Novel metal-encapsulated caged clusters of silicon and germanium

We report the recent findings of metal (M) encapsulated clusters of silicon from computer experiments based on ab initio total energy calculations and a cage shrinkage and atom removal approach. Our results show that using a guest atom, it is possible to wrap silicon in fullerenelike (f) structures, as sp² bonding is not favorable to produce empty cages unlike for carbon. Transition M atoms have a strong bonding with the silicon cage that are responsible for the compact structures. The size and structure of the cage change from 14 to 20 Si atoms depending upon the size and valence of the M atom. Fewer Si atoms lead to relatively open structures. We find cubic, f, Frank-Kasper (FK) polyheral type, decahedral, icosahedral and hexagonal structures for M@Si_n with n = 12-16 and several different M atoms. The magic behavior of 15 and 16 atom Si cages is in agreement with experiments. The FK polyhedral cluster, M@Si₁₆ has an exceptionally large density functional gap of about 2.35 eV calculated within the generalized gradient approximation. It is likely to give rise to visible luminescence in these clusters. The cluster-cluster interaction is weak that makes such clusters attractive for cluster assembled materials. Further studies to stabilize Si₂₀ cage with M = Zr, Ba, Sr, and Pb show that in all cases there is a distortion of the f cage. Similar studies on M encapsulated germanium clusters show FK polyhedral and decahedral isomers to be more favorable. Also perfect icosahedral M@Ge₁₂ and M@Sn₁₂ clusters have been obtained with large gaps by doping with divalent M atoms. Recent results of the H interaction with these clusters, hydrogenated silicon fullerenes as well as assemblies of clusters such as nanowires and nanotubes are briefly presented.     

Energetics and electronic properties of BN nanocones with pentagonal rings at their apexes

The geometric structures, energetics and electronic properties of the recently discovered BN nanocones are investigated using first-principles calculations based on the density-functional theory. We have proposed one particular structure for BN nanocones associated with the 240^° disclination, derived by the extraction of four 60^° segments, presenting as characteristic four pentagons at the apex and termination in two atoms. The cones are simulated by three clusters containing 58 B plus N atoms and additional 12 H atoms to saturate the dangling bonds at the edge. The most stable configuration is obtained when the two terminating atoms are one B and one N. For the cases where the two terminating atoms are of the same kind, the tip with B atoms is determined to have lower binding energy than with N atoms. The local densities of states of these BN nanocones are investigated and sharp states are found in the regions close (below and above) to the Fermi energy. Received 14 October 2002 / Received in final form 6 December 2002 Published online 11 February 2003 RID="a" ID="a"e-mail: ppiquini@smail.ufsm.br     

Structures and stability of Al<Subscript><Emphasis Type="Bold">7</Emphasis></Subscript>C and Al<Subscript><Emphasis Type="Bold">7</Emphasis></Subscript>N clusters

We report results of the atomic and electronic structures of Al₇C cluster using ab initio molecular dynamics with ultrasoft pseudopotentials and generalized gradient approximation. The lowest energy structure is found to be the one in which carbon atom occupies an interstitial position in Al₇ cluster. The electronic structure shows that the recent observation [Chem. Phys. Lett. 316, 31 (2000)] of magic behavior of Al₇C^- cluster is due to a large highest occupied and lowest unoccupied molecular orbital (HOMO-LUMO) gap which makes Al₇C^- chemically inert. These results have further led us to the finding of a new neutral magic cluster Al₇N which has the same number of valence electrons as in Al₇C^- and a large HOMO-LUMO gap of 1.99 eV. Further, calculations have been carried out on (Al₇N)₂ to study interaction between magic clusters. Received 28 July 2001     

A density functional theoretic study of novel silicon-carbon fullerene-like nanostructures: Si40C20, Si60C20, Si36C24, and Si60C24

