Structural and bonding properties of ScSi_n~-(n=2～6) clusters:photoelectron spectroscopy and density functional calculations

Anion ion photoelectron spectroscopy and density functional theory (DFT) are used to investigate the electronic and structural properties of ScSi_n^- (n=2sim6) clusters and their neutrals. We find that the structures of ScSi_n^- are similar to those of Si_n+1^-. The most stable isomers of ScSi_n^- cluster anions and their neutrals are similar for n=2, 3 and 5 but different for n=4 and 6, indicating that the charge effect on geometry is size dependent for small scandium-silicon clusters. The low electron binding energy (EBE) tails observed in the spectra of ScSi_4,6^- can be explained by the existence of less stable isomers. A comparison between ScSi_n^- and VSi_n^- clusters shows the effects of metal size and electron configuration on cluster geometries.     

The velocity component effect to the mass resolution within de Heer and Milani criteria

The velocity component effect to the mass resolution was considered for two different positions of beam source in the time-of-flight mass spectrometer based on de Heer and Milani criteria. The results estimated for various potassium cluster sizes showed that resolution is reduced at considerable level and the cluster range is limited to the small mass sizes for the position along with the cluster beam axis. The resolution is high and the effect appears close to K₁₀₀₀ cluster sizes depending upon perpendicular axis used.     

Thermal Disorder, Fluctuations, Growth and Fragmentation of Finite One-Dimensional Atomic Chains

Ordering in one-dimensional atomic chains is studied using computer simulation. We find that dense ordered chains may exist if the system is cold enough and not macroscopically long. Growth of finite length chains from the vapor and by vapor exchange between chains begins rapidly, then slows down exponentially in time. As temperature rises density fluctuations increase, causing the chains to fragment. Independent of fragmentation, disordering begins at the ends, a condition similar to the precursor of edge and surface melting in two and three dimensions. The chemical potential of finite ordered chains is a function of length and temperature, due to the competition between attraction and internal thermal excitation. Equilibrium of chains coexisting with one-dimensional vapor produces a distribution of sizes, peaked at a temperature dependent chain length. Several results may be relevant to experimental studies of adsorption on carbon nanotubes     

团簇LaO的理论研究

采用密度泛函理论研究LaO团簇体系。中性分子LaO的基态是两重态(2Σ),阴离子LaO-和阳离子LaO 的基态都是单重态(1Σ)。使用不同的方法计算团簇LaO的电子亲和能和电离能。计算结果表明用BLYP方法和弥散极化基组计算结果和实验数据吻合较好。用含时密度泛函理论计算团簇LaO的低能激发态,从理论上归属LaO-的光电子能谱的谱峰和LaO的吸收光谱的谱峰。计算得到与实验一致的结果。     

Stability of charged metal clusters in the vicinity of an ionic charge

Stability of highly charged metal clusters in the electric field of an external ion is investigated with the classical liquid drop model. We study the optimum shape of the cluster which has a local minimum of the total energy, taking account of the effects of the surface charge polarization on the Coulomb energy and the cluster deformation on the surface energy. We find that the cluster deformation greatly affects the total energy of the system and that a cluster with a fissility larger than some critical value 0.7-0.8 can become unstable against deformation. We investigate the local competition between the Coulomb force and the surface tension at the cluster surface and show that the surface charge polarization which is induced by the external electric field significantly affects the shape of the cluster and its stability. Received 5 November 2002 / Received in final form 27 January 2003 Published online 11 March 2003 RID="a" ID="a"e-mail: hamada@konan-u.ac.jp     

Conformally Invariant Quantization at Order Three

Let (M, g) be a pseudo-Riemannian manifold and the space of densities of degree on M. Denote the space of differential operators from to of order k and S _k with = – the corresponding space of symbols. We construct (the unique) conformally invariant quantization map . This result generalizes that of Duval and Ovsienko.     

