Prediction of compositional ordering and separation in alloy nanoclusters

The statistical-mechanical free-energy concentration expansion method (FCEM) in conjunction with semi-empirical coordination-dependent energetic parameters was used for atomistic modeling of Ni-Cu-Al, Ni-Cu-Rh and the corresponding binary Ni-Cu, Ni-Al and Rh-Cu nanocluster systems, containing from 13 to 923 atoms with icosahedral and cuboctahedral shapes. The high efficiency of FCEM enables computations of such relatively large binary or ternary alloy clusters. Remarkable differences, governed by the opposite Ni-Cu and Ni-Al heteroatomic interactions, were noted in the surface segregated “magic-number” ordered compositional patterns of the two ternary clusters. Due to the strong Ni-Al interactions, the compositional ordering extends into the cluster core, and at elevated temperatures a sharp order-disorder transition occurs, depending on the cluster size, shape and composition. The computed site-specific atomic concentrations form the basis for evaluating pertinent thermodynamic functions. For all the alloy clusters a Schottky-type heat capacity anomaly is predicted and attributed to gradual desegregation excitation processes. In addition, inter-cluster compositional separation is computed for Rh-Cu clusters, and transition temperatures estimated from the disappearance of convexity in the free-energy vs. composition curves.     

Methods for calculating the desorption rate of an isolated molecule from a surface: Water on MgO(0 0 1)

We present two types of Molecular Dynamics (MD) simulation for calculating the desorption rate of molecules from a surface. In the first, the molecules move freely between two surfaces, and the desorption rate is obtained either by counting the number of desorption events in a given time, or by looking at the average density of the molecules as a function of distance from the surface and then applying transition state theory (TST). In the second, the potential of mean force (PMF) for a molecule is determined as a function of distance from the surface and the desorption rate is obtained by means of TST. The methods are applied to water on the MgO(0 0 1) surface at low coverage. Classical potentials are used so that long simulations can be performed, to minimise statistical errors. The two sets of MD simulations agree well at high temperatures. The PMF method reproduces the 0 K adsorption energy of the molecule to within 5 meV, and finds that the well depth of the PMF is not linear with temperature. This implies the prefactor frequency f in the Polanyi-Wigner equation is a function of temperature, increasing at lower temperatures due to the reduction of the available configuration space associated with an adsorbed molecule compared with a free molecule.     

Response of surface monolayer to electric field of approaching gas-phase molecule near temperature of orientational phase transition

Consideration is given to an orientationally structured surface monolayer near the temperature of the orientational phase transition in the electric field of a gas-phase molecule approaching the surface. As shown, under certain conditions this field gives rise to a cluster, with its radius nonmonotonically depending on the distance between the gas-phase molecule and the surface.     

Effects of level broadening and electron overheating in tunneling structures based on metal clusters

The effect of level broadening and electronic subsystem overheating of disk-shaped and spherical gold clusters/islands on the current-voltage characteristic of the three-electrode structure has been studied. A scheme for calculating the electronic level broadening in the one-dimensional case of rectangular barriers has been proposed. In the two-temperature electron-ion model of a metal cluster, taking into account the size dependence of the Debye frequency, the kinetic electron temperature has been estimated as a function of the bias voltage. At low ion temperatures, the broadening and electron overheating effects result in disappearance of steps of quantum and Coulomb staircases, i.e., a strong smoothness of the current-voltage characteristic even in structures on clusters consisting of a denumerable number of atoms, which is actually observed experimentally.     

Adsorption in one-dimensional channels arranged in a triangular structure: Theory and Monte Carlo simulations

Adsorption thermodynamics of interacting particles adsorbed on one-dimensional channels arranged in a triangular cross-sectional structure is studied through Bragg-Williams approximation (BWA), Monte Carlo (MC) simulations and the recently reported Effective Substates approximation (ESA) [J.L. Riccardo, G. Zgrablich, W. A. Steele, Appl. Surf. Sci. 196 (2002) 138]. Two kinds of lateral interaction energies have been considered: (1) w_L, interaction energy between nearest-neighbor particles adsorbed along a single channel and (2) w_T, interaction energy between particles adsorbed across nearest-neighbor channels. We focus on the case of repulsive transversal interactions (w_T>0), for which a rich variety of ordered phases are observed in the adlayer, depending on the value of the parameters k_BT/w_T (being k_B the Boltzmann constant) and w_L/w_T. Comparisons between analytical data and MC simulations are performed in order to test the validity of the theoretical models. Appreciable differences can be seen for the different approximations, ESA being the most accurate for all cases.     

