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

本研究项目的目的是通过系统研究异质溶剂化环境中气相簇阴离子的电子特性，从微观上了解溶剂化电子和阴离子的稳定机制。 1． (H_2O)_n^- 中的键合网络：我们证明了将单个 D_2O 或 CH_3OH 并入 (H_2O)_<6,7>^- 中可以有效进行在不损失任何H_2O成分的情况下，通过利用“Ar介导”过程，例如(H_2O)_n^-Ar_m+M→[M·(H_2O)_n^-Ar_m]^†→[(H_2O)_nM]^-+ mAr。光电子能谱测量表明，通过在[(H_2O)_nM]^-过程中氢键网络的广泛重建，发生了异构体互变。 2. 双偶极结合阴离子的形成和光破坏：通过氩溶剂化水六聚体阴离子的结合反应产生了一种由水和 μ>2.8 D 极性分子组成的新型偶极结合阴离子，(H_2O)_6^-Ar_m，新发现的阴离子可以被视为双偶极结合物种，描述为(H_2O)_6{e^-}。 M，其中扩散的过量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可作为 [(CO_2. )_n(ROH)_m]^-(R=H, CH_3) 簇阴离子：[(CO_2)_n(ROH)_m]^-的溶剂化结构通过以下方法研究红外光解光谱结合从头算，观察到了显着的夹带剂效应，使得掺入的质子分子通过单离子氢键相互作用有效地稳定了CO_2。4． -通过光电子成像研究了丙酮和水分子的带电簇[(Me_2CO)_n(H_2O)_m]^-测量表明，一种新型的稳定机制可能在 [(Me_2CO)_n(H_2O)_m]^- 中发挥作用：即，Me_2CO 的价阴离子被周围的多偶极子产生的静电场稳定。较少的

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

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

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

(H_2O)_n^-にクラスタ-と極性溶媒分子の反応-サイズ依存性と反応機構-

(H_2O)_n^-簇与极性溶剂分子之间的反应-尺寸依赖性和反应机理-

• 发表时间: 2006
• 作者: S. Kato;R. Nakanishi;T. Nagata;村岡梓;須藤虎太郎;中西隆造
• 通讯作者: 中西隆造