Density Functional Calculation of the Photoelectron Emission Spectra of BiSCl Crystal and Molecular Clusters

The photoelectron emission spectra of BiSCl crystal and molecular clusters have been calculated by the Density Functional Theory (DFT) method. Molecular clusters consists from 2 to 20 molecules in one double chain along z(c) axis. Total and partial density of states of BiSCl crystal and clusters have been weighted with atomic photoemission emission cross-section. The molecular clusters have been investigated including all normal modes of vibration. Theoretical results of BiSCl crystal and molecular clusters have been compared with experimental X-ray photoelectron emission spectra (XPS) of BiSI crystal.     

Chemistry of tantalum clusters in solution and on SiO2 supports: analogies and contrasts

Tantalum clusters have been synthesized from Ta(CH2Ph)5 on the surface of porous fumed SiO2. When these clusters are small, incorporating, on average, several Ta atoms, their chemistry is similar to that of molecular tantalum clusters (and other early transition-metal) clusters. For example, The Ta-Ta bonds in these small supported clusters have been characterized by extended X-ray absorption fine structure (EXAFS), IR, and UV-vis spectroscopy, being similar to those in molecular analogues. The redox reactions of the supported clusters, characterized by X-ray absorption near-edge structure, are analogous to those of early transition-metal clusters in solution. In contrast to the largest of these clusters in solution and in the solid state, those supported on SiO2 are raftlike, facilitating the substantial metal-support-oxygen bonding that is evident in the EXAFS spectra. Samples consisting of tantalum clusters on SiO2 catalyze alkane disproportionation and the conversion of methane with n-butane to give other alkanes, but catalytic properties of analogous clusters in solution have barely been explored.     

Formation and stability of charged amino acid clusters and the role of chirality

Amino acid clusters have been studied by several groups and most notably magic number clusters and chiral recognition have been reported. In this work, we have studied the formation of amino acid clusters by electrospray ionization (ESI) and their stability by high-energy collision-induced dissociation (CID). Appearance sizes were determined for multiply charged clusters where the charge is either due to protons or to sodium ions. Finally, we conclude that chiral selectivity plays an important role in cluster formation but seems to be of minor importance for the fragmentation of mixed clusters.     

Recent Developments of Tellurium- and Selenium-Containing Iron Carbonyl Clusters

In recent years, quite a number of tellurium-or selenium-containing iron carbonyl clusters have been synthesized and structurally characterized, and some interesting structural transformations and reactivity of these clusters have been systematically investigated as well. The syntheses and reactivity of these clusters are reviewed and compared.     

M4C9+(M = Ti, V): New gas phase clusters

New metal-carbon clusters, M₄C₉ ⁺ (M = Ti, V), generated using a combined thermal arc discharge evaporation set-up, have been studied with quadrupole mass spectrometry. Reactivities of these clusters have been investigated by means of association reactions with H₂O. Metal-carbon clusters of other compositions have also been studied. We speculate on the mechanism of formation of larger metal-carbon clusters.     

Chiral recognition in diaziridine clusters and the problem of racemization waves

Theoretical calculations (B3LYP/6-31+G**) of chiral clusters of diaziridines have been carried out. Five configurations of chiral and nonchiral clusters with up to eight monomers have been considered. The proton transfer within the neutral and protonated clusters has been studied as a possible source of racemization waves. The optical rotatory power (ORP) has been calculated for the neutral and protonated homochiral clusters. The results show that the clusters with alternated chiral molecules are the preferred ones and that the proton transfer proceeds with low energetic barriers in the protonated systems. The ORP results are very dependent on the shape of the clusters and the neutral or protonated state of them.     

Adsorption of polar molecules on krypton clusters

The formation process of binary clusters has been studied using synchrotron based core level photoelectron spectroscopy. Free neutral krypton clusters have been produced by adiabatic expansion and doped with chloromethane molecules using the pickup technique. The comparison between the integrated intensities, linewidths, and level shifts of the cluster features of pure krypton and of chloromethane-krypton clusters has been used to obtain information about the cluster geometry. We have shown that most of the chloromethane molecules remain on the surface of the clusters.     

Size selective spectroscopy of Se microclusters

The electronic structure and photofragmentation in outer and inner valence regions of Se(n) (n ≤ 8) clusters produced by direct vacuum evaporation have been studied with size-selective photoelectron-photoion coincidence technique by using vacuum-ultraviolet synchrotron radiation. The experimental ionization potentials of these clusters were extracted from the partial ion yield measurements. The calculations for the possible geometrical structures of the Se(n) microclusters have been executed. The ionization energies of the clusters have been calculated and compared with the experimental results. In addition, theoretical fragment ion appearance energies were estimated. The dissociation energies of Se(n) clusters were derived from the recurrent relation between the gas phase enthalpies of the formation of corresponding cationic clusters and experimental ionization energies.     

