Theoretical studies of hydrogen molecule adsorption on flat and stepped platinum surfaces

Theoretical calculations have been applied to the adsorption of hydrogen molecule on flat and stepped platinum surfaces. The method of large unit cell is modified to deal with the stepped surface as well as the flat one. This method is free from the boundary effect which is inevitable in the cluster method. The results calculated for the d-band width and the highest occupied level are in good agreement with the experiments. For the dissociative adsorption, the bottom of the step site is the most favorable, and the result is attributed to the extra orbital interactions at this site.     

Ellipsometric studies of adsorption reactions on clean surfaces

The ellipsometric effects measured upon adsorption in the monolayer range are discussed. In general there are two possible contributions, the effect of the adsorbed layer itself and the effect due to a change in the substrate surface induced by the adsorbed layer. The latter effect occurs mainly in the case of chemical adsorption.The ellipsometric measurements on a number of clean semiconductor surfaces are treated and the results are compared with those obtained by other methods, e.g. electron energy loss spectroscopy and ultra-violet photon spectroscopy.     

LEED studies of adsorption on vicinal copper surfaces

As a means for studying the role of atomic steps in adsorption phenomena LEED has been used to investigate the properties of vicinal copper surfaces. Single crystalline surfaces were cut at angles up to 20° from the (100) pole along [001] and [011̄] zones. The diffraction patterns obtained for the clean surfaces and after adsorption of oxygen, nitrogen ions, carbon and sulphur are described. The emphasis of the paper is on the method of interpretation of the geometry of the patterns, which may be done by straightforward kinematic analyses. In the case of nitrogen it is found that if the steps are widely separated the structure of the layer adsorbed on the terrace is the same as that on the low index surface. When the step spacing is small, and comparable with the crystalline parameter of the adsorbed layer, modifications occur which give rise to different superlattices which extend over several terraces. Adsorption of sulphur on 〈11〉 steps can produce a change in the periodicity of the adsorbed layer parallel to the step direction. The study of diffraction patterns for vicinal surfaces with different step spacings may provide an interesting technique for verifying the interpretation of patterns for low index surfaces.     

Theoretical studies of adatom diffusion on metal surfaces

We propose in this paper a theoretical model to investigate surface self-diffusion of single adatoms on two different low-index planes, closely packed (001) and densely packed (111), of face-centered-cubic rhodium, nickel and copper metal crystals. Two realistic model potentials are applied to describe the interatomic interaction of the adatom-substrate systems. The first model is a Morse-type potential, which involves several empirical fittings of bulk of solid. The second, newly popular, potential was introduced by Sutton and Che, which incorporates many-body effects. With these potentials, conventional molecular dynamics (MD) is employed to obtain trajectories of the atoms. The average squared didplacements are computed for a range of initial kinetic energies, and the surface diffusion constants can be obtained by means of the Einstein relation. The estimated random walk exponential prefactors and activation energies exhibit an Arrhenius behavior, and are compared with previous results.     

Theoretical insight of adsorption thermodynamics of multifunctional molecules on metal surfaces

Adsorption thermodynamics based on density functional theory (DFT) calculations are exposed for the interaction of several multifunctional molecules with Pt and Au(1 1 0)-(1 × 2) surfaces. The Gibbs free adsorption energy explicitly depends on the adsorption internal energy, which is derived from DFT adsorption energy, and the vibrational entropy change during the chemisorption process. Zero-point energy (ZPE) corrections have been systematically applied to the adsorption energy. Moreover the vibrational entropy change has been computed on the basis of DFT harmonic frequencies (gas and adsorbed phases, clean surfaces), which have been extended to all the adsorbate vibrations and the metallic surface phonons. The phase diagrams plotted in realistic conditions of temperature (from 100 to 400 K) and pressure (0.15 atm) show that the ZPE corrected adsorption energy is the main contribution. When strong chemisorption is considered on the Pt surface, the multifunctional molecules are adsorbed on the surface in the considered temperature range. In contrast for weak chemisorption on the Au surface, the thermodynamic results should be held cautiously. The systematic errors of the model (choice of the functional, configurational entropy and vibrational entropy) make difficult the prediction of the adsorption-desorption phase boundaries.     

