Island nucleation in thin-film epitaxy: A first-principles investigation

We describe a theoretical study of the role of adsorbate interactions in island nucleation and growth, using Ag/Pt(111) heteroepitaxy as an example. From density-functional theory, we obtain the substrate-mediated Ag adatom pair interaction and we find that, past the short range, a repulsive ring is formed about the adatoms. The magnitude of the repulsion is comparable to the diffusion barrier. In kinetic Monte Carlo simulations, we find that the repulsive interactions lead to island densities over an order of magnitude larger than those predicted by nucleation theory and thus identify a severe limitation of its applicability.     

Sticking of rare gases: the effect of lateral interactions

A theory of sticking, based on the kinetic lattice gas that accounts for intrinsic and extrinsic precursors and incorporates the effects of lateral interactions, is used to develop a model for the sticking of rare gases on metals and to derive analytically the model of Zeppenfeld et al. [Surf. Sci. 318 (1994) L1187] that explains their data as due to the formation and coalescence of condensed islands in the adsorbate.     

Surface nucleation and growth in the system of interacting particles

Recent experiments on epitaxial growth of metals on graphene have shown a strong dependence of island densities on coverage. These investigations cannot be explained by the standard mean-field nucleation theories. To understand them, we extend to higher coverage the former theory of rate equations developed for the initial state of nucleation, in a system where adsorbate interaction is included. We account for that, in the case of high coverage, the repulsive interaction influences both the attachment of monomers to clusters and the mobility of atoms. In our work we analyze the modification of the dependence of the island density on coverage, temperature and F/D ratio. In some regimes our theory results in the experimentally observed substantial growth of island density with coverage for a high deposited amount and a weak dependence on deposition rate F. We also find out the local maxima in temperature dependence of island density, as a consequence of long-range repulsive interactions.     

Onset of 3D collective surface diffusion in the presence of lateral interactions: Na/Cu(001)

3He spin-echo measurements are used to follow the picosecond motion of sodium atoms on a copper (001) substrate. 2D correlated motion arising from repulsive adsorbate interactions is observed for coverages as low as 0.04 ML. At coverages greater than 0.05 ML there is a pronounced onset of motion perpendicular to the surface. The perpendicular motion is thermally activated and seems related to the basic translational hopping diffusion process. The correlated motion is modeled successfully using a molecular dynamics simulation and a dipolelike lateral interaction. A simple model which relates the apparent height of the atom with its local coverage is shown to reproduce the experimental observations.     

Angle-resolved UV photoelectron spectroscopy of ethylene and benzene on nickel

A review of results obtained by Angle-Resolved UV-Photoelectron Spectroscopy (ARUPS) using linearly polarized synchrotron radiation is presented for two model systems, ethylene/Ni and benzene/Ni. It is shown that for these systems detailed conclusions concerning adsorbate/substrate and adsorbate/adsorbate interactions can be derived from ARUPS spectra using symmetry selection rules, and in combination with model calculations. In particular, electronic structure, bonding, orientation and symmetry of the adsorbates in dilute and saturated layers will be discussed. It is shown that at high adsorbate coverages lateral interactions in the adsorbate layer play a dominant role. Steric effects in densely packed layers can lead to a reorientation of the molecules as compared to the orientation of the single molecules. The ARUPS spectra of well ordered, densely packed layers exhibit significant (up to 2 eV) dispersion of the various adsorbate bands and allow detailed conclusions on two-dimensional adsorbate band structures.     

Effect of side by side interactions on the thermodynamic properties of adsorbed CO molecules on the Ni(111) surface: a cluster model study

The effect of electrostatic interactions on vibrational frequencies and thermodynamic properties of CO adsorbate on the Ni(111) surface is calculated by taking the first and second nearest-neighbour interactions into account. In order to obtain reasonable results, the cluster model of various surface adsorption sites with CO adsorbate is partially optimized, using Density Functional Theory and also the MP2 method for the hcp site. Comparison between DFT and MP2 results shows that DFT results are more reliable for this system. The stretching and bending frequencies of CO adsorbate are calculated using both Partial Hessian Analysis and Cluster–Adsorbate Coupling methods. Stretching and bending frequencies are both shifted by the side by side interactions. The coupling of surface phonons and adsorbate vibrations reduces the side effects. The largest side effects on the vibrational internal energy, isochoric heat capacity, entropy and total Helmholtz free energy of adsorbed CO molecule calculated using the CAC method are found for 0.5 ML coverage. The results of the CAC method are better, but the PHA method can be used as a simple upper bound estimation. The adsorptive phase acts as an intelligent material in such a way that it changes its configuration in order to reduce the side effects.     

