Spectroscopy of size-selected neutral silicon clusters: Remarkably similar spectra for clusters containing between ∼15 and 70 atoms

Absorption spectra have been recorded for gas phase, size-selected neutral silicon clusters using resonant one- and two-color photodissociation spectroscopy. We now have spectra between 0.94 – 5.58 eV for clusters containing up to 70 atoms. Starting at ～15 atoms, the spectra are all amazingly identical. Comparisons of the silicon cluster spectra to those of various forms of bulk silicon show that the cluster spectra have much in common with the spectrum of the most stable diamond structure of bulk crystalline silicon.     

Aluminum and gallium clusters — a comparative study using simulated annealing

Density functional calculations with simulated annealing have been performed for clusters of aluminum and gallium with up to 10 atoms. There are many local minima in the energy surfaces and numerous stable isomers. As cluster size increases, there is a transition from planar to non-planar structures atn=5. All structures show regular patterns of bond and dihedral angles similar those found in the bulk materials. The bonds in gallium clusters are consistentlyshorter than those in clusters of the lighter element aluminum.     

A Study About Nanocluster Deposition of Thin-film Formation by Molecular Dynamics Simulation

The thin-film growth has been confirmed to be assembled by an enormous number of clusters in ICBD method. In sequence of clusters’ depositions proceeds to form the thin-film to understand quantitatively the interaction mechanisms between the cluster atoms and the substrate atoms, we use molecular dynamics simulation with EAM potential. The quantitative of flatness of deposition and percent of disordered atoms were proposed to evaluate the property of thin-film. In this simulation, three different Co cluster sizes of 55, 70, and 100 atoms with different velocities (100 up to 800 m/s) were deposited on a Al(0 0 1) substrate whose temperatures were set between 300 and 500 K. The simulations begin at specific equilibrium temperature of clusters and the substrate. The simulations are performed at different temperatures of the clusters and substrate and for different sizes of clusters. We showed that the percent of disordered atoms of substrate are affected by the cluster size and velocity of the clusters. Temperature dependence of the number of disordered atoms for different cluster’s velocity was observed. We investigated the effect of cluster size and initial velocity of cluster on the value of flatness.     

The local electronic and magnetic properties of Fe impurity in Al clusters

The local magnetic property,d electronic structure and the charge transfer effect of Fe impurity in Al clusters have been studied by using a tight-binding model Hamiltonian in the unrestricted Hartree-Fock approximation, which includes intra-atomic and interatomic Coulomb interactions. We have obtained that local magnetic moment of Fe impurity in FeAl _N clusters decreases with increasing cluster size and convergences to zero (that of bulk given by Anderson) withN larger than 12, meanwhile, the local magnetic moment for smaller clusters depends on the clusters size and it is a monotonous descent function of cluster size. We have also found that the spin splitting of the localizedd states decreases as the cluster size increases, which mainly results from the interaction between the localized electrons of Fe atom and the delocalized electrons of Al atoms.     

Structure of hydrogenated silicon clusters. Medium-sized clusters

The structures of the Si_nH_m clusters containing 10 to 70 silicon atoms and different numbers of hydrogen atoms are calculated in the MINDO/3 approximation using the Monte Carlo technique. The geometry optimization of the clusters showed the existence of several structural varieties that determine the optimal geometry of the clusters differing in size and hydrogen content. Small clusters (n < 20) with various geometrical configurations often have a hollow structure if the number of silicon atoms in the cluster is more than 12. For 20 ≤ n < 60 and the hydrogen content m ≤ n, hollow spheroidal geometry is most favorable. Staring from n ≈ 56−60, diamond structures are more favorable. The ratio c = m/n < 1, at which the spheroidal structure remains optimal, decreases with further increase in n.     

Structure and energetics of equiatomic K-Cs and Rb-Cs binary clusters

The basin-hopping algorithm combined with the Gupta many-body potential is used to study the structural and energetic properties of (KCs)(n) and (RbCs)(n) bimetallic clusters with N=2n up to 50 atoms. Each binary structure is compared to those of the pure clusters of the same size. For the cluster size N=28 and for the size range of N=34-50, the introduction of K and Rb atoms in the Cs alkali metal cluster results in new ground state structures different from those of the pure elements. In the size range N>/=38 the binary and pure clusters show not only structural differences, but they also display different magic numbers. Most of the magic Rb-Cs and K-Cs clusters possess highly symmetric structures. They belong to a family of pIh structures, where a fivefold pancake is a dominant structural motif. Such geometries have not been reported for alkali binary clusters so far, but have been found for series of binary transition metal clusters with large size mismatch. Moreover, tendency to phase separation (shell-like segregation) is predicted for both K-Cs and Rb-Cs clusters with up to 1000 atoms. Our finding of a surface segregation in Rb-Cs clusters is different from that of theoretical and experimental studies on bulk Rb-Cs alloys where phase separation does not occur.     