Features in atomic force microscopy studies of dielectric surfaces

To improve the accuracy of AFM measurements in air and the reproducibility of results, a clean room-based metrological facility has been designed and built. The main function of the facility is to control temperature and humidity in an operation zone in various combinations and to maintain them with high accuracy. Measurements under controlled conditions are particularly important for dielectric materials. It has been shown that special procedures allow one to avoid disturbances caused by static charges on the surface under study, i.e., to remove the already accumulated charge and prevent its appearance during experiments. The use of the proposed procedures makes it possible to adequately study the features of the dielectric surface relief at micro-and nanoscale levels.     

Solid-state NMR studies of bacterial lipoteichoic acid adsorption on different surfaces

Teichoic acids are important to bacteria for surface adhesion, metal ion coordination, and other biological processes crucial to bacterial survival. In particular, the surface adhesion of teichoic acids plays a crucial role in the formation of Gram-positive biofilms. Biofilms have been implicated as the major cause of various chronic infections. Biofilm formation is essentially a four-step process beginning with the adhesion of bacteria to a surface, followed by the excretion of an extracellular polymeric substance (slime), development and maturation of the biofilm architecture, and finally biofilm spreading through bacterial release. Currently, there is very little molecular level information available for the initial adhesion of bacteria to solid surfaces. Solid-state NMR is ideally suited for the study of these samples, thus we use (31)P solid-state NMR experiments to study the initial adhesion of lipoteichoic acid (LTA) to various surfaces. (31)P CP-MAS spectra and T(1)(rho) data demonstrate that the structure of LTA changes when adhered to cellulose, cell wall peptidoglycan (PGN), or TiO(2). However, when LTA is simultaneously adhered to PGN and TiO(2) the observed structure is dependent on the amount of retained water. For LTA on TiO(2), we suggest that the alanine and glucosamine groups interact with the surface. However, during simultaneous adhesion to TiO(2) and PGN, the glucosamine groups bind to the PGN while the alanine groups bind to the surface. This arrangement traps water between the PGN and TiO(2) surface.     

Theoretical studies on adsorption heat transformer using zeolite-water vapour pair

An adsorption heat transformer can raise the temperature level of a fraction of waste heat by rejecting the remaining heat to a low temperature level. In this work some alternatives in the design of an adsorption heat transformer, such as a 2-tank system, 3-tank system and 4-tank system, are evaluated using zeolite-water vapour as the adsorbent-adsorbate pair. The values of coefficient of performance (COP) are computed for each system for various temperatures of waste heat source at which the heat is available and heat sink at which the heat is delivered.It is found that an adsorption heat transformer can be used for a gross temperature lift as high as 50°C with a fairly good COP value. Moreover the 4-tank system gives a much improved COP value as compared to the 2-tank and 3-tank systems for the same operating conditions. It is also found that the effect of temperature driving force for heat transfer on the COP value is quite pronounced.     

Theoretical studies of the electronic structure of semiconductor surfaces

Methods developed by the author and J.A. Appelbaum have been used to examine the electronic Structure of semiconductor surfaces in a variety of situations. These essentially first principles calculations self-consistently determine the potential in a surface region several atom layers thick which continuously join to a semi-infinite bulk region whose self-consistent potential is previously determined. Model potentials adjusted to fit bulk and atomic levels represent the ion cores, and a local functional of the density represents the exchange and correlation potential. Electronic states are found in a mixed real-space Fourier-space representation using a transfer matrix technique. A primary emphasis in the problems studied has been to relate features in experimentally accessible surface spectra to hypothesized rearrangements in the atomic geometry and chemical bonding at the surface. Studies of the unreconstructed and reconstructed clean Si(100) surface and of H chemisorption on several Si surfaces will be described as examples of the utility of the methods.     