Stochastic resonance in a realistic model for surface adsorption

We study a model for a monolayer single adsorbate system used to describe pattern formation on adsorbates with lateral interactions, when it is submitted to pressure oscillations. Through numerical and analytical (based on a two-state approximation) methods to analyze the existence of stochastic resonance in such a bistable system. This is a first step toward the study of resonant phenomena in adsorbate systems with moving fronts and/or with presence of micro-reactors or spots.     

Self-organization in two- and three-dimensional adsorbates with attractive lateral interactions

Self-consistent lattice gas models for the dynamics of monolayer and multilayer adsorbates with attractive lateral interactions are investigated. The existence of spinodal regions with uphill diffusion is shown. For monolayer growth, periodic stationary distributions of adsorbate density are found analytically. Generalized kinetic BET-model for multilayer growth is studied numerically. A possibility for surface transformation into self-organized arrays of quantum dot-like structures is shown.     

Benzene adsorbed at a metal surface: Which vibrational modes are observable?

The effect of a metal surface on the vibrational spectroscopic activity of an adsorbate is discussed, with benzene as example. The metal influences are classified to show that the intensity of certain adsorbate bands provides information on particular metal/adsorbate interactions.     

Self-organized nanostructures in surface chemical reactions: Mechanisms and mesoscopic modeling

Nanoscale patterns can form in reactive adsorbates on catalytic surfaces as a result of attractive lateral interactions. These structures can be described within a mesoscopic theory that is derived by coarse graining the microscopic master equation thus providing a link between microscopic lattice models and reaction-diffusion equations. Such mesoscopic models allow to systematically investigate mechanisms responsible for the formation of nanoscale nonequilibrium patterns in reactive condensed matter. We have found that stationary and traveling nanostructures may result from the interplay of the attractive lateral interactions and nonequilibrium reactions. Besides reviewing these results, a detailed investigation of a single reactive adsorbate in the presence of attractive lateral interactions and global coupling through the gas phase is presented. Finally, it is outlined how a mesoscopic theory should be constructed for a particular scanning tunneling microscopy experiment [the oxidation of hydrogen on a Pt(111) surface] in order to overcome the failure of a corresponding reaction-diffusion model to quantitatively reproduce the experiments. (c) 2002 American Institute of Physics.     

Effect of oxygen surface groups on adsorption of benzene derivatives from aqueous solutions onto active carbon samples

The process of adsorption of selected benzene derivatives from aqueous solution is investigated on two carbonaceous materials of differentiated surface properties - quantity of oxygen functional groups. Carbon samples were prepared by removal of external layers from granules of unmodified and oxidized active carbon. The surface and structure characteristics of carbon samples were estimated by various methods. The experimental isotherms of organics adsorption from liquid phase were measured and interpreted in terms of the theory of adsorption on heterogeneous solid surfaces. The influence of differences in adsorbate and adsorbent properties on adsorption uptake was analyzed. The adsorption effectiveness was regarded as a result of the differences in adsorbate hydrophobicities and the effect of specific interactions of its functional groups with active sites on carbon surface.     

Surface molecules and chemisorption: I. Adatom density of states

A useful picture of chemisorption on metal surfaces is one in which a localized molecule is formed between the adatom and its nearest neighbor substrate atoms. The interaction responsible for the molecule formation is treated as the coupling between the adsorbate state and a group orbital formed from a linear combination of atomic orbitals on the substrate atoms. Within the surface molecule picture, level width and level shift functions, given by Newns modification of the Anderson theory, have been calculated and the resulting adatom density of states function has been obtained. This has been done for model systems in which the substrate is either a free electron metal or a tightbinding p-band metal and the adsorbate is s or p like. The results show how it is possible to simultaneously have narrow virtual levels due to chemisorption (～ 1 eV) which previously implied weak interactions and also high binding energies (? 3 eV) as are observed experimentally.     

