Co@Aun(n=1-8)团簇的几何结构和电子性质的理论研究

本文利用密度泛函PW91方法研究了Co@Aun(n=1-8)团簇的平衡结构、稳定性和磁矩。结构优化显示Co原子在低能异构体中趋于占据最高配位位置,基态Co@Aun(n=2-6)团簇为二维结构,Co@Au7和Co@Au8转变为三维结构。原子平均结合能、二阶能量差分及HOMO-LUMO能级间隙分析表明掺杂Co原子提高了金团簇的稳定性,改变了金团簇能级间隙的奇偶振荡性,n=5为掺杂团簇的幻数。磁矩的计算揭示Co@Aun团簇的磁性主要源于Co原子的3d轨道。     

(TiO2)n(n=3—6)团簇吸附水分子的理论研究

给出了优化小分子在团簇表面吸附结构的遗传算法.结合经验势函数,搜寻了水分子在(TiO₂)_n(n=3—6)团簇上可能的吸附方式;利用B3LYP/6-31G^**方法对各种吸附结构进行了优化.结果表明水分子主要通过O原子以非解离方式吸附到团簇中配位数较低或位置比较凸出的Ti原子上.分子轨道分析表明,水分子与团簇之间的成键主要来自吸附位Ti原子3s3p轨道的贡献,水分子的轨道保持了气相水分子中的基本特征,但离域化程度增大 关键词： 2团簇')" href="#">TiO₂团簇 2O吸附')" href="#">H₂O吸附 遗传算法 DFT     

Application of the multireference equation of motion coupled cluster method,including spin–orbit coupling,to the atomic spectra of Cr,Mn, Fe and Co

The recently introduced multireference equation of motion (MR-EOM) approach is combined with a simple treatment of spin–orbit coupling, as implemented in the ORCA program. The resulting multireference equation of motion spin–orbit coupling (MR-EOM-SOC) approach is applied to the first-row transition metal atoms Cr, Mn, Fe and Co, for which experimental data are readily available. Using the MR-EOM-SOC approach, the splittings in each L-S multiplet can be accurately assessed (root mean square (RMS) errors of about 70 cm^?1). The RMS errors for J-specific excitation energies range from 414 to 783 cm^?1 and are comparable to previously reported J-averaged MR-EOM results using the ACESII program. The MR-EOM approach is highly efficient. A typical MR-EOM calculation of a full spin–orbit spectrum takes about 2 CPU hours on a single processor of a 12-core node, consisting of Intel XEON 2.93 GHz CPUs with 12.3 MB of shared cache memory.     

Direct Observation of the Binding Mode of the Phosphonate Anchor to Nanosized Polyoxotitanate Clusters

The structures of three newly synthesized phosphonate‐substituted polyoxotitanates are reported. The Ti/O core of [Ti₄O(OEt)₁₂(PhenylPO₃)] ( 1 ) is the building block for two larger phosphonate‐substituted nanoclusters, [Ti₂₅O₂₆(OEt)₃₆(PhenylPO₃)₆] ( 2 ) and [Ti₂₆O₂₆(OEt)₃₉(PhenylPO₃)₆]Br ( 3 ). All compounds exhibit a not previously recognized triply bridging binding mode of the phosphonate anchor with short connecting Ti? O bonds, the average of which is 2.010(7) Å. Comparison with previously reported work suggests that the binding mode of the phosphonate anchor is strongly dependent on the structure of the underlying substrate.     

低能C36团簇在金刚石(100)晶面沉积时的影响因素

"使用Brenner-LJ拟合势描述了金刚石与C36团簇原子间的相互作用,并用分子动力学模拟的方法研究单个C36(D6h)在金刚石(100)晶面的沉积机制．通过仿真实验分析了C36团簇的入射能量、入射点位置、入射姿势、入射角度等因素对其成核初期化学吸附过程以及沉积后其稳定性的影响．研究发现：由于C36入射点位置及入射姿势的不同,其在金刚石(100)晶面沉积时的沉积阈值最小值为20 eV,最大值为60 eV;在入射角不超过60o斜射时,由于水平运动分量的存在,C36可能翻滚及平滑至成键能量较小的区域后再成键     

面向数据挖掘的静态电源综合故障诊断研究

静态电源是机场桥载设备最重要的组成部件之一,应用非常广泛。然而,其产生的频发故障会造成设备利用率低、修复率时长和经济损失等问题,在基于桥载设备的安监系统上,提出了静态电源综合故障诊断方法,通过数据挖掘软件,建立了静态电源故障诊断预测模型。通过在线数据库测试结果表明得到了综合故障诊断方法在预测静态电源故障上显现的特点,得到了静态电源的未来状态,实现了对静态电源的实时故障进行预测,进而为解决故障提供方向和目标,最终达到降低经济损失最大化的目的。     

