Laser Spectroscopic Study of IonーMolecule Reactions in Photoionized Organo Molecular Clusters

光离子化有机分子簇中离子分子反应的激光光谱研究

• 批准号: 01470014
• 负责人: MIKAMI Naohiko
• 金额: $ 4.42万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-01470014/
• 关键词: molecular clusters; intracluster reaction; ion-molecule reaction; photoionized complexes; van der Waals cluster; SN reactions; ファン・デル・ワ-クス錯覚; 分子クラスタ-内求核置換反応; レ-ザ-光イオン化質量分析法; ハロベンゼン・アンモニア錯体

1) Efficient generation of C_6H_5NH^+_ was found after the selective ionization of the van der Waals complex C_6H_5C1-NH_3 which was prepared in a supersonic molecular beam. The action spectrum of the product and its appearance energy were observed by using the two-color mass-selected multiphoton ionization spectroscopy. From the energetics of the reaction it was concluded that the ion-molecule reaction is responsible for the process and the product is generated by the nucleophilic substitution reaction occurring within the photoionized van der Waals complex.2) Intracluster ion-molecule reactions of the photoionized van der Waals complexes c_6H_5F with NH_3 and with H_2O have been investigated. Two different intracluster reactions of C_6H_5F-NH_3, the substitution reaction yielding C_6H_5NH^_ and the dissociation yielding C_6H_5F^+ were induced by the selective photoionization of different isomers of the complexes. Energetics of the reactions was discussed on the bases of the experimental results and of the calculated geometries of the isomers. It was concluded that the nucleophilic substitution reaction is responsible for the C_6H_5NH^+_ production.

1)超声分子束中制备的范德华配合物C_6H_5C1-NH_3选择性电离后,发现C_6H_5NH^+_的高效生成。采用双色质量选择多光子电离光谱观察了产物的作用谱及其表观能量。从反应的能量学可以得出结论，离子-分子反应是该过程的原因，产物是由光离子化范德华配合物内发生的亲核取代反应生成的。2) 光离子化范德华配合物的团簇内离子-分子反应研究了c_6H_5F与NH_3和H_2O的德华配合物。配合物不同异构体的选择性光电离诱导了C_6H_5F-NH_3的两种不同的簇内反应，即产生C_6H_5NH^_的取代反应和产生C_6H_5F^+的解离反应。根据实验结果和计算的异构体几何形状讨论了反应的能量学。结论是亲核取代反应是C_6H_5NH^++生成的原因。

项目成果

Naohiko MIKAMI, Yasushi MIYATA, Shin SATO and Toshiki SASAKI,: "Ion Trap Method Combined with two-color Laser Spectroscopy of Supersonic Molecular Beams : Photodissociation of Trapped C_6H_5C1^+" Chem. Phys. Lett.166,. 470-4 (1990)

Naohiko MIKAMI、Yasushi MIYATA、Shin SATO 和 Toshiki SASAKI，：“离子阱方法与超音速分子束的双色激光光谱相结合：捕获的 C_6H_5C1^ 的光解离” Chem。

Naohiko MIKAMI: "Ion Trap Method Combined with TwoーColor Laser Spectroscopy of Supersonic Molecular Beams:Photodissociation of Trapped c_6H_5Cl^+" Chem.Phys.Lett.166. 470-474 (1990)

Naohiko MIKAMI：“离子陷阱法与超音速分子束的双色激光光谱相结合：捕获的 c_6H_5Cl^+ 的光解离”Chem.Phys.Lett.166（1990）。

Naohiko MIKAMI: "Photodissociation of JetーCooled Acetylacetonato Complexes of the First Transition Methods Free Metal Generation and Fragmentational Ionization" Chem.Phys.141. 431-440 (1990)

Naohiko MIKAMI：“第一种过渡方法的喷射冷却乙酰丙酮配合物的光解离，自由金属生成和碎片电离”Chem.Phys.141（1990）。

Naohiko MIKAMI, Toshiki SASAKI and Shin SATO,: "Trapped Ion Photodissociation Spectroscopy : Electronic Spectrum of the Hydrogen-Bonded Complex Cation [C_6H_5OH-N(CH_3)_3]^+."

Naohiko MIKAMI、Toshiki SASAKI 和 Shin SATO，：“俘获离子光解离光谱：氢键复合阳离子的电子光谱 [C_6H_5OH-N(CH_3)_3]^”。

N.Mikami: "Photodissociation of Jet-Cooled Acetylacetonato Complexes of the First Transition Metals." Chem.Phys.141. 431-440 (1990)

N.Mikami：“第一种过渡金属的喷射冷却乙酰丙酮络合物的光解。”