Polarization anisotropy in the optical properties of silicon ellipsoids

A new real space quantum mechanical approach with local field effects included is applied to the calculation of the optical properties of silicon nanocrystals. Silicon ellipsoids are studied and the role of surface polarization is discussed in details. In particular, surface polarization is shown to be responsible for a strong optical anisotropy in silicon ellipsoids, much more pronounced with respect to the case in which only quantum confinement effects are considered. The static dielectric constant and the absorption spectra are calculated, showing that the perpendicular and parallel components have a very different dependence on the ellipsoid aspect ratio. Then, a comparison with the classical dielectric model is performed, showing that the model only works for large and regular structures, but it fails for thin elongated ellipsoids.     

Phase transition at finite temperature in one dimension: Adsorbate ordering in Ba/Si(1 1 1)3 × 2

We demonstrate that the Ba-induced Si(1 1 1)3 × 2 reconstruction is a physical realization of a one-dimensional antiferromagnetic Ising model with long-range Coulomb interactions. Monte Carlo simulations performed on a corresponding Coulomb-gas model, which we construct based on density-functional calculations, reveal an adsorbate-ordering phase transition at finite temperature. We show numerically that this unusual one-dimensional phase transition should be detectable by low-energy electron diffraction.     

Reflection characterization of anisotropic ultrathin dielectric films on absorbing isotropic substrates

The reflection of linearly polarized light from an ultrathin anisotropic dielectric film on isotropic absorbing substrate is investigated analytically in the long-wavelength limit. All analytical results are correlated with the numerical solution of the anisotropic reflection problem on the basis of rigorous electromagnetic theory. Simple analytical approach developed in this work not only gives a physical insight into the reflection problem but also provides a way of estimating the necessary experimental accuracy for optical diagnostics by reflection characteristics. It is shown that obtained expressions are of immediate interest for determining the parameters of anisotropic surface layers. Innovative possibilities for optical diagnostics of anisotropic properties of ultrathin dielectric layers upon absorbing materials are discussed.     

The adsorption of methylcyclopentane on Pt(1 1 1)

The adsorption of methylcyclopentane (MCP) on Pt(1 1 1) has been studied using the atom superposition and electron delocalization (ASED-MO) molecular orbital method. Results show a weak interaction with the metallic surface. The adsorption energy is rather independent of the adsorption site coordination number. We find that Pt 6s, 6p_z and 5d_z² orbitals are involved in the bonding with MCP. There is no bonding between the carbon ring and the Pt surface and the interaction comes from the hydrogen atoms to the surface.     

Effects of intersubband interaction on multisubband electron transport in single and double quantum wells

The multisubband electron transport properties are studied for doped single quantum well and gated double asymmetric quantum well structures. The effects due to intersubband interaction and screening of the ionized impurity scattering are also investigated. We show that intersubband coupling plays an essential role in describing the screening properties as well as the effect of ionized impurity scattering on the mobility in a doped single quantum well. For coupled double quantum well structures, negative transconductance is found theoretically which is due to resonant tunneling between the two quantum wells.     

Configurational entropy of adsorbed rigid rods: Theory and Monte Carlo simulations

The configurational entropy of straight rigid rods of length k (k-mers) adsorbed on square, honeycomb, and triangular lattices is studied by combining theory and Monte Carlo (MC) simulations in grand canonical and canonical ensembles. Three theoretical models to treat k-mer adsorption on two-dimensional lattices have been discussed: (i) the Flory-Huggins approximation and its modification to address linear adsorbates; (ii) the well-known Guggenheim-DiMarzio approximation; and (iii) a simple semi-empirical model obtained by combining exact one-dimensional calculations, its extension to higher dimensions and Guggenheim-DiMarzio approach. On the other hand, grand canonical and canonical MC calculations of the configurational entropy were obtained by using a thermodynamic integration technique. In the second case, the method relies upon the definition of an artificial Hamiltonian associated with the system of interest for which the entropy of a reference state can be exactly known. Thermodynamic integration is then applied to calculate the entropy in a given state of the system of interest. Comparisons between MC simulations and theoretical results were used to test the accuracy and reliability of the models studied.     

