Electronic and magnetothermal properties of ferromagnetic clusters

The electronic structures and the magnetothermal properties of nickel clusters have been investigated. Their effective magnetic moments and specific heat capacities have been calculated assuming that the clusters undergo superparamagnetic relaxation. The average magnetic moments are computed adopting Friedel's model of ferromagnetic clusters. The surface effect and the cluster size effect on the thermodynamic properties of these clusters have been analysed based on the mean field theory approximation. The specific heat capacity of Ni clusters for N=300, where N is the number of atoms in the cluster, shows the peak value at T=550 K and exhibits a steady increase with N. The effective potentials and energy eigen values of the clusters as a function of the number of atoms and radius of the cluster have also been calculated self-consistently using the local density approximation (LDA) of the density functional theory (DFT); this has been performed within the framework of the spherical jellium background model (SJBM). The results of this study have been compared with the Stern-Gerlach experimental data and other theoretical results already reported in literature     

Surface diffusion of Pb clusters on Cu(1 1 1) influenced by size dependent cluster-substrate misfit: Monte Carlo tight binding simulation model

The migration of two-dimensional Pb clusters on Cu(1 1 1) surface is studied in the framework of three-dimensional (3D) continuum space tight binding (TB) computational model. Monte Carlo simulations based on many-body TB interactions reveal significant influence of cluster-substrate misfit on diffusion behavior of two-dimensional (2D) clusters. The analysis of pair distribution function (PDF) demonstrates that cluster lattice constant depends on the number of atoms N for 1 < N < 10. The observed effect is more pronounced for heteroepitaxial than homoepitaxial systems. It can be explained in the framework of model accounting for enhanced charge transfer in heteroepitaxy and strong influence of surface potential on cluster atomic arrangement. The variation of lattice constant leads to variable misfit which affects the island migration behavior. The results are discussed in a physical model that implies cluster diffusion with size dependent cluster-substrate misfit.     

Structures and stability of Ag clusters on Ag(1 1 1) and Ni(1 1 1) surfaces

The structures of the lowest total energy for small Ag_N clusters with N = 2-20, which are grown on Ag(1 1 1) and Ni(1 1 1) surfaces, have been determined using a combination of the embedded-atom method and the basin-hopping algorithm. It is found that the particularly stable Ag clusters with N<18 have similar geometries on both surfaces when comparing clusters of the same size. On the other hand, the geometries of the less stable Ag clusters in the same size range differ for the two surfaces. From N?18, the sizes of the particularly stable structures are different for the two different substrates. Due to the large size mismatch of the two types of atoms it is energetically unfavorable for Ag to form a pseudomorphic monolayer structures on Ni(1 1 1) and there is considerable strain produced at the interface. The effect of this strain and the increased adatom-substrate interactions lead to irregular and elongated structures of the adsorbed Ag clusters.     

Density functional study of TaSin (n = 1-3, 12) clusters adsorbed to graphene surface

A plane-wave density functional theory (DFT) calculations have been performed to investigate structural and electronic properties of TaSi_n (n = 1-3, 12) clusters supported by graphene surface. The resulting adsorption structures are described and discussed in terms of stability, bonding, and electron transfer between the cluster and the graphene. The TaSi_n clusters on graphene surface favor their free-standing ground-state structures. Especially in the cases of the linear TaSi₂ and the planar TaSi₃, the graphene surface may catalyze the transition of the TaSi_n clusters from an isomer of lower dimensionality into the ground-state structure. The adsorption site and configuration of TaSi_n on graphene surface are dominated by the interaction between Ta atom and graphene. Ta atom prefers to adsorb on the hollow site of graphene, and Si atoms tend to locate on the bridge site. Further, the electron transfer is found to proceed from the cluster to the surface for n = 1 and 2, while its direction reverses as n > 2. For the case of TaSi, chemisorption is shown to prevail over physisorption as the dominant mode of surface-adsorbate interaction by charge density analysis.     

Giant fullerenes formed on C60 films irradiated with electrons field-emitted from scanning tunneling microscope tips

It has been found that spherical large clusters of carbon atoms are formed by irradiation of crystalline C₆₀ films grown on Si(1 1 1)-(7 × 7) surfaces with electrons field-emitted from a scanning tunneling microscope probe tip. The size distribution of the clusters deduced from surface profile measurements suggests that the dominant clusters were not necessarily C_60n (n = 2-4) expected from the simple fusion of C₆₀ molecules. It was proposed that electronic excitations of C₆₀ molecules caused the fragment and coalescence of the molecules to form the giant fullerenes as in the photo-induced similar effects.     