Analysis of plant genomic DNAs and the genetic relationship among plants by using surface-enhanced Raman spectroscopy

The study aimed to distinguish genomic DNAs from nine species of plants belonging to six families and analyze their genetic relationship by using surface-enhanced Raman scattering (SERS). The silver nano-colloid and excitation wavelength of 785 nm used in this study yielded excellent quality of the SERS spectra. Raman signals were remarkably enhanced. Although the spectra for the nine species of plants appeared very similar, there were significant differences according to the analysis of variance analysis. There were three strong characteristic peaks. The peak at 625 cm⁻¹ was due to the vibration overlap of C3′-endo/anti deoxyribose, cytosine, and guanine; the one at 715 cm⁻¹ was due to the scissoring vibrations of C2N1C6 of adenine; and that at 1011 cm⁻¹ was due to the stretching vibration of the CO bond of deoxyribose and vibrations of cytosine. The SERS data were smoothed and standardized and evaluated using second derivative analysis, principal component analysis, and hierarchical cluster analysis. A model was established using the data from hierarchical cluster analysis and principal components of the second derivative. The clustering result of this model was highly consistent with the traditional classification of plants; all plant species investigated were correctly clustered into classes according to the cluster distance coefficient among them; the accuracy of clustering was 100%. Chinese cabbage (Brassica pekinensis Rupr.) and green cabbage (Brassica chinensis L.) belonging to Cruciferae, maize (Zea mays L.) and bamboo (Sinocalamus affinis McClure) belonging to Gramineae, and magnolia (Magnolia delavayi Franch.) and champaca (Michelia alba DC.) belonging to Magnoliaceae were clustered into three separate classes, and fern (Nephrolepis auriculata L., Nephrolepidaceae), garlic (Allium sativum L., Amaryllidaceae), and ginkgo (Ginkgo biloba L., Ginkgoaceae) were each clustered into separate classes. These findings suggest that the SERS spectra of plant genomic DNAs can be used to classify species and analyze their genetic relationship. It is an effective and perfect supplement to traditional classification and can form the basis for genetic analysis.     

Protecting structure analyses of organic molecule-protected nanoscopic noble metal clusters

The stabilizing structure of cationic surfactant-protected platinum clusters in water and tertiary amine-protected rhodium clusters in chloroform, prepared by photo- and hydrogen-reduction, respectively, was investigated. These nanoscopic noble metal clusters present a narrow size distribution and are stable. The structural information of protective organic molecules on the surface of metal clusters was studied by transmission electron microscopy and hydrodynamic radius measurements according to the Taylor dispersion method. The size of the entire cluster with the protective layer surrounding the metal surface, obtained as Stokes' radii by the Taylor dispersion method, is considered to be fairly consistent with the sum of the naked particle size, obtained by transmission electron micrographs, and the size of the adsorbed protective layer, supporting the conformational information.     

Heteroctanuclear Au4Ag4 Cluster Complexes of 4,5-Diethynylacridin-9-One with Luminescent Mechanochromism

Two heteroctanuclear Au₄Ag₄ cluster complexes of 4,5-diethynylacridin-9-one (H₂L) were prepared through the self-assembly reactions of [Au(tht)₂](CF₃SO₃), Ag(tht)(CF₃SO₃), H₂L and PPh₃ or PPh₂Py (2-(diphenylphosphino)pyridine). The Au₄Ag₄ cluster consists of a [Au₄L₄]⁴⁻ and four [Ag(PPh₃)]⁺ or [Ag(PPh₂Py)]⁺ units with Au₄L₄ framework exhibiting a twisted paper clip structure. In CH₂Cl₂ solutions at ambient temperature, both compounds show ligand fluorescence at ca. 463 nm as well as phosphorescence at 650 nm for 1 and 630 nm for 2 resulting from admixture of ³IL (intraligand) of L ligand, ³LMCT (from L ligand to Au₄Ag₄) and ³MC (metal-cluster) triplet states. Crystals or crystalline powders manifest bright yellow-green phosphorescence with vibronic-structured emission bands at 530 (568sh) nm for complex 1 and 536 (576sh) nm for complex 2. Upon mechanical grinding, yellow-green emission in the crystalline state is dramatically converted to red luminescence centered at ca. 610 nm with a drastic redshift of the emission after crystal packing is destroyed.