Theory and Computation methods for the Design and Reaction of Nonomolecules

非分子设计和反应的理论和计算方法

• 批准号: 14340225
• 负责人: NAGASE Shigeru
• 金额: $ 9.47万
• 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 (B)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14340225/
• 关键词: Molecular Theory; Parallel Calculation; Nanostructure; Multiple Bond; Heavier Atoms; Fullerene; Nanotube; Functionalization; ナノ分子; 分子設計; 並行計算; 金属内包フラーレン; ドーピング効果; ナノ構造分子

(1)Efficient theoretical and computational methods as well as parallelization algorithms were developed, which are useful for high-speed ab initio and density functional calculations at reliable levels.(2)By introducing very bulky silyl groups, stable silicon-silicon triply bonded compounds were theoretically predicted which are currently the focus of considerable interest in main group chemistry.(3)Temperature dependence of entropy effects were systematically investigated to predict the isomer distributions of representative metallofullerenes such as Ca@C_<72>, Ca@C_<74>, Ca@C_<82>, and La@C_<82>.(4)The random circular motion of two La atoms in La_2@C_<80> can be highly controlled by attaching exohedrally electron-donating molecules such as disilirane. It is expected that the restricted motion will help to induce a unique electronic or magnetic field. The spin densities on N and P in N@C60 and P@C60 are also controlled upon exohedral addition of disilirane. It is also verified how the electronic properties of single-walled carbon nanotubes are modified by endohedral organomolecule-doping.(5)Structural and electronic properties of metal-doped silicon and germanium clusters were investigated to reveal how the formation of endohedral structures depend on the size of clusters. Modulation and tuning of homoaromaticity of silicon and germanium polyhedral molecules are also investigated.

（1）开发了有效的理论和计算方法以及平行化算法，这些算法可用于可靠水平的高速促进和密度功能计算。（2）通过引入非常稳定的硅藻基团，稳定的硅硅硅硅质粘结式键合的化合物的理论上是有意义的，这是良好的组成型的焦点。为了预测代表性金属氟烯的异构分布，例如CA@c_ <72>，ca@c_ <74>，ca@c_ <82>和la@c_ <82>。（4）在la_2@c_ <80>中，可以通过附加exohehedrally electron-diveare molecules arecules and c_ <80>在La_2@c_ <80>中高度控制的两个LA原子的随机圆形运动。预计受限制的运动将有助于诱导独特的电子或磁场。 N@C60和P@C60的N和P上的旋转密度也得到了disilirane的外部添加。还验证了如何通过内hor有机分子掺杂来修饰单壁碳纳米管的电子性能。（5）金属掺杂硅和锗簇的结构和电子性能如何研究以揭示内形内结构的形成如何取决于夹子尺寸的内膜结构的形成。还研究了硅和多面体分子的同质性调节和调节。

项目成果

A.Sekiguchi: "The First Halogen-Substituted Cyclotrigermenes : A Unique Halogen Walk over the Three-Membered Ring Skeleton and Facial Stereoselectivity in the Diels-Alder Reaction"J. Am. Chem. Soc.. 124. 1158-1159 (2002)

A.Sekiguchi：“第一个卤素取代的环三甲烯：独特的卤素在三元环骨架上行走和狄尔斯-阿尔德反应中的面立体选择性”J。

J.Lu: "Structural and Electronic Properties of Metal-Encapsulated Silicon Clusters in a Large Size Range"Phys.Rev.Lett.. 90. 115506-115510 (2003)

J.Lu：“大尺寸范围内金属封装硅团簇的结构和电子特性”Phys.Rev.Lett.. 90. 115506-115510 (2003)

J.Kobayashi: "Synthesis, Structure, and Bonding Properties of 5-Carbaphophatranes : A New Class of Main Group Atrane"J. Am. Chem. Soc.. 124. 3703-3712 (2002)

J.Kobayashi：“5-Carbaphophatranes 的合成、结构和键合特性：一类新的主族阿曲烷”J.

J.Lu: "Structural and Electronic Properties of Metal-Encapsulated Silicon Clusters in a Large Size Range"Phys.Rev.Lett.. 90. 115506-1-115506-4 (2003)

J.Lu：“大尺寸范围内金属封装硅簇的结构和电子特性”Phys.Rev.Lett.. 90. 115506-1-115506-4 (2003)

永瀬 茂: "現代化学への入門17「分子理論の展開」"岩波書店. 167 (2002)

长濑茂：“现代化学导论 17 ‘分子理论的发展’”岩波书店 167 (2002)。