Reaction Dynamics of Transition Metal Atoms and Complexes

本课题旨在阐明过渡金属原子及其配合物的反应动力学。由于过渡金属原子中电子态密度高，其碰撞态变化极快，因此只能在单一碰撞条件下进行态特异反应的研究。本项目建立了一种新型的研究气相过渡金属原子及其配合物反应的交叉光束装置。尝试了不同的喷嘴源来获得强原子束，并研究了它们的特性。利用该装置，研究了以下两种氧化反应。Ti(a^3Fj) + O_2（X^3 Σ^- _g）→TiO(a^ 3φ) +O(^3P_j) (R-1)Al(^2P_<1/ 2,3 /2>) + 0_2（X^3Σ^-g）→AIO(X^2Σ^+)+O(^3P_j) （R-2）反应（R-1）是一个高度放热的反应，对产物的化学发光进行了测量和分析，得到了有效能的能量分配。采用激光诱导荧光技术对反应产物a10 （R-2）进行了检测。测定了Al， A1（^2P_<1/2,3/2>）的两个自旋轨道组分a10的旋转和振动态分布。提出了符合实验结果的反应机理。

This research project has been carried out to clarify the reaction dynamics of transition metal atoms and their complexes. Because of the high density of electronic states in the transition metal atom its collisional state change is extremely fast, then state specific reaction study can be achieved only under single collision condition.In this project, new crossed-beam apparatus was constructed to study reactions of gas-phase transition metal atoms and their complexes. Various nozzle sources were tried to obtain intense atomic beam and their characteristics were studied. By using this apparatus, the following two oxidation reactions were studied.Ti(a^3Fj) + O_2(X^3 Σ^- _g) → TiO(A^3φ) + O(^3P_j) (R-1)Al(^2P_<1/2, 3/2>) + 0_2(X^3Σ^-g) → AIO(X^2Σ^+)+O(^3P_j) (R-2)Reaction (R-l) is highly exothermic and chemiluminescence from the product was measured and analyzed to obtain energy partition of available energy. The product, A1O of reaction (R-2) was detected by the laser-induced fluorescence technique. Rotational and vibrational state distribution of A1O was determined for two spin-orbit components of Al, A1(^2P_<1/2,3/2>). The reaction mechanism was proposed to satisfy the experimental results.