Metastability of gold-carbonyl cluster complexes, Au N(CO) M -

Smaller gold-cluster anions, typified by Au ₇ ^- , adsorb multiple CO molecules in a high-pressure, room-temperature flow-reactor, tending toward previously unknown saturation compositions, Au₇(CO) ₄ ^- . The weakness of the gold-carbonyl adsorption bond is evidenced indirectly by the high CO partial pressure required and more directly by the high probability of fragmentation in the field-free flight region of the reflectron-type time-of-flight mass spectrometer. The analysis of this metastability reveals that the actual distribution f_N,M of products Au₇(CO) _M ^- in the reactor may be highly non-statistical, e.g. with only even-M species present. Received 17 April 2001     

纳米碳管的电化学贮锂性能

用透射电镜、高分辨透射电镜、X射线衍射和拉曼光谱表征了用催化热解法制备的纳米碳管的结构,研究了纳米碳管的电化学嵌脱锂性能。以纳米级铁粉为催化剂热解乙炔气得到的纳米碳管石墨化程度较低,结构中存在褶皱的石墨层、乱层石墨和微孔等缺陷,具有国交高的贮锂容量,初始容量为640mAh/g,但循环稳定性较差。而以纳米级氧化铁粉为催化剂热解乙烯得到的纳米碳管结构比较规则,循环稳定性较好,但贮锂容量较低,初始容量为282mAh/g。讨论了纳米碳管的结构对其温度特性和不同电流密度下的充放电容易的影响。     

Molecular dynamics simulations of the freezing of gold nanoparticles

A set of molten gold clusters, each with 1157 gold atoms, was studied by molecular dynamics simulations as the clusters underwent freezing at three different temperatures. Most of the clusters attained an icosahedral structure upon freezing, a structure found to be stable to mild annealing. Other structures observed were imperfect truncated decahedral, truncated octahedral and hexagonal close packed structures. The role of kinetics in the process of cluster solidification is discussed. Received 6 November 2000     

SiC bonding in ( C 60 ) n Si m clusters

This paper deals with a new type of SiC bonding where silicon atom seems to bridge C₆₀ molecules. We have studied films obtained by deposition of (C₆₀)_nSi_m clusters prepared in a laser vaporization source. Prior deposition, free ionized clusters were studied in a time-of-flight mass spectrometer. Mixed clusters (C₆₀)_nSi_m were clearly observed. Abundance and photofragmentation mass spectroscopies revealed the relatively high stability of the (C₆₀)_nSi _n ⁺ , (C₆₀)_nSi _{n - 1} ⁺ and (C₆₀)_nSi _{n - 2} ⁺ species. This observation is in favor of the arrangement of these complexes as polymers where the C₆₀ cages may be bridged by a silicon atom. Free neutral clusters are then deposited onto substrate making up a nanogranular thin film (≃ 100 nm). The film is probed by Auger and X-ray photoemission spectroscopies, but above all by surface enhanced Raman scattering. The results suggest an unusual chemical bonding between silicon and carbon and the environment of the silicon atom is expected to be totally different from the sp³ lattice: ten or twelve carbon neighbors might surround silicon atom. The bonding is discussed to the light of the so-called fullerene polymerization as observed for pure fullerite upon laser irradiation. This opens a new route for bridging C₆₀ molecules together with an appreciable energy bonding, since the usual van der Waals bonding in fullerite could be replaced by an ionocovalent bond. Such an assumption must be checked in the future by XAS and EXAFS experiments. Received 15 November 2000     

Neutron diffraction study of the magnetic ordering in the series R 2 BaNiO 5 (R = Rare Earth)