Fluorescence of rare gas clusters excited with synchrotron radiation

A cluster beam experiment for fluorescence measurements on rare gas clusters has been built up. First results on the evolution of energy levels of neutral krypton clusters with a cluster size between 200–8500 atoms/cluster are reported. The well known bulk excitons of solid krypton do not merge into the first atomic lines and appear only in clusters larger than 300 atoms/cluster. Smaller clusters absorb only at energies which fit well with surface excitons of the solid.     

Atom desorption energies for sodium clusters

The desorption energies of supported sodium clusters have been determined as a function of cluster size. Na _n clusters were formed by surface diffusion of sodium atoms adsorbed from a thermal atomic beam on a LiF(100) single crystal. Measurements have been performed by temperature programmed thermal desorption. The signals reflect fractional order desorption kinetics. The average cluster size could be controlled by varying the total number of sodium atoms on the surface. It was determined from scattering experiments. We find that the binding energies vary between 0.55 and 0.8 eV and only approach a constant value for clusters with diameters as large as 1,000 Å.     

Electronic properties of isolated GaNAsM clusters: photoionization-, photodissociation- and photoluminescence quantum yields

Photoionization quantum yields of Ga_NAs_M clusters with N + M = 85 ± 5 atoms in the spectral range of ω = 3.5–6.4 eV have been investigated by measuring their total photoabsorption and photoionization cross sections. It is found that the photoionization quantum yields of these clusters are strongly increased by about two orders of magnitude against the values of bulk GaAs. Photodissociation of the cluster provides another efficient channel whereas photoluminescence plays a minor role for the observed cluster size distributions with N + M typically between 30 and 130 atoms.     

Effect of particle size on the oxidizability of platinum clusters

The catalytic properties of transition metal particles often depend crucially on their chemical environment, but so far, little is known about how the effects of the environment vary with particle size, especially for clusters consisting of only a few atoms. To gain insight into this topic, we have studied the oxygen affinity of free Pt(x) clusters as a function of cluster size (x = 1, 2, 3, 4, 5, and 10) using density functional theory (DFT) calculations (GGA-PW91). DFT-based Nosé-Hoover molecular dynamics has been used to explore the configuration space of the Pt(x)O(x) and Pt(x)O(2x) clusters, leading to the discovery of several novel Pt-oxide structures. The formation of small Pt-oxide clusters by oxidizing the corresponding Pt(x) clusters is found to be significantly more exothermic than the formation of bulk Pt-oxides from Pt metal. The exothermicity generally increases as cluster size decreases but exhibits strongly nonlinear dependence on the cluster size. The nanoclusters are also structurally distinct from the bulk oxides and prefer one- and two-dimensional chain and ringlike shapes. These findings help elucidate the oxidation behavior of Pt nanoclusters and lay the foundation for understanding the reactivity of Pt nanoclusters in oxidizing chemical environments.     

Dipole polarizabilities of germanium clusters

Dipole polarizabilities of Ge_n clusters with 2–25 atoms are calculated using finite field (FF) method within density functional theory. The dipole moments and polarizabilities of clusters are sensitively dependent on the cluster geometries and electronic structures. The clusters with low symmetry and large HOMO–LUMO gap prefer to large dipole moments. The polarizabilities of the Ge_n clusters increase rapidly in the size range of 2–5 atoms and then fluctuate around the bulk value. The larger HOMO–LUMO gap may lead to smaller polarizability. As compared with the compact structure and diamond structure, the prolate cluster structure corresponds to a larger polarizability.     

Structural and energetic properties of Ni-Cu bimetallic clusters

The lowest-energy structures for all compositions of Ni n Cu m bimetallic clusters with N = n + m up to 20 atoms, N = 23, and N = 38 atoms have been determined using a genetic algorithm for unbiased structure optimization in combination with an embedded-atom method for the calculation of the total energy for a given structure. Comparing bimetallic clusters with homoatomic clusters of the same size, it is shown that the most stable structures for each cluster size are composed entirely of Ni atoms. Among the bimetallic clusters in the size range N = 2-20, the Ni N-1 Cu 1 clusters possess the highest stability. Further, it has been established that most of the bimetallic cluster structures have geometries similar to those of pure Ni clusters. The size N = 38 presents a special case, as the bimetallic clusters undergo a dramatic structural change with increasing atom fraction of Cu. Moreover, we have identified an icosahedron, a double, and a triple icosahedron with one, two, and three Ni atoms at the centers, respectively, as particularly stable structures. We show that in all global-minimum structures Ni atoms tend to occupy mainly high-coordination inner sites, and we confirm the segregation of Cu on the surface of Ni-Cu bimetallic clusters predicted in previous studies. Finally, it is observed that, in contrast to the bulk, the ground-state structures of the 15-, 16-, and 17-atom bimetallic clusters do not experience a smooth transition between the structures of the pure copper and the pure nickel clusters as a function of the relative number of the two types of atoms. For these sizes, the concentration effect on energy is more important than the geometric one.     