Fullerene-like silicon nanostructures with twenty and twenty-four carbon atoms on the surface of the Si₆₀ cage by substitution, as well as inside the cage at various orientations have been studied within the generalized gradient approximation to density functional theory. Full geometry optimizations have been performed without any symmetry constraints using the Gaussian 03 suite of programs and the LANL2DZ basis set. Thus, for the silicon atom, the Hay-Wadt pseudopotential with the associated basis set is used for the core electrons and the valence electrons, respectively. For the carbon atom, the Dunning/Huzinaga double zeta basis set is employed. Electronic and geometric properties of these nanostructures are presented and discussed in detail. Optimized silicon-carbon fullerene like nanostructures are found to have increased stability compared to the bare Si₆₀ cage and the stability depends on the number and the orientation of carbon atoms, as well as on the nature of silicon-carbon and carbon-carbon bonding.     

Theoretical study of small silicon clusters on a graphite layer

In a series of recent experiments, the HOMO-LUMO energy gaps of small Si clusters deposited on a graphite substrate have been determined by Scanning Tunneling Microscopy (STM). The values obtained were found to be substantially smaller than the energy gaps of corresponding passivated clusters. This work considers dimensional reduction as a possible mechanism for a sizeable energy gap narrowing by the example of the system Si₅. The impact of the graphite substrate on the deposited species is investigated in the framework of a pseudocluster model. Received 30 November 2000     

The continuum gauge field-theory model for low-energy electronic states of icosahedral fullerenes

The low-energy electronic structure of icosahedral fullerenes is studied within the field-theory model. In the field model, the pentagonal rings in the fullerene are simulated by two kinds of gauge fields. The first one, non-abelian field, follows from so-called K spin rotation invariance for the spinor field while the second one describes the elastic flow due to pentagonal apical disclinations. For fullerene molecule, these fluxes are taken into account by introducing an effective field due to magnetic monopole placed at the center of a sphere. Additionally, the spherical geometry of the fullerene is incorporated via the spin connection term. The exact analytical solution of the problem (both for the eigenfunctions and the energy spectrum) is found.     

Photoemission spectra of deuterated silicon clusters: experiment and theory

We compare experimentally measured and ab initio computed photoelectron spectra of negatively charged deuterated silicon clusters ( , 4m10, 0n2) produced in a plasma environment. Based on this comparison, we discuss the kinetics and thermodynamics of the cluster formation and the effect of deuterium on the geometrical and electronic structure of the clusters.     

A comparative study on the interaction between tin(II) porphyrin and selected group 8B metals for potential application as reduction catalysts

We study the interaction between tin(II) porphyrin (SnPor) with platinum and non-precious Group 8B metals (iron, cobalt and nickel) by density functional theory and discuss the electronic properties of the resulting products. We also model the interaction of the resulting compounds with water where applicable. Our studies indicate that, SnPor-Ni possesses electronic properties similar to SnPor-Pt, suggesting that it may possess similar photocatalytic properties for reduction reactions, such as converting water to hydrogen gas.     

Core size effects on electrodeposition of gold nanoparticles attached with biferrocene derivatives

Biferrocene-modified gold nanoparticles (Au_n-BFc) comprising 1.7, 2.2 and 2.9 nm in average core diameter, d, were synthesized by a substitution reaction of octyl thiolate-covered nanoparticles with biferrocene-terminated alkanethiol, 1-(9-thiononyl-1-one)-1, 1-biferrocene (BFcS). All sizes of Au_n-BFc undergo two-step oxidation reactions in 0.1 mol dm^-3 Bu₄NClO₄-CH₂Cl₂ and consecutive potential scans including the second oxidation process lead to the formation of an adhesive redox-active gold nanoparticle film on an electrode. The thickness of the Au_n-BFc film is controllable by the number of potential scans. The scanning tunneling microscope images reveal that the Au_n-BFc (d = 2.9 nm) film forms many domains of the assembled Au_n-BFcs, especially the particles are isotropically assembled in line.     

