Reaction Dynamics of Transition Metal Atoms and Complexes

本研究旨在阐明过渡金属原子及其络合物的反应动力学。由于过渡金属原子的电子态密度高，其碰撞态变化极快，因此只能在单碰撞条件下实现态特定反应的研究。在本项目中，构建了一种新型的交叉束装置来研究气相过渡金属原子及其络合物的反应。为了获得强原子束，尝试了不同的喷嘴源，并对它们的特性进行了研究。利用该装置研究了Ti(a^3Fj)O_2(X^3Σ^-g)→TiO(A^3φ)O(^3P_j)(R-1)Al(^2P_&lt；1/2，3/2&gt；)0_2(X^3Σ^-g)→AlO(X^2Σ^)O(^3P_j)(R-2)反应(R-L)是高放热反应。用激光诱导荧光技术检测反应产物AlO(R-2)。测定了Al的两个自旋轨道组分A1(^2P&lt；1/2，3/2&gt；)的转动和振动态分布。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.