得了吡嗪类化合物的高分辨荧光光谱，现在正在尝试获得磷光激发光谱。我们还与IMS的K. Kimura教授小组合作，试图获得azabenes的So-Tl跃迁的两色MPI光谱，并成功获得吡嗪光谱。以下研究是在凝聚相中进行的。1) Tl态的磁性和衰减性质以及振动激发Tl态性质的温度依赖性。2)杜伦晶体中Tl态氮原子的吸氢反应。钌二亚胺配合物的激发态及其弛豫过程。(4)三联苯在溶液中的状态依赖反应。结果表明，振动激发态对体系的三重态性质和反应速率起着重要的决定作用。然而，还有许多问题需要进一步的调查来澄清。

The purpose of this project was to investigate the properties of vibrationally excited triplet states in isolated molecules (gas phase) and condensed phases.1. Isolated moleculesWe have constructed an apparatus for studying excited molecules in isolated molecule conditions(gas phase). The apparatus consists of an excimer laser pumped dye-laser as a light source, a vacuum chamber system with a supersonic jet source and a detection system for emission and MPI measurements. We have already obtained well resolved fluorescence spectra of pyrazines and are now trying to obtain phosphorescence excitation spectra. We have also attemped to obtain two color MPI specfra of So-Tl transitions of azabenzenes in collaboration with Prof. K. Kimura's group at IMS and succeeded in obtaining the pyrazine spectrum.2. Condensed phasesThe following studies were made in condensed phases. 1) Temperature dependences of the magnetic and decay properties of Tl states and the properties of the vibrationally excited Tl states. 2) Hydrogen abstraction reactions of the Tl states azaaromatics in durene crystals. 3) Excited triplet states of Ru diimine complexes and their relaxation processes. (4) State dependent reactions of triplet benzil in solution. It was shown that the vibrationally excited states play important roles in determining the triplet properties and the reaction rates in there systems. However, there are numerous points to be clarified by further investigations.