Gas-phase structures of neutral silicon clusters

Vibrational spectra of neutral silicon clusters Si(n), in the size range of n = 6-10 and for n = 15, have been measured in the gas phase by two fundamentally different IR spectroscopic methods. Silicon clusters composed of 8, 9, and 15 atoms have been studied by IR multiple photon dissociation spectroscopy of a cluster-xenon complex, while clusters containing 6, 7, 9, and 10 atoms have been studied by a tunable IR-UV two-color ionization scheme. Comparison of both methods is possible for the Si(9) cluster. By using density functional theory, an identification of the experimentally observed neutral cluster structures is possible, and the effect of charge on the structure of neutrals and cations, which have been previously studied via IR multiple photon dissociation, can be investigated. Whereas the structures of small clusters are based on bipyramidal motifs, a trigonal prism as central unit is found in larger clusters. Bond weakening due to the loss of an electron leads to a major structural change between neutral and cationic Si(8).     

Sub-nanometre sized metal clusters: from synthetic challenges to the unique property discoveries

Sub-nanometre sized metal clusters, with dimensions between metal atoms and nanoparticles, have attracted more and more attention due to their unique electronic structures and the subsequent unusual physical and chemical properties. However, the tiny size of the metal clusters brings the difficulty of their synthesis compared to the easier preparation of large nanoparticles. Up to now various synthetic techniques and routes have been successfully applied to the preparation of sub-nanometre clusters. Among the metals, gold clusters, especially the alkanethiolate monolayer protected clusters (MPCs), have been extensively investigated during the past decades. In recent years, silver and copper nanoclusters have also attracted enormous interest mainly due to their excellent photoluminescent properties. Meanwhile, more structural characteristics, particular optical, catalytic, electronic and magnetic properties and the related technical applications of the metal nanoclusters have been discovered in recent years. In this critical review, recent advances in sub-nanometre sized metal clusters (Au, Ag, Cu, etc.) including the synthetic techniques, structural characterizations, novel physical, chemical and optical properties and their potential applications are discussed in detail. We finally give a brief outlook on the future development of metal nanoclusters from the viewpoint of controlled synthesis and their potential applications.     

Geometrical Structures and Electronic Properties of Copper-Doped Aluminum Clusters

Using density function theory (DFT), the Cu-doped Aln (n=1?15) clusters have been stud-ied. The electron a±nity, ionization potential, Mulliken population analysis of Cu, mean polarizability, polarizability anisotropy, dipole moments and HOMO-LUMO gaps have also been calculated on the basis of optimized geometries. The results indicate that there is magic numbers in copper-doped aluminum clusters and electronic characteristic depended on the size of clusters. As n=13, the electron affinity and ionization potential of cluster changed more than 0.3 and 0.6 eV respectively, compared with neighborhood clusters.     

Ni3Al合金液态与非晶中的原子团簇

采用常温常压分子动力学模拟技术，模拟了液态Ni3Al中原子团簇在快速凝固条件下的演变过程，模型采用的是TB(tight binding)作用势.用偶分布函数、键对和多面体等结构参数来描述快速凝固条件下团簇种类和数量的变化，并将团簇结构可视化.在2 000 K下，液态Ni3Al中团簇数量较少，且都是由缺陷二十面体构成；在4×1013 K•s－1的冷速下，团簇的数量随温度的降低不断增加，且出现完整二十面体团簇，体系最终形成了由二十面体和缺陷二十面体团簇网络所组成的非晶结构.     

液态金属Al快速凝固过程中团簇结构的形成特性

A simulation study on the formation characteristics of clusters in a large-scale liquid Al system consisting of 105 atoms has been performed by the molecular dynamics method. And a cluster-type index method（CTIM）has been used to describe the structural configurations of various clusters. The results demonstrate that the icosahedron clusters（12 0 12 0）and their combinations play the most important role in the microstructure transition. The nanoclusters（containing up to 104 atoms）have been formed by combining some middle clusters which have been formed by combining smaller basic clusters. The structures of these nano-clusters are very different from those of nano-clusters obtained by evaporation,ionic spray methods,and so on. The latter is formed by the multi-shell crystals accumulated with an atom as the center and the surrounding atoms arranged according to octahedron configuration. The center atoms of these basic clusters are bond-connected each other with the linear or twisting mode. The corners of the nano-cluster just could become the starting points of the dendrite growth in the solidification processes of liquid metals.     

