Reaction Control by Cluster-Mediaipd Chemistry

通过簇-Mediaipd 化学控制反应

• 批准号: 11166217
• 负责人: NAGATA Takashi
• 金额: $ 18.24万
• 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 on Priority Areas (A)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11166217/
• 关键词: Cluster-mediated chemistry; Electronic structures; Electronic isomers; Triiodide anion; Microsolvation; Cluster anions; 光解離ダイナミクス; NO不均化反応; 分子クラスター負イオン; 二酸化炭素クラスター; ポリハロゲン負イオン; 負イオン-分子反応; 原子・分子クラスター負イオン; 溶媒和構造; 反応制御; クラスター内ラジカル重合

One of the fundamental issues regarding chemical reactions concerns the effects of week interactions exerted by solvent on the reaction dynamics. In the present study, our efforts have been focused on the following research projects to investigate the effects of "microsolvation" in chemical reactions and to explore the new field of cluster-mediated chemistry :1. Structure of (C0_2)^-_n as a gas-phase nucleophile : The electronic structures of (CO_2)^-_n and [(CO_2)_nROH]^- (R = H, CH_3) are investigated by photoelectron spectroscopy combined with ab initio calculations, demonstrating the coexistence of isomers having different electronic structures. These "electronic isomers" are well described as [C_2O^-_4磁ROH(CO_2)_<n-2>] and [CO^-_2磁ROH(CO_2)_<n-1>]. The calculations have also revealed quantitatively the behavior of the excess charge flow during the CO^-_2磁CO_2 。レtautomer。ロ C_2O^-_4 electronic isomerization, which might play a crucial role in the reductive activation of carbon dioxi … More de in the course of gas-phase reactions mediated via (CO_2)^-_n.2. Single-molecule solvent effects in I^-_3 photodissociation。。:。。Photodissociation dynamics of gas-phase I^-_3 along with its weakly bound clusters, I^-_3磁M (M = CH_3CN, C_2H_5OH), was investigated for a microscopic understanding of solvent effects on the photodissociation dynamics. The experimental results demonstrate convincingly that even single-molecule solvation results in a drastic change in the I^-/I^-_2 product branching, which opens up a possibility of controlling the photofragmentation process by exploiting week intermolecular interactions. We also performed ab initio SOCI calculations of the I^-_3 potential energy surfaces, which have revealed a strong nonadiabatic nature of the I^-_3 dissociation dynamics involving dense avoided crossings among the excited-state potentials.3. Development of a cluster anion-molecule reaction apparatus : New apparatus has been developed for the investigation of collisional reactions between mass-selected negatively-charged clusters with neutrals in the collision energies ranging from few electron volts to several tens of eV. Less

One of the fundamental issues regarding chemical reactions concerns the effects of week interactions exerted by solvent on the reaction dynamics. In the present study, our efforts have been focused on the following research projects to investigate the effects of "microsolvation" in chemical reactions and to explore the new field of cluster-mediated chemistry :1. Structure of (C0_2)^-_n as a gas-phase nucleophile : The electronic structures of (CO_2)^-_n and [(CO_2)_nROH]^- (R = H, CH_3) are investigated by photoelectron spectroscopy combined with ab initio calculations, demonstrating the coexistence of isomers having different electronic structures. These "electronic isomers" are well described as [C_2O^-_4magneticROH(CO_2)_<n-2>] and [CO^-_2Magnetic ROH(CO_2)_<n-1>]. The calculations have also revealed quantitatively the behavior of the excess charge flow during the CO^-_2 magnetic CO_2.レtautomer.ロ C_2O^-_4 electronic isomerization, which might play a crucial role in the reductive activation of carbon dioxi … More in the course of gas-phase reactions mediated via (CO_2)^-_n.2. Single-molecule solvent effects in I^-_3 photodissociation. . :. . Photodissociation dynamics of gas-phase I^-_3 along with its weakly bound clusters, I^-_3 magnetic M (M = CH_3CN, C_2H_5OH), was investigated for a microscopic understanding of solvent effects on the photodissociation dynamics. The experimental results demonstrate convincingly that even single-molecule solvation results in a drastic change in the I^-/I^-_2 product branching, which opens up a possibility of controlling the photofragmentation process by exploiting week intermolecular interactions. We also performed ab initio SOCI calculations of the I^-_3 potential energy surfaces, which have revealed a strong nonadiabatic nature of the I^-_3 dissociation dynamics involving dense avoided crossings among the excited-state potentials.3. Development of a cluster anion-molecule reaction apparatus : New apparatus has been developed for the investigation of collisional reactions between mass-selected negatively-charged clusters with neutrals in the collision energies ranging from few electron volts to several tens of eV. Less

项目成果

K.Kanda et al.: "Photodissociation spectroscopy of ClCN in the vacuum ultraviolet region"Chemical Physics. 255. 369-378 (2000)

K.Kanda 等：“ClCN 在真空紫外区的光解离光谱”化学物理。

T. Tsukuda, L. Zhu, M. Saeki, and T. Nagata: "Photochemistry of (NO)^-_n as studied by photofragment mass spectrometry"International Journal of Mass Spectrometry and Ion Processes. in press..

T. Tsukuda、L. Zhu、M. Saeki 和 T. Nagata：“通过光碎片质谱法研究 (NO)^-_n 的光化学”国际质谱与离子过程杂志。

T. Tukuda, N. Kimura, T. Sasaki, and T. Nagata: "Growth mechanism of metal clusters in ligand exchange processes"Trans. Of Materials Research Soc. Of Japan. 25. 929-932 (2000)

T. Tukuda、N. Kimura、T. Sasaki 和 T. Nagata：“配体交换过程中金属簇的生长机制”Trans。

T.Tsukuda et al.: "Growth mechanism of metal clusters in ligand exchange processes"Transaction of Materials Research Society of Japan. 25. 929-932 (2000)

T.Tsukuda等人：“配体交换过程中金属簇的生长机制”日本材料研究会学报。

M. Saeki et al.: "Electronic isomers in 〔(CO_2)_nROH]^- cluster anions. II. Ab initio calculations."Journal of Chemical Physics. 111. 6333-6344 (1999)

M. Saeki 等人：“[(CO_2)_nROH]^- 簇阴离子中的电子异构体。II. 从头计算。”化学物理杂志 111. 6333-6344 (1999)