Comparison of the Bonding of Benzene and C60 to a Metal Cluster: Ru3(CO)9(μ3-η2,η 2,η2-C6H6) and Ru3(CO)9(μ3-η2,η2,η2-C60)

The electron distributions and bonding in Ru₃(CO)₉( ³- ², ², ²-C₆H₆) and Ru₃(CO)₉( ³- ², ², ²-C₆₀) are examined via electronic structure calculations in order to compare the nature of ligation of benzene and buckminsterfullerene to the common Ru₃(CO)₉ inorganic cluster. A fragment orbital approach, which is aided by the relatively high symmetry that these molecules possess, reveals important features of the electronic structures of these two systems. Reported crystal structures show that both benzene and C₆₀ are geometrically distorted when bound to the metal cluster fragment, and our ab initio calculations indicate that the energies of these distortions are similar. The experimental Ru–C_fullerene bond lengths are shorter than the corresponding Ru–C_benzene distances and the Ru–Ru bond lengths are longer in the fullerene-bound cluster than for the benzene-ligated cluster. Also, the carbonyl stretching frequencies are slightly higher for Ru₃(CO)₉( ³- ², ², ²-C₆₀) than for Ru₃(CO)₉( ³- ², ², ²-C₆H₆). As a whole, these observations suggest that electron density is being pulled away from the metal centers and CO ligands to form stronger Ru–C_fullerene than Ru–C_benzene bonds. Fenske-Hall molecular orbital calculations show that an important interaction is donation of electron density in the metal–metal bonds to empty orbitals of C₆₀ and C₆H₆. Bonds to the metal cluster that result from this interaction are the second highest occupied orbitals of both systems. A larger amount of density is donated to C₆₀ than to C₆H₆, thus accounting for the longer metal–metal bonds in the fullerene-bound cluster. The principal metal–arene bonding modes are the same in both systems, but the more band-like electronic structure of the fullerene (i.e., the greater number density of donor and acceptor orbitals in a given energy region) as compared to C₆H₆ permits a greater degree of electron flow and stronger bonding between the Ru₃(CO)₉ and C₆₀ fragments. Of significance to the reduction chemistry of M₃(CO)₉( ³- ², ², ²-C₆₀) molecules, the HOMO is largely localized on the metal–carbonyl fragment and the LUMO is largely localized on the C₆₀ portion of the molecule. The localized C₆₀ character of the LUMO is consistent with the similarity of the first two reductions of this class of molecules to the first two reductions of free C₆₀. The set of orbitals above the LUMO shows partial delocalization (in an antibonding sense) to the metal fragment, thus accounting for the relative ease of the third reduction of this class of molecules compared to the third reduction of free C₆₀.     

试论电子出版物呈缴制度设计的若干问题

通过对国外电子出版物呈缴制度建设特点和经验的分析,阐述了我国电子出版物呈缴制度的设计问题.     

ArcGIS在武夷山保护区林业有害生物分布电子地图制作中的应用

本文详细介绍了利用ArcG IS 9.0制作林业有害生物分布电子地图的方法,包括创建要素图层,建立连接,数据符号化以及图层标注。     

基于ebXML的电子商务交易系统的DTD模型

Web服务并非设计用来帮助标准商业流程的规划和建模,所以在用于电子商务中存在一些技术问题。本文在ebXML体系结构应用的基础上,提出基于ebXML技术建构电子商务交易模型,并以网上书店为试用例实现其交易系统。     

网络时代合同法的最新发展

目前，联合国贸法会电子商务工作组的核心工作是在合同法领域起草一个有关电子订约的公约。电子合同的规则集中反映了网络时代合同法的最新发展。在信息技术的推动下，网络时代的合同法发生了巨大的演变，电子合同产生了许多不同于传统合同的法律规则，其中典型的电子合同法律规则有：电子形式规则、电子意思表示规则、电子签名与认证规则以及计算机信息交易合同中的电子错误规则和电子自助规则等。     

TiFe合金电子结构与储氢性能的相关性研究

利用电荷自洽离散变分(SCC—DV—Xa)电子结构计算方法，计算TiFe储氢合金及其氢化物的电子结构，分析电子结构与储氢性能的相关性。结果表明，在TiFe合金氢化物中，H原子进入八面体晶胞中，H原子与Fe原子间成键作用明显比H原子与Ti原子间的成键作用强，使晶胞体积主要沿晶格的[110]方向发生膨胀；TiFe合金八面体晶胞中Ti原子与Fe原子间形成离域键，在吸氢后成键作用有所增强，使合金吸氢后的体积膨胀率较小，这是其反复吸放氢过程不容易粉化的原因之一。     

圆纬机电脑提花的花型数据准备

对单面3工位电子选针的花型数据准备及其算法作了较全面的论述。对提花原理、花型准备系统进行了阐述，探讨了3类花数据及其相互转换的方法，为电子提花圆纬机花型软件的开发提供一些理论基础。     

一类特殊的LF-网空间

本文研究了LF-网空间和它的几个子空间类,考虑了LF-k-网空间与几类广义度量化空间的关系,并且给出了LF-k-网空间的一个等价条件.     

磁浮轴承转子系统的稳定性研究

针对非线性磁浮轴承转子系统的具体特点，用数值积分和庞加莱映射方法对刚性磁浮轴承转子系统进行稳定性研究，得到了系统在某些参数域中的时域波形、频谱图、相图、轴心轨迹以及庞加莱映射图，并给出了系统产生混沌运动诱发失稳的参数域。为更好控制磁浮轴承转子系统运行状态提供理论参考。     

Pattern formation in Rayleigh-Bénard convection: Numerical simulation with a coupled-map-lattice model

The various patterns formed in Rayleigh-Bénard convection under different conditions are numerically simulated with a coupled-map-lattice model. In the case of a lower aspect ratio (L/d=5), the simulations vividly depicted the main features of the transition process from a laminar state to a soft turbulence and then to a hard turbulence. In this case, the cellular structure in a horizontal section is also reproduced. In the case of a larger aspect ratio (L/d=30), the simulations successfully reproduced the spiral-defect chaos and target chaos in the initial stage of the pattern evolution which were recently found in experiments. In this case, for a fluid ofPr=1, it is verified in simulations that both the ideal straight rolls and spiral-defect chaos are stable attractors in the same parameter regime, and that the initial condition is a decisive factor for which one of the two is formed. In the same case, for a fluid ofPr=4, the target patterns are dominant instead of the spirals, the sizes and distributions of the target are also notably dependent on the initial condition.