AC Stark effect in toroidal carbon nanotubes threaded with an ac magnetic flux

The ac Stark effect is investigated in the toroidal carbon nanotube system threaded with an ac magnetic flux. The Floquet theory is employed to deal with the time-dependent quantum problems. The time-averaged energy of the system is derived and is found to exhibit a strong relationship with an external field, and the modified energy gap has been presented. The ac flux enhances energy gaps to cause metal-semiconductor transition. The steady current has been obtained by employing the free energy approach, and the persistent current is a special case as the magnitude of the ac flux approaches zero. The photon-assisted current is quite different from the persistent current due to the absorption and emission of photons. The local density of states is obtained by calculating the Green's function in the Floquet state, and photon-resonant structures are observed. All of the novel features are associated with the ac Stark effect, which is caused by the modification of energy levels. Received 20 November 2002 / Received in final form 7 February 2003 Published online 20 June 2003 RID="a" ID="a"e-mail: zhaohonk@yahoo.com     

Water-silica interaction in clusters

The interaction of water with SiO ₂ is an important problem in geophysics, materials physics, and environmental science. In this paper, we present recent results on studies of H ₂ O-silica clusters from first-principles Born-Oppenheimer molecular dynamics calculations. Bond strength and chemical stability are investigated as a function of cluster size and chemical composition. Both physisorption and chemisorption of water molecules on the clusters are discussed via analysis of energetics. Calculations of clusters are compared with the results from extended surfaces. The validity of clusters as models of surfaces is discussed.     

Optical properties of 4 Å single-walled carbon nanotubes inside the zeolite channels studied from first principles calculations

The structural, electronic, and optical properties of 4 ? single-walled carbon nanotubes (SWNTs) contained inside the zeolite channels have been studied based upon the density-functional theory in the local-density approximation (LDA). Our calculated results indicate that the relaxed geometrical structures for the smallest SWNTs in the zeolite channels are much different from those of the ideal isolated SWNTs, producing a great effect on their physical properties. It is found that all three kinds of 4 ? SWNTs can possibly exist inside the Zeolite channels. Especially, as an example, we have also studied the coupling effect between the ALPO₄-5 zeolite and the tube (5,0) inside it, and found that the zeolite has real effects on the electronic structure and optical properties of the inside (5,0) tube. Received 26 January 2003 Published online 11 April 2003 RID="a" ID="a"e-mail: yxptl@hotmail.com     

Electronic properties of Ge–Si nanoparticles

Using a parameterized density-functional tight-binding method we have calculated the electronic and structural properties of Ge–Si nanoparticles. Starting with a spherical part of a zinc-blende/diamond crystal (with the center of the sphere at the mid-point of a nearest-neighbour bond) we have constructed initial structures that subsequently were allowed to relax. Structures consisting solely of Ge atoms or solely of Si atoms were studied, together with core-shell structures for which one semiconductor forms a shell on the core of the other semiconductor. Moreover, homogeneous, ordered SiGe structures as well as structures with a semisphere of one semiconductor and a semisphere of the other were also considered. In analysing the results special emphasis is put on identifying particularly stable structures, on explaining the occurrence of those, on the spatial distribution of the frontier orbitals, and on the variation of the total energy with structure and composition.     

Superparamagnetism in small Fe clusters on Cu(111)

Fe clusters of 105±2 atoms/cluster were mass selectively deposited onto Cu(111) at cryogenic temperatures. XMCD was used to measure temperature and direction dependent magnetization curves. The clusters are superparamagnetic at the lowest temperature measured (10 K). Their magnetization curves are consistent with magnetic moments of ≈2.5μ_B per atom which are thus enhanced over the bulk values. Within experimental accuracy, the clusters do not present magnetocrystalline anisotropy in the temperature range of 10 K to 60 K.     

Electronic structure of dendrimer-encapsulated Au nanocluster

We have carried out optical and X-ray photoemission studies of the dendrimer-encapsulated Au nanoclusters. The dendrimer-encapsulated Au nanoclusters are prepared by the chemical reduction of Au ions loaded within the dendrimer templates. Photoluminescence spectrum of the dendrimer-encapsulated Au nanoclusters with diameter of about 1.0 nm shows the visible luminescence centered at about 2.8 eV. In addition, we have measured the nanocluster-size dependent photoemission spectra in the valence-band region. From line shape analysis of Au 4f X-ray photoemission spectra, Au 4f core-level spectra of the dendrimer-encapsulated Au nanoclusters reflect the size dependent chemical-states. From these results, we discuss electronic structures and chemical states of the dendrimer-encapsulated Au nanoclusters.     

