Study of intermediate species in organometallic reactions

过渡金属原子在有机金属化学中扮演着各种重要的角色。在本研究计划中，我们研究了气相过渡金属原子，以阐明它们与一些简单分子的相互作用。采用了两种实验方法，即动力学方法和光谱方法。首先，采用放电流动-激光诱导荧光法测定了特定电子态过渡金属原子的反应速率常数。提出了在与氧化剂和烃类反应中电子构型及其能量的重要性。这些研究提供了关于势能面交叉或避免交叉的定性信息，这些势能面交叉控制过渡金属原子的反应。第二种方法是对过渡金属原子（本研究项目中选择了Ni）-稀有气体原子货车德瓦耳斯配合物的电子跃迁进行光谱研究。这些研究为Ni-Ar和Ni-Kr相互作用势曲线提供了定量的认识。电子激发态的动力学也进行了研究。

Transition metal atoms play various important roles in the organometallic chemistry. In this research project, gas-phase transition metal atoms were studied to clarify their interaction with some simple molecules. Two experimental approaches were taken, i.e. kinetic and spectroscopic ones. At first, reaction rate constants of electronic state specific transition metal atoms were determined by using a discharge flow-LIF method. Importances of electronic configurations as well as their energy were proposed in the reactions with oxidants and hydrocarbons. These studies provided qualitative information about potential energy surface crossing or avoided crossing which governs the reactions of transition metal atoms. Second approach was spectroscopic studies of electronic transitions of transition metal atom (Ni was selected in this research project)-rare gas atom van der Waals complexes. These studies provided quantitative knowledge about Ni-Ar and Ni-Kr interaction potentials curves. Dynamics of electronically excited states were also studied.