Structural Properties of Gas-Phase Solvated Electrons and Anions-Toward the Microscopic Understanding of Stabilization Mechanism-

气相溶剂化电子和阴离子的结构性质-稳定机制的微观理解-

• 批准号: 18550007
• 负责人: NAGATA Takashi
• 金额: $ 2.57万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2006
• 资助国家: 日本
• 起止时间: 2006 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18550007/
• 关键词: cluster; hydrated electron; valence anion; hydrogen-bonding network; photoelectron spectroscopy; IR photodissociation spectroscopy; 溶媒和電子

The aim of the present research project was to attain a microscopic understanding of the stabilization mechanism at play in solvated electrons and anions through the systematic study about the electronic properties of gas-phase cluster anions in heterogeneous solvation environments.1. Reconstruction of the hydrogen-bonding network in (H_2O)_n^-: We demonstrated that the incorporation of a single D_2O or CH_3OH into (H_2O)_<6,7>^-proceeded efficiently without losing any H_2O constituent, by exploiting the "Ar-mediated" process such as (H_2O)_n^-Ar_m+M→[M・(H_2O)_n^-Ar_m]^†→[(H_2O)_nM]^-+mAr. The photoelectron spectroscopic measurements revealed that isomeric interconversion occurred in [(H_2O)_nM]^-through an extensive reconstruction of the hydrogen-bonding network during the incorporation processes.2. Formation and photodestruction of dual dipole-bound anion: A new type of dipole-bound anion composed of water and a polar molecule with μ>2.8 D was generated by the incorporation reaction … More of argon-solvated water hexamer anions, (H_2O)_6^-Ar_m. The newly-found anion can be regarded as a dual dipole-bound species described as (H_2O)_6{e^-} M, where the diffuse excess electron interacts with both (H_2O)_6 and M via the individual electron-dipole interaction. The dual dipole-bound anion also serves as a precursor to the hydrated valence anion of M.3. Structures of [(CO_2)_n(ROH)_m]^-(R=H, CH_3) cluster anions: The solvation structures of [(CO_2)_n(ROH)_m]^-were investigated by infrared photodissociation spectroscopy combined with ab initio calculations. A significant entrainer effect was observed such that the incorporated protic molecule stabilizes CO_2 effectively through the single ionic hydrogen-bonding interaction.4. Valence anions stabilized by surrounding multi-dipoles: The electronic properties of the negatively-charged clusters of acetone and water molecules, [(Me_2CO)_n(H_2O)_m]^-, were studied by photoelectron imaging spectroscopy. The measurement indicates possibility that a new type of stabilization mechanism is operative in [(Me_2CO)_n(H_2O)_m]^-: i. e., the valence anion of Me_2CO is stabilized by an electrostatic field generated by the surrounding multi-dipoles. Less

本研究的目的是通过系统研究非均相溶剂化环境中气相簇阴离子的电子性质，从微观上理解溶剂化电子和阴离子的稳定机理。（H_2O）_n^-中氢键网络的重建：我们证明了单个D_2O或CH_3OH结合到（H_2O）_<6,7 bb0 ^-中，通过利用“ar介导”的过程，如（H_2O）_n^- ar_m +M→[M·（H_2O）_n^- ar_m]^†→[(H_2O)_nM]^-+mAr，有效地进行而不损失任何H_2O成分。光电子能谱测量通过对掺入过程中氢键网络的广泛重建，揭示了[(H_2O)_nM]^-中发生了同分异构体相互转化。双偶极结合阴离子的形成与光破坏：通过掺入反应生成了一种由水与极性分子μ>2.8 D组成的新型偶极结合阴离子。新发现的阴离子可以看作是双偶极结合的物质，描述为（H_2O）_6{e^-} M，其中弥散的多余电子通过单独的电子-偶极相互作用与（H_2O）_6和M相互作用。双偶极结合阴离子也作为M.3水合价阴离子的前体。[(CO_2)_n(ROH)_m]^-(R=H, CH_3)簇阴离子的结构：用红外光解光谱结合从头计算研究了[(CO_2)_n(ROH)_m]^-的溶剂化结构。通过单离子氢键作用，观察到明显的夹带剂效应，掺入的质子分子能有效地稳定CO_2。用光电子成像能谱研究了带负电的丙酮和水分子簇[(Me_2CO)_n(H_2O)_m]^-的电子性质。测量结果表明，在[(Me_2CO)_n(H_2O)_m]^-中可能存在一种新的稳定机制，即Me_2CO的价阴离子被周围多偶极子产生的静电场稳定。少

项目成果

Reactions of (H_2O)_n^- with polar molecules -Size-dependent reaction mechanism-

(H_2O)_n^-与极性分子的反应-尺寸依赖性反应机制-

• 发表时间: 2006
• 作者: R. Nakanishi;T. Nagata
• 通讯作者: T. Nagata

[(CO_2)_n(CH_3OH)_m]^-におけるイオン芯とメタノール分子の配位形態

[(CO_2)_n(CH_3OH)_m]^-中离子核与甲醇分子的配位形式

• 发表时间: 2007
• 作者: Y. Inokuchi;A. Muraoka;Y. Kobayashi;T. Nagata;T. Ebata;加藤修吾;村岡 梓
• 通讯作者: 村岡 梓

水和電子クラスター(H_2O)_n^-の分子取込み反応 : 原子価負イオン生成vsネットワーク構造転移

水合电子簇(H_2O)_n^-的分子摄取反应：价态负离子生成与网络结构转变

• 发表时间: 2008
• 作者: Jun Ochiai;Tetsuya K.Yanai;Seiji Mori;Tsunehiko Higuchi;A. Sekiguchi;H. Yasuda;野内哲也;M. Igarashi;Y.Inokuchi;R.Nakanishi;Seiji Mori;A. Sekiguchi;A.Muraoka;五十嵐正安;森聖治;A. Muraoka;安田浩之;山口直人;Y. Matsuyama;稲垣佑亮;吉川孝;Y. Inokuchi;横山たか;内記達哉;T.Nagata;関口章;中西隆造;中西隆造
• 通讯作者: 中西隆造

Formation of O2CNO− in the reaction of (CO2)n- with NO

(CO2)n- 与 NO 反应生成 O2CNO−

• DOI: 10.1016/j.cplett.2006.11.011
• 发表时间: 2006
• 期刊: Chemical Physics Letters
• 影响因子: 2.8
• 作者: Kotaro Sudoh;Y. Matsuyama;Azusa Muraoka;Ryuzo Nakanishi;T. Nagata
• 通讯作者: T. Nagata

I3^-光解離過程におけるミクロ溶媒効果

I3^-光解过程中的微溶剂效应

• 发表时间: 2007
• 作者: Y. Inokuchi;A. Muraoka;Y. Kobayashi;T. Nagata;T. Ebata;加藤修吾
• 通讯作者: 加藤修吾