Direct observation of the non-supported metal nanoparticle electron density of states by X-ray photoelectron spectroscopy

Synchrotron-based X-ray photoelectron spectroscopy on copper and silver cluster beams created by a magnetron-based gas-aggregation source has allowed mapping the electron density of states (DOS) of free metallic nanoparticles. The cluster DOS profiles obtained in the experiments strongly resemble the infinite solid DOS shapes, but the extracted cluster work-functions are lower than those for the bulk metal. The latter observation is explained by the initial negative charge on most of the clusters, created by the source.     

Electronic properties of arrayed K clusters in zeolite LTA with Si/Al = 1.5

Arrayed cationic K clusters including one 4s-electron in each cluster, i.e., K_m+1 ^m+, were incorporated into α-cages of zeolite LTA with Si/Al=1.5. Although no magnetic phase transition was observed regarding the temperature (T) dependence of magnetic susceptibilities originating from the 4s-electron spins (χ_spin) between 2 and 300 K, the χ_spin-T curve could be fitted by the sum of magnetic susceptibilities based on the Curie-Weiss law and Pauli paramagnetism. A possible explanation of this behavior is the existence of a narrow energy band formed out of 1s-cluster orbitals of arrayed K clusters, and the existence of a finite density of state at the Fermi energy.     

Transmission resonance via quantum bound states in confined arrays of antidots

We have studied the transmission resonances for a confined array of antidots, using the lattice Green's function method. Two kinds of resonant peaks via quasibound states are found. One kind of resonant peak corresponds to the split quasibound states. The split states originate from the superposition of quasibound states respectively localized in different (T or crossed) junctions, while the number of quasibound states in each junction is associated with the arm-width of the junction. Electrons in these split states are mainly localized in the junctions. The other kind of resonant peaks correspond to the high quasibound states which exist in (transverse and longitude) multi-period confined arrays of antidots. It is interesting to note that electrons in some of the high quasibound states are mainly localized in the intersection of the junctions rather than in the junctions themselves.     

Magnetic anisotropy of deposited transition metal clusters

We present results of magnetic torque calculations using the fully relativistic spin-polarized Korringa-Kohn-Rostoker approach applied to small Co and Fe clusters deposited on the Pt(111) surface. From the magnetic torque one can derive amongst others the magnetic anisotropy energy (MAE). It was found that this approach is numerically much more stable and also computationally less demanding than using the magnetic force theorem that allows to calculate the MAE directly. Although structural relaxation effects were not included our results correspond reasonably well to recent experimental data.     

Optical properties of silver clusters formed by ion irradiation

Precipitation of silver clusters in silica is achieved by different methods: ion implantation, ion beam mixing of superimposed layers and ion irradiation of films deposited by means of co-sputtering or sol-gel technique. Main features of the nanoparticles depending on the preparation method are investigated by TEM. The optical extinction resonance of these clusters is analysed in terms of sizes and interaction between the clusters on the basis of calculations. We found that resonances in sputtered and gel films with low metal concentrations are well described by plasmon polaritons in isolated clusters and calculations based on Mie theory allow the study of their growth under irradiation. This theory is not appropriate to describe the optical response of silver clusters in silica implanted with Ag concentrations higher than 5 at.% or in ion beam mixed films, because of the interaction between clusters. Using an effective medium model, it is demonstrated that the random dispersion of clusters in implantation films causes fluctuations and, on average, an increase of the clusters polarization. On the contrary, the particular arrangement of the clusters with a bimodal size distribution in ion beam mixed films induces a screening effect between the clusters of largest size. Received 10 January 2002 / Received in final form 26 April 2002 Published online 19 July 2002