Molecular Spectroscopy and Chemical Reactions of Molecular Clusters : Computational Studies

分子光谱和分子簇的化学反应：计算研究

• 批准号: 09304057
• 负责人: IWATA Suehiro
• 金额: $ 23.87万
• 依托单位: OKAZAKI NATIONAL RESEARCH INSTITUTES
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09304057/
• 关键词: Computational Chemistry; Quantum Chemistry; Molecular Clusters; Water Clusters; Photoelectron Spectrum

1) The noble structures of water cluster anions (H2O)n- were found in a series of ab initio molecular orbital calculations. The excess electron is trapped under the electrostatic field of HO bonds of water molecules. The similar structure was found in the water cluster complexes with the group 1 metal atom, M(HィイD22ィエD2O)ィイD2nィエD2 (n≧4). In the complexes, the metal atom is ionized, and the ejected electron is trapped within HO bonds. The ionization threshold of the complexes are size-independent as well as metal-independent.2) The coupling of the OH stretching with the intermolecular O-X stretching and O-X-H bending was examined for XィイD1-ィエD1(HィイD22ィエD2O) complex anions (X=F, Cl, Br and I). The observed vibrational bands for X=Cl are assigned if the internal energy of the anions is high.3) By combining the multicanonical sampling for Monte-Carlo simulation, the reweighting technique and the ab initio MO calculations, the temperature dependence of averaged structures of water dimers was examined. A few changes of the dominant structures were found. At high temperature, the structures similar to the transition states, which are entropy-favored, are dominant.The technique was applied for successfully assigning the photoelectron spectrum of SiィイD22ィエD2CィイD22ィエD2ィイD1-ィエD1, which was recently experimentally reported.

1）水簇阴离子（H2O）n-的贵族结构在一系列的初始分子轨道计算中发现。多余的电子被困在水分子HO键的静电场下。与1组金属原子M（HII D22IE D2O）II D2NIE D2（n≧4）的水簇复合物中发现了相似的结构。在复合物中，金属原子被离子化，并且弹出电子被困在HO键内。复合物的电离阈值与金属无关。如果阴离子的内部能量较高，则分配了X = Cl的观察到的振动带。发现了一些主要结构的变化。在高温下，类似于熵最大的过渡状态的结构是主要的。该技术用于成功分配SII D22，D22，D22，D22，D22，D1-IE D1的光电谱，最近进行了实验报告。

项目成果

H. Watanabe, S. Iwata: "Theoretical assignment of the photo-dissociation excitation spectra of the Mg^+ion complexes with water clusters: Multi-reference Cl studies"J. Chem. Phys. 108. 10078-10083 (1998)

H. Watanabe，S. Iwata：“Mg^2 离子与水簇络合物的光解离激发光谱的理论分配：多参考 Cl 研究”J。

A. Fiedler, S. Iwata: "Variety of [Fe, N, O] isomers. A theoretical study"J. Phys. Chem.. 102. 3618-3624 (1998)

A. Fiedler、S. Iwata：“[Fe、N、O] 异构体的多样性。理论研究”J。

F.R. Ornellas, S. Iwata: "A theoretical study of the electronic structure and spectroscopic properties of the low-lying electronic states of the molecule AlSi"Chem. Phys.. 232. 95-110 (2998)

FR.

T. Ikegami, S. Iwata: "Intracluster Reaction Dynamics of ArィイD24ィエD2ィイD1+ィエD1."Ed.by Fueno, Transition State Theory. (in press). (1998)

T. Ikegami、S. Iwata：“AriD24D2D1+D1 的簇内反应动力学”，Fueno 编着，过渡态理论（1998 年出版）。

S. I.. Gheyas, T. Uris, S. Hirano, H. Watanabe, S. Iwata, M. Aoyagi, M. Nishino and H. Ogawa: "Chemisorption of Deuterium on an Ultrathin Ge Film Deposited over Si(100)-2x1: Existence of a Dideuteride Phase"Phys. Rev. B.. 58. 9949-9954 (1998)

S. I.. Gheyas、T. Uris、S. Hirano、H. Watanabe、S. Iwata、M. Aoyagi、M. Nishino 和 H. Okawa：“沉积在 Si(100)-2x1 上的超薄 Ge 薄膜上氘的化学吸附：