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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

基本信息

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

项目摘要

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)通过一系列从头算分子轨道计算，发现了水簇阴离子（H2O）n-的惰性结构。多余的电子被困在水分子HO键的静电场下。在含有1族金属原子的水簇配合物中，也发现了类似的结构，M（H (φ φ φ) φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ）。在配合物中，金属原子被电离，射出的电子被困在HO键中。配合物的电离阈值与尺寸无关，也与金属无关。2)哦拉伸与分子间的耦合O-X拉伸和O-X-H弯曲检查XィイD1 -ィエD1 (HィイD22摊位ィエD2O)复杂阴离子(X = F, Cl, Br和我)。如果阴离子的内能较高，则X=Cl所观察到的振动带。3)结合蒙特卡罗模拟的多谐采样、重加权技术和从头算MO计算，研究了水二聚体平均结构对温度的依赖关系。主要结构发生了一些变化。在高温下，与过渡态相似的、熵有利的结构占主导地位。该技术已成功地应用于Si的光电子能谱的分配，并在最近的实验中得到了报道。