Study of isomer-dependent reactions of organic molecular clusters

有机分子簇异构体依赖性反应的研究

• 批准号: 03640423
• 负责人: MIKAMI Naohiko
• 金额: $ 1.28万
• 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 (C)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03640423/
• 关键词: molecular cluster; reaction within cluster; photoionized cluster; 分子クラスタ-内反応; クラスタ-内イオン分子反応; フルオロベンゼン:アンモニア錯体; 配向異性体の反応性

Intracluster ion-molecule reactions of the photoionized van der Waals Complexes of C_6H_5F with NH_3 and with H_2O have been investigated by means of two-color multiphoton ionization spectroscopy in combination with mass analysis. Two different intracluster reactions of C_6H_5F-NH_3, the substitution reaction yielding C_6H_5NH_2^+ and the dissociation yielding C_6H_5F^+, were induced by the selective photoionization of different isomers of the complexes. Ionization threshold specra of the complexes and appearance energies of the reaction products were observed. Energetics of the reactions was discussed on the bases of the experimental results and the calculated geometries of the isomers. It was concluded that the nucleophilic substitution reaction is responsible for the C_6H_5NH_2^+ production. Isomer-dependent reactions occurring within the H_2O complexes were also presented, and their energetics was discussed in relation to a barrier height to the substitution reaction.

用双色多光子电离光谱结合质谱法研究了C_6H_5F与NH_3和H_2O形成的光离范德华络合物的簇内离子-分子反应。C_6H_5F-NH_3的两个不同的簇内反应，即生成C_6H_5NH_2~+的取代反应和得到C_6H_5F~+的解离反应，是由不同异构体的选择性光致电离引起的。观察了络合物的电离阈值、光谱和反应产物的出现能。根据实验结果和计算的异构体几何构型，讨论了反应的能量学。亲核取代反应是C_6H_5NH_2~+生成的主要原因。文中还介绍了H2O络合物内发生的异构体相关反应，并讨论了它们的能量与取代反应势垒高度的关系。

项目成果

T.Maeyama: "Intracluster Ion-Molecule Reactions within the Photoionized van der Waals Complexes of C_6H_5F with NH_3 and H_2O." J.Phys.Chem.95. 7197-7204 (1991)

T.Maeyama：“C_6H_5F 与 NH_3 和 H_2O 的光离子化范德华配合物内的簇内离子分子反应。”

T. Maeyama: "Intracluster Ion-Molecule Reactions within the photoionized van der Waals Complexes of C_6H_5F with NH_3 and H_2O." J. Phys. Chem.95. 7197-7204 (1991)

T. Maeyama：“C_6H_5F 与 NH_3 和 H_2O 的光离子化范德华配合物内的簇内离子分子反应。”

N.MIKAMI: "Trapped Ion Photodissociation Spectroscopy:the Electronic Spectrum of the Hydrogen-Bonded Complex Cationa[C_6H_5OH-N(CH_3)_3]^+." Chem.Phys.Lett.180. 431-435 (1991)

N.MIKAMI：“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: "Stable Forms of the Phenol-Complex Cations as Revealed by Trapped Ion Photodissociation Spectroscopy." Chem.Phys.Lett.202. 431-436 (1993)

N.Mikami：“俘获离子光解离光谱揭示了酚络合物阳离子的稳定形式。”

T.MAEYAMA: "Intracluster Ion-Molecule Reactions within the Photoionized van der Waals Complexes of C_6H_5F with NH_3 and H_2O." J.Phys.Chem. 95. 7197-7204 (1991)

T.MAEYAMA：“C_6H_5F 与 NH_3 和 H_2O 的光离子化范德华配合物内的簇内离子分子反应。”