Diffuse LEED intensities of disordered crystal surfaces: II. Multiple scattering on disordered overlayers

The diffraction of low energy electrons from disordered overlayers adsorbed on ordered substrates is treated theoretically by an extension of Beeby's multiple scattering method. A lattice gas model is assumed for the disordered adsorbate layer. Multiple scattering within a certain area around each atom — each atom of the overlayer and within the ordered substrate — is treated self-consistently, the remaining contributions to the total scattering amplitude being averaged. The theory can be used in the limiting cases of random distribution and of long range order within the adsorbate layer.     

Tunneling spectroscopy as a probe of adsorbate-surface interactions

Tunneling spectroscopy is a sensitive probe of two classes of adsorbate-surface interactions: interactions of the adsorbate with the substrate on which it is adsorbed and adsorbate interactions with the top metal electrode that is evaporated on top of it. The talk by Professor Hipps focuses on the first of these classes. This talk focuses on the second. In general, the interaction of the adsorbed molecules with the top metal electrode produces a down-shift in the vibrational mode position ranging in size from 0.1% to 10% depending on the dipole derivative of the mode and the type of top metal electrode.     

Infrared spectroscopy of CO on NaCl(100) III. Submonolayers and isotopic mixtures

In this paper we explore lateral interactions within the CO adsorbate on NaCl(100) through its infrared spectroscopy.

The infrared absorption of a monolayer of CO on NaCl(100) at 55 K presents a symmetric band that can be fitted to a Lorentzian profile. As the coverage is reduced the integrated absorbance decreases, the band shifts to higher wavenumber, and its profile broadens and becomes less symmetric. These observations are consistent with a random arrangement of the molecules for submonolayer coverages. This spectroscopic behavior is likely due to myriad electric multipolar interactions plus dispersion and repulsion contributions that become diminished as coverage is reduced. Heterogeneities at the surface can also give rise to coverage dependent spectroscopic profiles. Finally, increased mobility of the adsorbate for decreasing coverages can effect the spectroscopic response. Because of these complications the quantitative behavior of the submonolayer absorption frequency and bandshape has not been successfully modeled. Isotopic composition of the monolayer also affects the spectroscopy. Dilution of ¹²C¹⁶O with ¹³C¹⁶O shifts the absorption to lower wavenumber and its band profile becomes broader and asymmetric. A similar behavior is exhibited by the ¹³C¹⁶O band on dilution with ¹²C¹⁶O. Models based on dynamic dipole coupling can account for the spectroscopic behavior of the isotope mixtures in the monolayer.     

Kinetics of multilayer adsorption and desorption

The equations describing the nonequilibrium kinetics of multilayer adsorption and desorption are derived. The method is based on a generalized lattice gas model and includes the mobility of adsorbate particles and their mutual interactions. For the two layer adsorbate having the structure of a square lattice the isothermal adsorption characteristics are calculated.     

Structural rearrangement of solid surfaces due to competing adsorbate-substrate interactions

Employing a generalized lattice gas theory and the Brownian dynamics simulation, we show that the competing displacive interaction in an adsorbate may cause a continuous distortive transition in the underlying substrate. The threshold for the transition is determined by the competition of the substrate rigidity and the quasielastic energy induced by the adsorbate. In the presence of a strong pinning and repulsive lateral interaction, the resulting structure appears as a compromise between the square lattice of the substrate and the hexagonal arrangement of the adsorbate. For hexagonal substrate lattices the simulation demonstrates that various adsorbate structures (from honeycomb lattices to quasicrystalline pentagonal configurations) may be observed, depending on the effective radii of interaction. Due to the long-ranged coupling the substrate may acquire a substructure induced by the adsorbate. This paper represents a generalization of the work published in Phys. Rev. Lett. 81, 3904 (1998).     

Adsorption isotherms for fluids with strong interparticle repulsions

We derive adsorption isotherms for an adsorbate of hard-sphere particles with sticky interactions at any fluid density being adsorbed onto a plane, sticky surface. The theory is based on the Percus-Yevick theory for bulk fluids and explicitly includes the equilibrium between the adsorbed fluid and the bulk adsorbate. The theory predicts a surface condensation at low temperatures and low bulk densities in good agreement with surface condensations found in experimental studies of adsorption of gases onto graphite. An approximate law of corresponding states for these transitions is developed. At higher bulk densities and room temperatures, the adsorption isotherms can show a maximum, in accord with recent experimental work.Supported by the Australian Research Grants Commission.