中小尺寸CdS和CdTe团簇结构与电子性质的第一性原理研究

基于密度泛函理论(DFT)的第一性原理方法(DMOL3程序),在广义梯度近似(GGA)下,计算了中小尺寸II~VI族(CdS)n和(CdTe)n团簇的基态结构、最高占据轨道(HOMO)和最低未占据轨道(LUMO)的能隙、结合能等,比较了(CdS)n和(CdTe)n两种团簇的基态结构,能隙与结合能随尺寸变化关系的差异等.     

Fabrication and characterization of SERS‐active silver clusters on glassy carbon

In this article, a novel technique for the fabrication of surface enhanced Raman scattering (SERS) active silver clusters on glassy carbon (GC) has been proposed. It was found that silver clusters could be formed on a layer of positively charged poly(diallyldimethylammonium) (PDDA) anchored to a carbon surface by 4‐aminobenzoic acid when a drop containing silver nanoparticles was deposited on it. The characteristics of the obtained silver clusters have been investigated by atomic force microscopy (AFM), SERS and an SERS‐based Raman mapping technique in the form of line scanning. The AFM image shows that the silver clusters consist of several silver nanoparticles and the size of the clusters is in the range 80–100 nm. The SERS spectra of different concentrations of rhodamine 6G (R6G) on the silver clusters were obtained and compared with those from a silver colloid. The apparent enhancement factor (AEF) was estimated to be as large as 3.1 × 10⁴ relative to silver colloid, which might have resulted from the presence of ‘hot‐spots’ at the silver clusters, providing a highly localized electromagnetic field for the large enhancement of the SERS spectra of R6G. The minimum electromagnetic enhancement factor (EEF) is estimated to be 5.4 × 10⁷ by comparison with the SERS spectra of R6G on the silver clusters and on the bare GC surface. SERS‐based Raman mapping technique in the form of line scanning further illustrates the good SERS activity and reproducibility on the silver clusters. Finally, 4‐mercaptopyridine (4‐Mpy) was chosen as an analyte and the lowest detected concentration was investigated by the SERS‐active silver clusters. A concentration of 1.6 × 10⁻¹⁰ M 4‐Mpy could be detected with the SERS‐active silver clusters, showing the great potential of the technique in practical applications of microanalysis with high sensitivity. Copyright © 2006 John Wiley & Sons, Ltd.     

Photoinduced dissociation reactions of silver fluoride cluster ions

Photoinduced dissociation in the ultraviolet region has been investigated for Ag _nF _n-1 ⁺ cluster ions. Photodissociation spectrum of Ag₂F⁺ in the energy of 3.8–5.6 eV exhibits several sharp bands corresponding to the transition to electronically excited states. In this dissociation, only the Ag₂ ⁺ ion was observed as a fragment ion. Theoretical calculation indicates that the parent Ag₂F⁺ ion has a linear Ag-F-Ag equilibrium geometries in the ground and excited states. Since conformational changes by excitation of bending vibration are necessary for the fragmentation of an F atom, this indicates that production of Ag₂ ⁺ from Ag₂F⁺ is a result of internal conversion and following conformational changes.     

Cooling efficiency in collisions between Pd and He,Ne, Ar and Kr

The cooling of the metal cluster Pd₁₃ in an atmosphere of rare gas has been studied by means of computer simulation. By simulation, the average energy transfer in collisions between one cluster and one gas atom has been obtained. Emphasis has been placed on conditions when the temperatures of the colliding species are almost equal. All modes of motion, inclusive the translation, must be considered in order to obtain vanishing energy transfer at equilibrium. A simulation scheme is presented by which the energy transfer is zero to the cluster when the gas and the cluster temperatures are equal. At equilibrium the energy transfer does however not vanish for all impact parameters. In the collisions with Pd₁₃, the cluster is heated by collisions with a small impact parameter but equally cooled by collisions with a large impact parameter. Argon and krypton are found to cool Pd₁₃ equally efficiently while neon and helium are less efficient cooling agents. Received 28 September 2001 / Received in final form 8 August 2002 Published online 12 November 2002 RID="a" ID="a"e-mail: JanW@phc.gu.se