CO adsorption studies on pure and Ni-covered Cu(111) surfaces

The adsorption of CO on pure and Ni-covered Cu(111) surfaces has been studied by means of LEED, TDS, UPS and work function measurements during adsorption and desorption. Different Ni-coverages between 0.1 and 2 monolayers were obtained by Ni-evaporation controlled by a quartz micro balance and by AES. Near room temperature Ni grows in a layer-by-layer mode on Cu(111). The island structure of the surfaces with submonolayer Ni-coverages is clearly demonstrated by TDS und LEED results obtained after CO adsorption. As with surfaces of bulk Cu-Ni alloys CO adsorption on Cu(111) with submonolayer Ni-coverage is dominated by a site effect. Cu-, Ni-, and mixed adsorption sites can be distinguished. The CO induced work function changes for Ni- and Cu-site adsorption show the same sign as observed with the pure metals. Mixed site adsorption has only a minor influence on the work function. A “ligand effect” observed only for the Ni-site adsorption, and only at small Ni-coverages is discussed in detail. Studies on the adsorption kinetics reveal that the Cu-sites may serve as precursor sites for Ni-site adsorption. Detailed UPS studies demonstrate that the CO-induced emission maxima observed on Cu surfaces with submonolayer Ni-coverages can be interpreted as a superposition of the respective adsorption features observed with the pure metals, roughly separated by their work function difference.     

Theoretical study of the influence of laser-induced defects on the adsorption of gases on solid surfaces

Laser treatment of a solid surface was modeled by applying an analytical theory as well as by using Monte Carlo simulations. The crystalline surface was assumed to be initially smooth and chemically uniform, that is free of impurities built into the structure. Creation of surface defects by a laser beam was assumed to have entirely random nature. In particular, the surface was assumed to have been scanned by the beam focused successively on randomly chosen points. In the course of the ablation process, the beam produces a pyramidal crater whose dimensions are proportional to the applied laser power. According to the assumed nature of the scanning procedure, the craters formed by the beam are allowed to overlap. The influence of the number of laser pulses and the crater dimensions on the structural and adsorptive properties of the surface were examined by analysis of the variation of the mean surface depth and the surface width. Changes in the adsorptive properties were also estimated by the calculation of the thermally programmed desorption (TPD) spectra of monomolecular adsorbates desorbed from laser-treated surfaces. Additionally, equilibrium adsorption isotherms were calculated for the obtained surfaces.     

Theoretical and experimental studies on the adsorption behavior of thiophenol on gold nanoparticles

FT‐Raman spectra were obtained for thiophenol (TP) and TP on gold nanoparticles. All vibrational fundamentals for the TP molecule are assigned on the basis of the scaled quantum force field procedure. Three model systems are studied and compared for the interactions of TP with the Au atom: (1) TP with a Au atom, C₆H₅SH Au; (2) TP anion with a Au atom, C₆H₅S⁻ Au; and (3) TP with a Au atom and subsequent formation of thiophenylate, C₆H₅SAu. The equilibrium structures and Raman spectra were calculated for the model systems using density functional theory (DFT) with the B3LYP functionals and the mixed basis set 6‐311 + G** (for C, S, H) and LANL2DZ (for Au), and theoretical Raman wavenumbers of C₆H₅SAu and C₆H₅S⁻ Au were assigned according to potential energy distributions. The third model system is shown to be preferred over the other two. The calculated binding energies are also shown to support the third model system. It is suggested that a simple model, such as the one used in the present study, is reasonable to describe surface‐enhanced Raman spectroscopy of thiophenol adsorbed on gold nanoparticles. Copyright © 2007 John Wiley & Sons, Ltd.     

