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对异质溶剂化环境中气相团簇阴离子的电子性质的系统研究，从微观上了解溶剂化电子和阴离子的稳定机制。1． (H_2O)_n^- 中氢键网络的重建：我们证明，通过利用“Ar 介导”过程，可以有效地将单个 D_2O 或 CH_3OH 掺入 (H_2O)_<6,7>^- 中，而不会丢失任何 H_2O 成分 (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，通过在掺入过程中氢键网络的广泛重建，在[(H_2O)_nM]^中发生异构体互变。 2．双偶极结合阴离子的形成和光破坏：通过氩溶剂化的水六聚体阴离子(H_2O)_6^-Ar_m的掺入反应，生成了一种由水和μ>2.8 D极性分子组成的新型偶极结合阴离子。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 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：通过红外光解离光谱结合从头计算研究了[(CO_2)_n(ROH)_m]^-的溶剂化结构。观察到显着的夹带剂效应，掺入的质子分子通过单离子氢键相互作用有效稳定CO_2。4．通过周围多偶极子稳定的价阴离子：通过光电子成像光谱研究了丙酮和水分子的带负电簇[(Me_2CO)_n(H_2O)_m]^-的电子性质。测量结果表明一种新型稳定机制在 [(Me_2CO)_n(H_2O)_m]^-: i 中起作用的可能性。即，Me_2CO 的价阴离子被周围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

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