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.     

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.     

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.     

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.     

Pure and Sb-doped SnO 2 nanoparticles studied by photoelectron spectroscopy

We describe photoemission results from pure and Sb-doped SnO₂ nanoparticles deposited on gold substrates. Photoelectron spectra with synchrotron radiation were recorded for Sn 3d, Sb 3d and O 1s core levels and valence bands in the 500-1200 eV energy range. For pure SnO₂ nanoparticles the surface is terminated by an oxygen rich layer with no obvious surface environment for Sn. When doped n-type with 9.1% or 16.7% Sb, dopant atoms are concentrated near the surface of the nanoparticles. The valence state of the dopant atoms is predominantly Sb^V. Plasmon satellite features are also observed in core level photoemission spectra and their intensity relative to the main peak increases with increasing photon energy. Received 30 November 2000     

Optical and photoelectron spectroscopic studies of alkyl-passivated silicon nanoparticles

We have performed the optical and photoelectron spectroscopic studies of alkyl-passivated Si nanoparticles synthesized by a solution route. The alkyl-passivated Si nanoparticle with mean diameter less than about 2 nm exhibits a strong ultraviolet-blue photoluminescence. Furthermore, we have directly investigated their electronic structures in the vicinity of Fermi level by means of valence-band photoemission measurements using synchrotron radiation. From these results, the detailed optical properties and electronic structures of alkyl-passivated Si nanoparticles are discussed.     

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.     

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.     

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.     

Bonds and Fermi surfaces studied by photoelectron spectroscopy

Photoelectron spectroscopy with synchrotron radiation employing high energy and angular resolutions is a very efficient tool for experimental investigations of the electronic structure of solids and their surfaces. In addition to standard band-mapping applications, photoemission intensity and line-shape analyses provide valuable information about wave functions, bonds and interactions of a many-electron system. In this report we choose covalent semiconductor surfaces as well as metallic clean and nanostructured surfaces of layered materials to serve as model systems for assessing the spatial origin of photoelectrons and the three-dimensional shape of Fermi surfaces. Received: 11 July 2001 / Accepted: 23 July 2001 / Published online: 3 April 2002     

Scanning tunneling lithography of silicon nanoparticle films

Monolayer and bi-layer silicon nanoparticle (SiNP) films with wide band gaps (up to 4 eV) have been produced in UHV with narrow size distributions of particles with 2-4 nm diameters and were studied using scanning tunneling microscopy (STM) and spectroscopy (STS). The films then were manipulated by applying different values for the tunneling resistance. Nanoparticle fusion and fission processes allow to shape the particles in the films in various ways and to write in white and black on the film template.     

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.     

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     

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.     

Predicting experimental signatures for the oxidation of magnesia supported palladium clusters by density functional theory

We showed in a recent density functional study that small palladium cluster on a MgO surface with F-centers can be oxidized to epitaxial Pd_xO_y nano-oxides below room temperature [1]. Here, we employ density functional theory in order to explore different methods for an experimental verification of the Pd_xO_y formation. The electronic density of states (DOS) of bare, O₂-decorated and of oxidized palladium cluster was calculated. For many cluster sizes a clear difference in the DOS could be observed allowing for a detection of the oxidation with surface sensitive spectroscopic methods. In addition, adsorption sites and stretch frequencies of a single CO molecule on bare and oxidized Pd₄ clusters were calculated. While CO prefers hollow sites on Pd₄, top adsorption sites are found for Pd₄O₂. Markedly different CO stretch frequencies indicate a possible discrimination of bare clusters and oxides by Fourier transform infrared spectroscopy.     

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.     

Mo6S6 nanowires: structural, mechanical and electronic properties

The properties of nanowires were investigated with ab initio calculations based on the density-functional theory. The molecules build weakly coupled one-dimensional chains, like and Mo₆S_9-xI_x, and the crystals are strongly uniaxial in their mechanical and electronic properties. The calculated moduli of elasticity and resilience along the chain axis are c₁₁ = 320 GPa and E_R = 0.53 GPa, respectively. The electronic band structure and optical conductivity indicate that the crystals are good quasi-one-dimensional conductors. The frequency-dependent complex dielectric tensor ε, calculated in the random-phase approximation, shows a strong Drude peak in ε_∥, i.e., for the electric field polarised parallel to the chain axis, and several peaks related to interband transitions. The electron energy loss spectrum is weakly anisotropic and has a strong peak at the plasma frequency ħω_p ≈20 eV. The stability analysis shows that is metastable against the formation of the layered .     

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.     

Electron transport in double-walled carbon nanotubes

The transport properties of finite length double-walled carbon nanotubes subject to the influences of a transverse electric field and a magnetic field with varying polar angles are investigated theoretically. The electrical conductance, thermal conductance and Peltier coefficient dependences on the external fields and symmetric configuration are studied in linear response regime. Prominent peak structures of the electrical conductance are predicted when varying the electric field strength. The features of the conductance peaks are found to be strongly dependent on the external fields and the intertube interactions. The heights of the electrical and thermal conductance peaks display the quantized behavior, while those of the Peltier coefficient do not. The conductance peaks are found to be broadened by the finite temperature.     

Structures and reactions of biomolecular ions produced with electrospray ionization

Photo-induced reaction of [Fe(III)-protoporphyrin]⁺ (hemin⁺) ions solvated with dimethylsulfoxide (DMSO) is investigated by using a tandem mass spectrometer with electrospray ionization. We measure the photodissociation yields of mass-selected hemin⁺(DMSO)_n clusters for n = 0-3. The mass spectra of the fragment ions show the -cleavage of carboxymethyl groups in addition to the evaporation of solvent molecules. Yield of the -cleavage reaction is found to depend strongly on the excitation energy and the number of solvent molecules. We also examine photo-induced reactions of multiply-charged cytochrome c ions, (M + nH)^{n +} ( n = 9-17). Photoionization is found to be the dominant process for the lower charged states ( n = 9-12) and its yield decreases rapidly with increasing the charge. The photoionization is ascribed to the emission of electron by multiphoton excitation of heme under the influence of Coulomb attractive potential arising from the charges in the polypeptide chain. Model calculations of the Coulomb potential suggest that the structure of the polypeptide chain is completely elongated.