A neutron diffraction study, as a function of temperature, of the title compounds is presented. The whole family (space group Immm, a ≈ 3.8?, b ≈ 5.8?, c ≈ 11.3?) is structurally characterised by the presence of flattened NiO₆ octahedra that form chains along the a-axis, giving rise to a strong Ni-O-Ni antiferromagnetic interaction. Whereas for Y-compound only strong 1D correlations exist above 1.5 K, presenting the Haldane gap characteristic of 1D AF chain with integer spin, 3D AF ordering is established simultaneously for both R and Ni sublattices at temperatures depending on the rare earth size and magnetic moment. The magnetic structures of R₂BaNiO₅ ( R = Nd, Tb, Dy, Ho, Er and Tm) have been determined and refined as a function of temperature. The whole family orders with a magnetic structure characterised by the temperature-independent propagation vector = (1/2, 0, 1/2). At 1.5 K the directions of the magnetic moments differ because of the different anisotropy of the rare earth ions. Except for Tm and Yb (which does not order above 1.5 K), the magnetic moment of the R³⁺ cations are close to the free-ion value. The magnetic moment of Ni²⁺ is around 1.4 , the strong reduction with respect to the free-ion value is probably due to a combination of low-dimensional quantum effects and covalency. The thermal evolution of the magnetic structures from T _N down to 1.5 K is studied in detail. A smooth re-orientation, governed by the magnetic anisotropy of R³⁺, seems to occur below and very close to T _N in some of these compounds: the Ni moment rotates from nearly parallel to the a-axis toward the c-axis following the R moments. We demonstrate that for setting up the 3D magnetic ordering the R-R exchange interactions cannot be neglected. Received 19 July 2001     

几种稠环芳烃有机EL材料性能的量子化学理论研究

采用量子化学半经验方法（ＲＨＦ／ＰＭ３）对几种稠环芳烃化合物电致发光（ＥＬ）材料的性质进行了理论研究。利用能量梯度法优化构型,对各优化的构型作振动分析,均未出现虚频率。在此基础上,采用ＲＨＦ／ＣＩＳ方法计算其电子光谱。并给出了化合物ＥＬ１,ＥＬ２电子光谱的最大波长λ与ＣＩＳ组态之间的关系。所有计算结果与实验值基本吻合。     

纳米颗粒材料表面形貌结构AFM表征中针尖干扰的修正与评价

原子力显微镜（ＡＦＭ）被广泛地用来进行纳米尺度和亚微米尺度结构材料的形貌表征,其优点是制样简单、无需进行导电处理,但会针尖与样品作用时,由于针尖自身的成像作用,导致得到的图像结果比实际结果要大,这就是针尖的放大效应,文章基于一种简单的数学模型,得到了对实测图像的修正结果,对于一般金字塔形针尖,ＡＦＭ的放大作用可导致粒子尺寸比真实尺寸大近２倍,实测图像的失真状况与针尖的形状因子、粒子的分散状态等因素     

有机小分子发光材料与聚合物发光材料在大气存放条件下的稳定性对比研究

分别采用紫外光电子能谱（UPS）、X光电子能谱（XPS）、原子力显微镜（AFM）、以及光致发光光谱（PL）等方法对在大气存放条件下的8－羟基喹啉铝（Alq)薄膜和聚（9,9－二辛烷基芴）（PFO）薄膜的电子结构、表面形 及发光特性进行了对比。研究结果表明,PFO的电子结构、表面形貌以及发光特性受外界气氛影响极小,是一种非常稳定的聚合物发光材料。这为聚合物发光器件的稳定性提供了有利的条件。     

几种含氮芳烃化合物EL材料的量子化学研究

采用量子化学半经验方法PM3对几种含氮芳烃电致发光材料(EL)的性质进 行了理论研究,对化合物FL-7,作了构象分析,找到了能量最低的构象。对各化合物优化后 的构型作振动分析,均未出现虚频率,在此基础上,采用CIS方法计算电子光谱,并给出了4 种化合物FL-4,FL-7,FL-10,FL-12的荧光光谱。所有计算结果与实验值基本吻合     

假火花开关初始放电过程的理论计算

假火花开关具有耐压高、放电电流大及电流上升速率快的优点。本文利用流体模型及当地场近似，对其放电过程进行了理论计算。结果表明，在放电初始阶段，空心阴极效应起关键作用。同时，对不同初始条件（初始电子、离子密度不同）及不同边界条件（开关结构尺寸不同）的放电过程进行了计算。给出了放电时间、放电电流、最佳阴阳极距离和阴极孔尺寸大小。