Comments on the structures observed for atomic adsorption on (110) surfaces of face-centred cubic metals

The hybridisation model for face-centred cubic metals, proposed by Altmann, Coulson and Hume-Rothery, is used for analysing some aspects of the surface structures reported by LEED crystallography for S adsorbed on the (110) surfaces of nickel and rhodium, and for O adsorbed on the (110) surfaces of nickel and iridium. The main objectives are to rationalise the different adsorption sites adopted by S and O, and to assess the measured bond lengths. For the latter, use is made of a bond length-bond order relationship given by Pauling.     

Theoretical studies of ultrathin film-induced faceting on W(111) surfaces

We have used local volume (or EAM) potentials to study the pyramidal faceting (or reconstruction) of a W(111) surface induced by face center cubic (fcc) metals Pd, Pt, Au, and a body center cubic (bcc) metal Mo. We found that the surface-energy differences of (211) and (111) surfaces of bcc W increases as one or few monolayers of Pd, Pt, Au, and Mo films are deposited. We found that the lateral relaxation which is allowed on the (211) surface further increases the surface energy anisotropy as the thickness of the fcc metal film increases. Our calculated results are consistent with the argument that the surface energy anisotropy is the driving force for the faceting, but do not rule out three-dimensional (3D) island growth as another possible mechanism for the (211) faceting. We also found that there is a possible bilayer growth mode in W(211) surfaces with Pt and Pd films.     

Theoretical studies of argon adsorption in MCM-41 mesoporous systems

Adsorption isotherms are predicted for spherical adsorbates in cylindrical channels of MCM-41 mesoporous materials over a wide range of temperatures by using the “fragment method”. This prediction shows that an equilibrium capillary condensation is impossible for pores with diameters smaller than 2.5 nm. The adsorbate distribution in relatively large pore channels was described by the quasi-chemical approximation (QCA) that takes into account direct pair correlations between interacting molecules. In order to improve the lattice-gas model in the vicinity of the critical point, a calibration function that takes into account information from the fragment method, was introduced into the QCA equations. The influence of the size factor of pores on argon adsorption isotherms was demonstrated.     

Hydrogen adsorption on metal surfaces

Extensive calculations of the ground state properties of hydrogen chemisorbed on transition metal surfaces are presented. The calculations are performed using the effective medium theory. The results for the chemisorption energies on all the 3d, 4d and 5d metals presented are in good agreement with experiment. The trends along a particular row are shown to be dominated by the degree of filling of the d band. The full adiabatic potential energy surface is presented for a number of experimentally interesting systems, including H/Ni(111), H/Ni(110), H/W(100) and H/W(110). Equilibrium sites, bond lengths, vibrational frequencies and surface diffusion energies are deduced and compared with experiment. Again, agreement is good. The surface and adsorbate parameters determining those observables are discussed. It is shown that a simple canonical relationship exists between the perpendicular vibrational frequency and the metal-hydrogen bond length. This formulation, which is not based on pair potentials, should be useful as a first estimate of bond lengths from measured vibrational data.     

Polymer adsorption on heterogeneous surfaces

The adsorption of a single ideal polymer chain on energetically heterogeneous and rough surfaces is investigated using a variational procedure introduced by Garel and Orland (Phys. Rev. B 55, 226 (1997)). The mean polymer size is calculated perpendicular and parallel to the surface and is compared to the Gaussian conformation and to the results for polymers at flat and energetically homogeneous surfaces. The disorder-induced enhancement of adsorption is confirmed and is shown to be much more significant for a heterogeneous interaction strength than for spatial roughness. This difference also applies to the localization transition, where the polymer size becomes independent of the chain length. The localization criterion can be quantified, depending on an effective interaction strength and the length of the polymer chain. Received: 29 October 1997 / Revised: 19 December 1997 / Accepted: 6 March 1998     

Electron spectroscopy studies of adsorption and oxidation processes at metal surfaces

A review of the problems involved and the success achieved in extracting analytical and chemical information from adsorption and oxidation studies at c