Semiempirical and ab-initio calculations of semiconductor clusters: variation of structure and symmetry with size for different compounds

Semiempirical (by extended Hückel method) and ab initio RHF SCF calculations are used for the wide range of cluster structures M_xX_y, where M = Cd,Ag; X = S,I: semiempirical - up to M₂₀X₃₅, and ab initio - for small clusters less than ten atoms. Variation of electronic structure with size for the fragments with tetrahedral coordination (bulklike sphalerite structures) and for some clusters of the lower symmetry allows to predict their possible geometries which are compared with experimental data. The chemical bonding factor (the chemical nature of bounded atoms, coordination number for metal and non-metal atoms, hybridization, etc) is of more importance in properties of the clusters than the familiar quantum confinement effect of semiconductor clusters (like CdS, CdSe, PbS, etc. ). The essential difference in regularities of small cluster formation is analysed for CdS- and AgI- based structures.     

The stability and structure of (N<Subscript>2</Subscript>)<Subscript>j</Subscript>(H<Subscript>2</Subscript>O)<Subscript>i</Subscript> and (Ar)<Subscript>j</Subscript>(H<Subscript>2</Subscript>O)<Subscript>i</Subscript> clusters

The stability and structure of water clusters absorbing nitrogen molecules or argon atoms was analyzed by molecular dynamics simulation at 233 K. The (?μ/?i)_{V, T} derivative of the chemical potential, a value characterizing the stability of a cluster with respect to its size, depends linearly on the number of molecules i. According to this criterion, the clusters under study become stable near i = 40. The average length of H-bonds increases monotonically in the growing cluster of pure water and exhibits oscillatory behavior if the growing cluster contains N₂ molecules or Ar atoms. The number of H-bonds per molecule oscillates between one and six as the cluster size changes. These oscillations are damped in pure water and sustained for clusters containing impurities, especially argon.     

Density-functional study of structural and electronic properties of Si(n)C(n) (n=1-10) clusters

Density-functional theory with generalized gradient approximation for the exchange-correlation potential has been used to calculate the structural and electronic structure of Si(n)C(n) (n=1-10) clusters. The geometries are found to undergo a structural change from two dimensional to three dimensional when the cluster size n equals 4. Cagelike structures are favored as the cluster size increases. A distinct segregation between the silicon and carbon atoms is observed for these clusters. It is found that the C atoms favor to form five-membered rings as the cluster size n increases. However, the growth motif for Si atoms is not observed. The Si(n)C(n) clusters at n=2, 6, and 9 are found to possess relatively higher stability. On the basis of the lowest-energy geometries obtained, the size dependence of cluster properties such as binding energy, HOMO-LUMO gap, Mulliken charge, vibrational spectrum, and ionization potential has been computed and analyzed. The bonding characteristics of the clusters are discussed.     

Sequential reactions of silicon clusters with SiD4: constrained heterogeneous nucleation of deuterated silicon particles

The sequential clustering reactions of gas phase silicon cluster ions are ideally suited for studying heterogeneous nucleation of silicon particles. Stepwise reactions of silicon cluster ions with silane have been observed which lead to growth of larger deuterated silicon clusters. Extensive information is obtained about their exothermic gas phase reaction rates and product distributions as a function of cluster size and degree of hydrogenation. What is found is that each size of silicon cluster exhibits a unique pattern of growth. Furthermore, nearly all of the silicon clusters encounter chemical constraints to rapid nucleation. These constraints are a consequence of specific electronic and structural requirements in the chemical reactions. The nature of these requirements are deduced using experimental results in concert with ab initio electronic structure theoretical calculations of the energetics and structures of various species.     

铝原子簇上化学吸附的尺度效应及其理论模型

对铝原子簇Al_n(n=1～10,12,13)已报导过的理论预测几何构型进行合理选择, 用量子化学CNDO/2法研究了单分子一氧化碳在这些簇上取不同吸附位形时的吸附作用。结果表明吸附强度随簇尺度的变化呈“幻数”特性: Al_2、Al_6、Al_(12)簇具有特别高的吸附能, 与实验观测结果相符。采用作者建议的推广电子壳模型可合理解释这一尺度效应。对Al_(12)和Al_(13)簇电子结构的分析进一步支持了壳模型的观点。随着簇的增大, 尺度效应逐步减弱并趋向于体相铝的性质。