Modeling multilayer adsorption of interacting polyatomic species on heterogeneous surfaces

In the present work, a generalized lattice-gas model to study multilayer adsorption of interacting polyatomic species on heterogeneous surfaces is introduced. Using an approximation in the spirit of the well-known Brunauer-Emmet-Teller (BET) model, a new theoretical isotherm is obtained in one- and two-dimensional lattices and compared with Monte Carlo simulation. In addition, the BET approach is used to analyze these isotherms and to estimate the monolayer volume. In all cases, the application of the BET equation leads to an underestimate of the true monolayer capacity. However, significant compensation effects were observed for heterogeneous surfaces and attractive lateral interactions.     

Stochastic switching of subphthalocyanine arrays triggered by scanning tunneling microscopy

Single-molecular switching phenomena in monolayer arrays of subphthalocyanine adsorbed on Cu(1 0 0) surface were investigated by scanning tunneling microscopy (STM) under ultrahigh vacuum. The molecules evaporated on the surface arranged in a square lattice taking the Cu(1 0 0)SubPc(5 × 5) epitaxy. During continuous STM imaging at fixed tunneling conditions the topography of the individual molecules spontaneously changed between the high and low states. This topographic change was attributed to orientational switching between the upward and downward adsorption of the axial Cl atom of the molecule on the Cu surface. Molecular energy calculations and statistical thermodynamic evaluation concluded that the tip-triggered disturbance in the close-packed molecular array induced the molecular rearrangement accompanied with the stochastic orientational switching.     

Evaluation of different models for the dissociation of silane on the Si(1 1 1)7 × 7 surface using the extended Brenner empirical potential

Several models have been proposed in the literature for the initial stages of the dissociative chemisorption of silane (SiH₄) on the Si(1 1 1)7 × 7 surface. In this paper, geometry optimisation calculations using the extended Brenner empirical potential have been performed to determine which of these models yields the minimum energy structure. The lowest energy configurations are found to correspond to the dissociation of silane into SiH₂ and two hydrogen atoms. The minimum energy structure involves the adsorption of the two hydrogen atoms onto the dangling bonds of an adjacent adatom and rest atom, and the insertion of the remaining SiH₂ fragment into one of the adatom backbonds. These results are discussed in the light of the existing experimental data.     

First principles study of the electronic and geometric structure of Cu(5 3 2)

Using density functional theory with the generalized gradient approximation and ultra-soft pseudo-potentials, we have calculated structural relaxations of the Cu(5 3 2) surface which contains steps and kinks. We find the relaxation pattern to oscillate dramatically for atoms in the first 10 layers before decaying rapidly in the bulk. The most striking feature is an outward expansion of the relative interlayer separation d₁₂ of 25%. We also find serious discrepancies with relaxation pattern and relaxation amplitudes calculated using embedded atom method potentials that may reflect the limitation of these potentials to accurately describe systems with complex geometries. Full potential calculations reveal a dispersionless surface state along a high symmetry direction in the surface Brillouin zone. Valence charge density along several planes show excess of charge around kink atom and the nature of bonding with other (5 3 2) atoms.     

Electronic theory of the chemisorption effect on surface segregation in transition-metal alloys

The tight-binding Ising model generalized for a system consisting of a transition-metal alloy with chemisorbed adatoms is used to calculate the effect of hydrogen chemisorption on surface segregation in a Cu---Ni alloy. The simple model of chemisorption and of the band structure of the alloy is assumed. The charge-neutrality condition is incorporated into the model.     

The possible role of intermediate NH species in oscillations of the NO+H2 reaction on noble metal surfaces

A comparative study of the thermodynamic properties of adsorbed NH_n species (n = 0, 1, 2, 3) on transition metal surfaces is performed by using the semi-empirical method of interacting bonds. The principal difference between single crystal surfaces exhibiting oscillatory behavior in the NO+H₂ reaction, and those surfaces which do not show such a behavior is that the combination reaction of NH species can easily proceed in the former case, whereas it is substantially endothermic on the latter surfaces.A trigger-like route for the oscillatory behavior is considered where the combination reaction of NH species operates as a temporary reaction pathway. This pathway practically does not contribute to the N₂ formation until the nitrogen coverage reaches some critical value, which ensures a sufficiently close distance between adjacent NH particles. The trigger pathway starts upon reaching that stage initiating the surface wave propagation, and stops immediately when the wave propagation is completed. The surface becomes then nearly clean and ready for the next oscillatory cycle. In this way, the feedback mechanism and the critical point of the regular wave initiation can be understood without any further assumptions. An alternative key reaction is also considered.