Charge stripe structure in FeTe

We report the STM study on a single-crystalline sample of FeTe at 7.8 K. FeTe is one of the iron-based superconductor. We measured the resistivity and the magnetization of FeTe. FeTe shows SDW transition at 58 K on these measurements. We study the electronic state of FeTe by using STM/STS for observing FeTe from a microscopic viewpoint. We observed the iron layer and the tellurium layer with atomic resolution. Moreover, we discover the charge stripe structure on STM/STS measurement. We find the charge stripe structure is caused by iron atoms from the analysis. The gap structure of 9 meV was observed in tunneling spectra. This gap size is consistent with the SDW gap which is expected from mean field theory with T_N=58 K.     

Density functional theoretical study of Cun, Aln (n = 4-31) and copper doped aluminum clusters: Electronic properties and reactivity with atomic oxygen

A DFT study of the electronic properties of copper doped aluminum clusters and their reactivity with atomic oxygen is reported. Firstly we performed calculations for the pure Cu_n and Al_n (n = 4, 9, 10, 13, 25 and 31) clusters and we determined their atomization energy for some frozen conformations at the B3PW91 level. The calculated work functions and M-M (M = Cu, Al) bond energies of the largest clusters are comparable with experimental data. Secondly, we focused our attention on the change of the electronic properties of the systems upon the substitution of an Al atom by a Cu one. This latter stabilizes the system as the atomization energy of the 31-atoms cluster increases of 0.31 eV when the substitution is done on the surface and of 1.18 eV when it is done inside the cluster. We show that the electronic transfer from the Al cluster to the Cu atom located at the surface is large (equal to 0.7 e⁻) while it is negligible when Cu is inserted in the Al_n cluster. Moreover, the DOS of the Al₃₁ and Al₃₀Cu systems are compared. Finally, the chemisorption energies of atomic oxygen in threefold sites of the Al₃₁, Cu₃₁ and Al₃₀Cu clusters are calculated and discussed. We show that the chemisorption energy of O is decreasing on the bimetallic systems compared to the pure aluminum cluster.     

Surface effect on the coalescence of Pt clusters: A molecular dynamics study

We have performed molecular dynamics simulations for Pt_N + Pt_N → Pt_2N (N = 147, 324, 500,792), to investigate the effect of size and substrate on coalescence temperature. Our simulations show that platinum nanoclusters coalesce at the temperatures lower than the cluster melting point. The difference between coalescence and melting temperatures decreases with the increase in cluster size and presence of substrate. These thermal behaviors affect catalytical properties of nanoclusters and the substrate, as an environment, has major effect on activity of metal nanoclusters.     

Surface structure and solidification morphology of aluminum nanoclusters

Classical molecular dynamics simulation with embedded atom method potential had been performed to investigate the surface structure and solidification morphology of aluminum nanoclusters Al_n (n=256, 604, 1220 and 2048). It is found that Al cluster surfaces are comprised of (1 1 1) and (0 0 1) crystal planes. (1 1 0) crystal plane is not found on Al cluster surfaces in our simulation. On the surfaces of smaller Al clusters (n=256 and 604), (1 1 1) crystal planes are dominant. On larger Al clusters (n=1220 and 2048), (1 1 1) planes are still dominant but (0 0 1) planes cannot be neglected. Atomic density on cluster (1 1 1)/(0 0 1) surface is smaller/larger than the corresponding value on bulk surface. Computational analysis on total surface area and surface energies indicates that the total surface energy of an ideal Al nanocluster has the minimum value when (0 0 1) planes occupy 25% of the total surface area. We predict that a melted Al cluster will be a truncated octahedron after equilibrium solidification.     

A DFT + U description of oxygen vacancies at the TiO2 rutile (1 1 0) surface

Experimental observations indicate that removing bridging oxygen atoms from the TiO₂ rutile (1 1 0) surface produces a localised state approximately 0.7 eV below the conduction band. The corresponding excess electron density is thought to localise on the pair of Ti atoms neighbouring the vacancy; formally giving two Ti³⁺ sites. We consider the electronic structure and geometry of the oxygen deficient TiO₂ rutile (1 1 0) surface using both gradient-corrected density functional theory (GGA DFT) and DFT corrected for on-site Coulomb interactions (GGA + U) to allow a direct comparison of the two methods. We show that GGA fails to predict the experimentally observed electronic structure, in agreement with previous uncorrected DFT calculations on this system. Introducing the +U term encourages localisation of the excess electronic charge, with the qualitative distribution depending on the value of U. For low values of U (?4.0 eV) the charge localises in the sub-surface layers occupied in the GGA solution at arbitrary Ti sites, whereas higher values of U (?4.2 eV) predict strong localisation with the excess electronic charge mainly on the two Ti atoms neighbouring the vacancy. The precise charge distribution for these larger U values is found to differ from that predicted by previous hybrid-DFT calculations.