Reaction Dynamics of Transition Metal Atoms and Complexes

过渡金属原子和配合物的反应动力学

• 批准号: 12440168
• 负责人: HAMA Kenji
• 金额: $ 8.64万
• 依托单位: Himeji Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12440168/
• 关键词: Transition metal atom; crossed-beam; reaction dynamics

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.

本研究旨在阐明过渡金属原子及其配合物的反应动力学。由于过渡金属原子的高电子态密度，其碰撞态的变化非常快，只有在单次碰撞条件下才能实现态特异性反应的研究，本项目构建了一种新的交叉束装置，用于研究气相过渡金属原子及其配合物的反应。为了获得强流的原子束，尝试了多种喷嘴源，并研究了它们的特性。利用该装置研究了Ti（a^3Fj）+ O_2的氧化反应（X^3 β ^- _g）→ TiO（A^3φ）+ O（^3P_j）（R-1）Al（^2P_<1/2，3/2>）+O_2（X_3 P_1-g）→ AIO（X_2 P_1+）+O（X_3 P_1）（R-2）反应（R-1）是高度放热的，并且测量和分析来自产物的化学发光以获得可用能量的能量分配。反应（R-2）的产物A1 O用激光诱导荧光技术检测。对Al的两个自旋轨道分量A1（^2P_<1/2，3/2>），测定了A1 O的转动和振动态分布。提出了反应机理，并与实验结果进行了比较。

项目成果

Katsuhiro Tanaka: "Microscopic solvation of acetonitrile to 9, 9'-bianthryl studied in gas phasecluster : Polar excited state formation"The Journal of Physical Chemistry. 106(印刷中). (2002)

Katsuhiro Tanaka：“在气相簇中研究乙腈到 9, 9-联蒽的微观溶剂化：极性激发态形成”《物理化学杂志》106（出版中）。

Y.Kawamoto, H.Honma: "Ni-Kr complex studied by laser spectroscopy"Phys. Chem. Chem. Phys.. 3. 925-931 (2001)

Y.Kawamoto、H.Honma：“通过激光光谱研究镍-氪配合物”Phys。

Katsuhiro Tanaka and Kenji Honma: "Microscopic solvation of acetonitrile to 9,9' - bianthryl studied in gas phase clusters: Polar excited state formation"J. Phys. Chem.. Vol. 106. 1926-1932 (2002)

Katsuhiro Tanaka 和 Kenji Honma：“在气相簇中研究乙腈到 9,9-联二蒽的微观溶剂化：极性激发态形成”J。

Y.Kawamoto, H.Honma: "Ni-Ar complex studied by laser spectroscopy"Phys. Chem. Chem. Phys.. 2. 3971-3976 (2000)

Y.Kawamoto、H.Honma：“通过激光光谱研究 Ni-Ar 配合物”Phys。

Shozo Ideue, Kunio Sakamoto, Kenji Honma, and David E. Clemmer: "Conformation change of electrosprayed cytochrome c studied by laser-induced fluorescence"Chem. Phys. Lett.. Vol. 337. 79-84 (2001)

Shozo Ideue、Kunio Sakamoto、Kenji Honma 和 David E. Clemmer：“通过激光诱导荧光研究电喷雾细胞色素 c 的构象变化”Chem。