STUDIES ON SYNTHESIS, STRUCTURE AND REACTIVITY OF ACTIVATED Os_6 RAFT-LIKE CLUSTERS

In this paper we report the synthesis and activation of OS-6 raft-llke planar clusters. The activated OS-66 raft-like clusters [OS-66(CO)_(20)(MeCN)] and [OS-66(CO)_(19) (MeCN)_2] have been prepared by involving PdCl_2 as catalyst. Trimethylamine oxide (Me_3NO) has been used as an activation reagent to oxidize several carbonyl ligands coordinated in the activated clusters and to get a series of activated OS-66 raft-like clusters [OS-66(CO)_(21-x)(MeCN)_x] (n = 1--5) and corresponding substituted clusters [OS-66(CO)_(21-x)(P(OMe)_3)_x] (n=1--5). The structures of these OS-66 raft-like clusters have been characterized by the infrared spectra (IR), nuclear magnetic resonance spectra (NMR) and mass spectra (MS), and the characters of the raft-like planar structure and reactivity above have also been discussed in this paper.     

Simulation of ab initio results for palladium and rhodium clusters by tight‐binding calculations*

The study of metal clusters is nowadays a very active field of research using both experimental and theoretical techniques. Regular trends as well as unexpected behaviors have been observed regarding size‐dependent properties such as ionization potentials and atomization energies. Palladium and rhodium clusters of small size have been extensively studied at various semiempirical and ab initio levels of the theory, but the achievement and the interpretation of these calculations are generally difficult to be performed because of the incomplete shell structure of transition metal clusters. So we have tried to mimic the most important conclusions of the ab initio results available for Pd and Rh clusters by means of tight‐binding calculations, in the original Wolfsberg–Helmholz form, with appropriate parametrized repulsion terms. The occupation numbers of the one‐electron energy levels have been determined by taking into account some predictions of the graph theory. This enables us to study the variation of the atomization energies per atom for these clusters and to derive a bond‐energy systematics for Pd–Pd, Rh–Rh, and Pd–Rh linked atoms. Magic clusters with 13 atoms are considered. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 82: 26–33, 2001     

Two-dimensional Monte Carlo simulations of a polydisperse colloidal dispersion composed of ferromagnetic particles for the case of no external magnetic field

We have investigated the aggregation phenomena in a polydisperse colloidal dispersion composed of ferromagnetic particles by means of the cluster-moving Monte Carlo method. The results have been compared with those for a monodisperse system. The internal structures of aggregates have been analyzed in terms of the radial distribution function in order to clarify the quantitative differences in the internal structures of clusters. In addition, the cluster size distribution and angular distribution function have been investigated. The results obtained in the present study are summarized as follows. In a monodisperse system, open necklacelike clusters are formed and they extend with increasing strength of the magnetic particle-particle interaction. In a polydisperse system with a small standard deviation in the particle size distribution, sigma=0.2, larger necklacelike clusters are formed and some looplike clusters can also be observed. In a polydisperse system with a larger standard deviation, sigma=0.35, clumplike clusters are formed for a weak magnetic particle-particle interaction. For a stronger magnetic interaction, larger size clusters that exhibit a complicated network structure are formed. These complicated cluster formations found in a polydisperse system are mainly due to the effect of the presence of larger particles.     

Reactivities and biological functions of iron-sulfur clusters

Iron-sulfur clusters are prevalent in biological systems. Through studies of iron-sulfur proteins and synthetic model clusters, it was realized early on that these clusters functioned as facile electron transfer agents. Until recently it was widely thought that they served exclusively in that capacity. However, in the last decade, it has become clear that their reactivities and biological functions are much more diverse. It is now apparent that these clusters can serve as the active sites of enzymes, as well as in the regulation of enzymatic activity. Synthetic clusters, which have been shown to undergo a variety of core rearrangements or structural changes, have provided insight into possible mechanisms of cluster formation or activity regulation in enzymes. Rigid tripodal ligands have been constructed which capture synthetic iron-sulfur clusters in a cavity which permits controlled reactivity studies. In this article, we review these recent developments and suggest some future directions the field may take.     

Hydrogen bond dynamics in the excited states: photodissociation of phenol in clusters

We have investigated the photodynamics of phenol molecules in clusters. Possible reaction pathways following the photoexcitation of hydrogen-bonded phenol clusters have been identified theoretically using ab initio calculations. Experimentally we have studied the phenol molecules and clusters of various size distributions in a molecular beam apparatus. In particular, we have measured the H-fragment kinetic energy distributions after the excitation with 243 nm and 193 nm laser radiation. At 243 nm the KED spectra did not show any significant difference between the photodissociation of isolated molecules and phenol in larger clusters, while at 193 nm the contribution of the fast H-fragments is significantly suppressed in clusters with respect to the bare phenol molecule. We have interpreted the experimental results within the framework of the suggested reaction pathways.