A theoretical study of the interaction between inter-molecular proton transfer and internal rotation

分子间质子转移与内旋转相互作用的理论研究

• 批准号: 13640508
• 负责人: SHIDA Norihiro
• 金额: $ 2.18万
• 依托单位: Nagoya Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13640508/
• 关键词: inter-molecular proton transfer; internal rotation; highly excited states; 5-methyl malonaldehyde; 2-methyl-malonaldehyde; tunneling splitting; Reaction Surface Hamiltonian; 5メチル9ヒドロキシフェナレノン; スペクトル分解法; 大振幅振動; 反応曲面法; トンネリングスプリッティング; 5メチルーマロンアルデ

This research project investigated theoretically the interaction between the inter-molecular proton transfer and the internal rotation. For this problem, an experimental research had already reported the existence of a peculiar interaction where the proton transfer reaction was enhanced by the excitation of the internal rotation. However, the detailed mechanism of this interaction has been completely unknown.In this project, new method and computer code to treat this problem were developed and were applied to the 5-methyl-9-hyodroxyphenalenone, 2-methyl-malonaldehyde and 5-methyl-tolopolone. The developed method and computer were essentially an extension of the Reaction Surface Hamiltonian method for the systems that have plural numbers of large amplitude motions. In the application, the interaction mentioned above was surely reconfirmed and the detailed mechanism of this interaction was also successfully analyzed. In addition to this analysis, a new fact was found when the internal rotation was in the highly excited states. It is that the proton transfer reaction was obstructed by the excitation of the internal rotation in the highly excited rotational states. In this project, the reason and the mechanism of this phenomenon were also analyzed.

本课题从理论上研究了分子间质子转移与内旋转的相互作用。对于这个问题，实验研究已经报道了一种特殊的相互作用的存在，其中质子转移反应被内旋转的激发所增强。本项目开发了一种新的方法和计算机程序，并将其应用于5-甲基-9-羟基非那烯酮、2-甲基-丙二醛和5-甲基-甲萘醌的研究。所开发的方法和计算机本质上是反应面哈密顿方法的扩展，适用于具有多个大振幅运动的系统。在实际应用中，上述相互作用得到了肯定，并成功地分析了这种相互作用的详细机理。除此之外，还发现了一个新的事实，即内转动处于高激发态。在高激发转动态，内转动的激发阻碍了质子转移反应。本课题还对这一现象产生的原因和机理进行了分析。

项目成果

Kouichi Takeshita, Norihiro Shida, Eisaku Miyoshi: "A theoretical study on the lonization of OCS with an analysis of vibrational structures of the nhotnelectron spectrum"Theoreticul Chemistry Accounts. 107. 33-37 (2001)

Kouichi Takeshita、Norihiro Shida、Eisaku Miyoshi：“通过分析电子能谱的振动结构对 OCS 电离进行理论研究”理论化学帐户。

Theoretical study on proton tunneling potential of 9-hydroxyphenalenone-CO_2 complex

9-羟基苯烯酮-CO_2配合物质子隧道效应的理论研究

• 发表时间: 2002
• 期刊: Japanese Journal of Deuterium Science 11
• 作者: Mori Hirotoshi;Norihiro Shida;Eisaku Miyoshi;Hiroshi Sekiya
• 通讯作者: Hiroshi Sekiya

A theoretical study of strong anharmonic coupling between OH stretching and bending modes in phenol-water cationic complex

酚-水阳离子配合物中OH伸缩和弯曲模式强非简声耦合的理论研究

• 发表时间: 2003
• 期刊: Chemical Physics Letters 371
• 作者: NorifiuniYamamoto;Norihiro Shida;Eisaku. Miyoshi
• 通讯作者: Eisaku. Miyoshi

N.Shida: "Onset dynamics of phase tansition in Ar_7"Adv.Chem.Phys.. (in press). (2004)

N.Shida：“Ar_7 中相变的起始动力学”Adv.Chem.Phys..（正在出版）。

Density functional study of n-propyltrichloro-germane and n-propyltrichlorostannane

正丙基三氯锗烷和正丙基三氯锡烷的密度泛函研究

• 发表时间: 2004
• 期刊: Journal of Molecular Structure 694
• 作者: Keijiro Taga;Yasuomi Jibu;Shigetaka Hamada;Yasushi Yamamoto;Tadayoshi Yoshida;Norihiro Shida;Hiroshi Yoshida;Keiichi Ohno;Hiroatsu Matsuura^*
• 通讯作者: Hiroatsu Matsuura^*