Investigations of the steric effect in chemical reactions by utilizing radical clusters

利用自由基簇研究化学反应中的空间效应

• 批准号: 21550006
• 负责人: SUMIYOSHI Yoshihiro
• 金额: $ 2.33万
• 依托单位: Gunma University (2011)The University of Tokyo (2009-2010)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2009
• 资助国家: 日本
• 起止时间: 2009 至 2011
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-21550006/
• 关键词: ラジカルクラスター; ラジカル反応; 立体効果; 分子間相互作用; 高分解能分光

The H_2O-HOCO cluster has been observed by Fourier-transform microwave spectroscopy for the first time, and it has been observed that a change of distribution of the unpaired electron in the HOCO radical is induced by complex formation with H_2O due to a strong intermolecular interaction. It has been revealed that the unpaired electron in the HOCO radical plays an important role in the strong attractive force ; a dependence of the attractive forces with respect to the relative configuration between H_2O and HOCO can be ascribed to that of the shape of SOMO of the HOCO radical.Intermolecular potential energy surfaces of NO and OH between Ne, Ar, and Kr have been investigated. It has been revealed that the shape of the intermolecular potential energy surfaces of the diatomic radicals which have degenerate highest occupied molecular orbital (HOMO) are in good agreement with the shape of the singly occupied molecular orbital (SOMO).

首次通过傅立叶转换微波光谱观察到了H_2O-HOCO簇，并且已经观察到，HOCO自由基中未配对电子的分布的变化是由于强烈分子相互作用而与H_2O的复合形成引起的。据透露，HOCO激进分子中未配对的电子在强大的吸引力中起着重要作用。吸引力相对于H_2O和HOCO之间的相对构型的依赖性可以归因于HOCO自由基Somo的形状。据揭示，具有最高占用的分子轨道（HOMO）的双原子激自线的分子间势能表面的形状与单人占据分子轨道（SOMO）的形状非常吻合。

项目成果

Handbook of High-resolution Spectroscopy : "Rotational Spectroscopy of Complexes Containing Free Radicals"

高分辨率光谱学手册：“含自由基的配合物的旋转光谱学”

• 发表时间: 2011
• 作者: Yasuki Endo;Yoshihiro Sumiyoshi
• 通讯作者: Yoshihiro Sumiyoshi

Microwave spectroscopy and potential energy surfaces of the Ne-OH and Kr-OH

Ne-OH 和 Kr-OH 的微波光谱和势能表面

• 发表时间: 2010
• 作者: 佐野充;水野和子;高柳敏幸;Yoshihiro Sumiyoshi
• 通讯作者: Yoshihiro Sumiyoshi

Microwave spectroscopy of the Ne. OH(^2・_i) complex and three-dimensional intermolecular potentials

Ne OH(^2·_i) 络合物和三维分子间势的微波光谱

• 发表时间: 2010
• 期刊: Physical Chemistry Chemical Physics
• 影响因子: 3.3
• 作者: Yoshihiro Sumiyoshi;Ippei Funahara;Kazuya Sato;Yasuhiro Ohshima;Yasuki Endo
• 通讯作者: Yasuki Endo

The H_2O.O_2 water vapor complex in Earth's atmosphere

地球大气中的H_2O.O_2水蒸气复合物

• 发表时间: 2011
• 期刊: Atmospheric Chemistry and Physics
• 影响因子: 6.3
• 作者: Y. Kasai;E. Dupuy;R. Saito;K. Hashimoto;A. Sabu;S. Kondo;Y. Sumiyoshi;Y. Endo
• 通讯作者: Y. Endo

Observation of the pure rotational spectra of trans- and cis-HOCO

• DOI: 10.1063/1.3578179
• 发表时间: 2011-05-07
• 期刊: JOURNAL OF CHEMICAL PHYSICS
• 影响因子: 4.4
• 作者: Oyama, Takahiro;Funato, Wataru;Endo, Yasuki
• 通讯作者: Endo, Yasuki