Theoretical Studies of Electronic Structure of Metal Clusters

金属团簇电子结构的理论研究

• 批准号: 05453024
• 负责人: IWATA Suehiro
• 金额: $ 4.8万
• 依托单位: OKAZAKI NATIONAL RESEARCH INSTITUTES (1994)Keio University (1993)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05453024/
• 关键词: metal cluster; many-electron theory; photoelectron spectroscopy; water cluster; reacton in clusters; 励起状態

1) Electronic structure in metal clusters is very different from those of bulk metal and of ordinal molecules. We try to develop the many-electron theory for small metal clusters from molecular orbital stand point.2) To analyze the experimental findings by Kaya's group in Keio University, the geometric and electronic structures of the binary clusters such as AlnSm, AlnNa, SinNa, SinCm, and their cations and anions are studied with ab intio MO methods. The size dependence of photoelectron spectra are successfully analyzed.3) The complexes and their reactions of groups 2 and 3 atoms (ions) with water clusters are studied with ab initio MO methods. The equilibrium constants of the reactions are evaluated and are compared with the experimental mass distribution in the time of flight (TOF) spectra reported by Fuke's group in Institute for Molecular Science. A peculiar intra-cluster reactions are found in the reaction of B+ with water clusters.4) The hydrogen boding complexes of phenol and water clusters are studied with ab initio MO methods. By comparing the theoretical infra-red (IR) absorption spectra with the experimental IR-ion dip spectra, the structures of the complexes are determined for the complexes with less than five waters. The spectra are systematical compared with those of pure water clusters, and the characteristics of the vibrational motion of in water clusters are elucidated.

1)金属团簇的电子结构与块体金属和有序分子的电子结构有很大的不同。2)为了分析庆应大学Kaya等人的实验结果，用从头算方法研究了AlnSm、AlnNa、SinNa、SinCm等二元团簇及其阳离子和阴离子的几何结构和电子结构。3)用从头算方法研究了2、3族原子(离子)与水原子团簇的络合物及其反应。计算了反应的平衡常数，并与Fuke在分子科学研究所报道的飞行时间(TOF)谱中的实验质量分布进行了比较。4)用从头算方法研究了苯酚与水团簇的氢键络合物。通过比较理论红外吸收光谱和实验红外离子浸渍光谱，确定了水含量小于5的配合物的结构。并与纯水团簇的光谱进行了系统的比较，阐明了水中团簇的振动运动特征。

项目成果

T.Ikegami: "Theoretical Studies on the Non-Adiabatic Photodissociation Process of Argon Cluster Ar_7^+" Int.J.Quantum Chem.Symp.28. 529-539 (1994)

T.Ikegami：“氩团簇 Ar_7^ 非绝热光解离过程的理论研究” Int.J.Quantum Chem.Symp.28。

Chang-Guo Zhan: "Ab Initio Studies on the Structures and Vertical Electron Detachment Energies of Copper-Water Negative Ion Clusters Cu ^- (H_2O) _n and CuOH^- (H_2O) _<n-1>" Chem.Phys.Lett.232. 72-784 (1995)

詹昌国：“铜-水负离子簇 Cu ^- (H_2O) _n 和 CuOH^- (H_2O) _<n-1> 结构和垂直电子脱离能的从头计算” Chem.Phys.Lett

T.Kobayashi: "Theoretical studies of ammonia-halogen and methylamine-halogen complexes:Geometries,harmonic vibrational frequencies and their infar-red intensities,and excited states of ammonia-chlorine monofluoride complex." Bull.Chem.Soc.Jpn.67. 3172-317

T.Kobayashi：“氨-卤素和甲胺-卤素配合物的理论研究：氨-一氟化氯配合物的几何形状、谐振频率及其远红光强度以及激发态。”

A.Nakajima: "Photoelectron spectroscopy of Al_nS-clusters(n=1-9)" J.Chem.Phys.102. 660-665 (1995)

A.Nakajima：“Al_nS 团簇的光电子能谱（n=1-9）”J.Chem.Phys.102。

R.Kishi: "Theoretical Study of Silicon-Sodium Binary Clusters:Geometrical and Electronic Structures of Si_nNa(n=1,7)" Chem.Phys.Lett.224. 200-206 (1994)

R.Kishi：“硅钠二元团簇的理论研究：Si_nNa(n=1,7)的几何和电子结构”Chem.Phys.Lett.224。