Direct observation of surface diffusion and atomic interactions on metal surfaces

The unique attributes of the field ion microscope permit the direct observation of surface diffusion of single atoms and simple atomic clusters on perfect crystal planes. A brief review of the principles and techniques of such studies is presented along with a collection of much of the existing experimental data. Emphasis is placed on more recent work such as the diffusion of adatoms under the influence of a driving force, the kinetics of cluster formation and dissociation, and how the interatomic force between two atoms on a surface is related to the diffusion parameters and the pair distribution function.     

Effect of the long-range adsorbate interactions on the atomic self-assembly on metal surfaces

Recent experimental studies have demonstrated that short linear chains are often formed in the early stage of heteroepitaxy on the (1 1 1) noble metal surfaces at low temperatures. Here, we show that the surface-state mediated long-range interaction between adsorbates is the driving force for the self-organization of adsorbates at very low temperatures. Our kinetic Monte Carlo simulations for Co adatoms on Cu(1 1 1) and for Ce adatoms on Ag(1 1 1) reveal that these interactions can lead to the formation of linear chains.     

Relaxation near transition metal surfaces

A simple calculation of the relaxation near transition metal surfaces is described. The d electrons are treated in a tight-binding approximation and Born-Mayer type potentials are used to simulate the repulsive part of the energy at short distances. The interplanar spacing is found to decrease at the center of the series and to increase on the wings. For almost empty or filled bands one obtains no relaxation.     

Interaction of atomic hydrogen with metal surfaces

Received: 23 March 1998/Accepted: 21 August 1998     

Adsorption of transition metal monolayers on tungsten surfaces

In a simple self-consistent band model, we calculate the work function change when one adsorbs monolayers of transition metals on tungsten. The work function change with the coverage is in agreement with the experimental results. It shows a maximum for one monolayer and is nearly equal to the difference between the work functions of W and the adsorbed element for a coverage equal to a few monolayers. In all the cases, the charge transfer between the adatoms and the tungsten surface atoms are small. This point allows us to simply calculate the binding energies of the monolayer. The same model is also applied to discuss the diffusion of a monolayer into a bulk transition metal.     

Theory of hydrogen vibrations on transition metal surfaces

The site dependence of the vibration frequency, normal to the surface, of a neutrally adsorbed atom such as hydrogen on a transition metal surface is studied. The vibration frequency in the atop position is compared with the value in the metal-atom dimer. The bond length at the surface is found to be greater than in the dimer and to increase with increasing number of nearest neighbours. For strong bonding, the vibration frequency in the atop position is close to that in the dimer, and a comparison of the adsorbate vibration spectrum with that of molecular systems is justified. For weak binding the vibration frequencies are strongly shifted from the values of the dimer and such a comparison is not valid. In this limit the model of Froitzheim et al. is found to apply. A simple relation between the adsorption energy and vibration frequency is given. Bond relaxation is found to be very important in determining the vibration characteristics of adsorbed species.     

On the interactions of adatoms on metal surfaces

Pariwise interactions of the adatoms and ions adsorbed on metal surfaces has been investigated with the help of the pole approximation in integral equations of the Lippman-Swinger type. These interactions have been shown to depend mainly both on the type of the metal spectrum and on the electron structure of the adatoms. The theory developed in this paper gives a satisfactory explanation of several facts observed in experiments, especially the longrange oscillating interaction between adatoms.     

Hydrogen vibrations at transition metal surfaces

Chemisorbed hydrogen has been studied on a variety of simple and composite transition metal surfaces using local density functional calculations. The goal of these studies is to elucidate trends and general principles in bond energies, atomic geometries, vibrational frequencies, and dynamic effective charges. The theoretical approach, based on the linear augmented plane wave method, will be reviewed. Results will be discussed for H in 2-, 3-, and 4-fold sites on W(001), Ru(0001), Cu(111), Pt(111), Rh(001), and the metal overlayer systems Cu-Ru(0001) and Ni-W(001). In most cases, all the harmonic vibrational modes were studied. Some anharmonic effects were examined. While good agreement has been obtained with much of the available experimental data, some outstanding disagreements will be discussed. Our results will be compared with the nearest-neighbor harmonic potential model and effective medium approach.     

Magnetic anisotropies of late transition metal atomic clusters

We analyze the impact of the magnetic anisotropy on the geometric structure and magnetic ordering of small atomic clusters of palladium, iridium, platinum, and gold. We have employed a noncollinear implementation of density functional theory where the spin-orbit interaction has been included self-consistently. The size of the clusters ranges from two to five, six, or seven atoms, depending on the element. Our results highlight the relevance of the spin-orbit interaction in the magnetic properties of small atomic clusters made of fourth- and fifth-row elements.     

Ultrafast electron interactions in metal clusters

The recent extension of time-resolved femtosecond optical techniques to the investigation of the ultrafast electron scattering processes in metal clusters offers the unique possibility to follow their evolution from a bulk to a confined metal. The size dependent results obtained in model materials, the noble metals, are presented, focusing on the impact of the confinement on energy redistribution processes (electron–electron and electron–phonon coupling). Their application to the investigation of the acoustic vibration property of cluster and to the cluster-surrounding matrix energy transfers are also discussed. To cite this article: N. Del Fatti, F. Vallée, C. R. Physique 3 (2002) 365–380.     

分子尺度上水和金属表面的相互作用

虽然水普遍存在,但人们在分子尺度上对水与固体表面的相互作用的理解却仍然处在初始阶段.文章简述了20年来人们对水在贵金属表面的吸附和浸润过程进行微观尺度上研究的进展,分析和讨论了水和表面作用的一般规律和所获得的经验教训,特别着重讨论了对上世纪80年代人们提出的经典双层冰模型的修正.     

2D atomic mapping of oxidation states in transition metal oxides by scanning transmission electron microscopy and electron energy-loss spectroscopy

Using a combination of high-angle annular dark-field scanning transmission electron microscopy and atomically resolved electron energy-loss spectroscopy in an aberration-corrected transmission electron microscope we demonstrate the possibility of 2D atom by atom valence mapping in the mixed valence compound Mn3O4. The Mn L(2,3) energy-loss near-edge structures from Mn2+ and Mn3+ cation sites are similar to those of MnO and Mn2O3 references. Comparison with simulations shows that even though a local interpretation is valid here, intermixing of the inelastic signal plays a significant role. This type of experiment should be applicable to challenging topics in materials science, such as the investigation of charge ordering or single atom column oxidation states in, e.g., dislocations.     

分子尺度上水和金属表面的相互作用

虽然水普遍存在,但人们在分子尺度上对水与固体表面的相互作用的理解却仍然处在初始阶段.文章简述了20年来人们对水在贵金属表面的吸附和浸润过程进行微观尺度上研究的进展,分析和讨论了水和表面作用的一般规律和所获得的经验教训,特别着重讨论了对上世纪80年代人们提出的经典双层冰模型的修正.     

Interaction of carbon monoxide with transition metal surfaces

XPS studies of the interaction of carbon monoxide with surfaces of Fe, Co and Ni indicate that at 300 K, the disproportionation reaction is prominent up to exposures of 10³ L giving rise to high surface concentrations of carbon. At higher exposures and higher temperatures, dissociation of carbon monoxide accompanied by the formation of surface oxide layers becomes more prominent. In the case of copper, disproportionation is prominent up to 10⁴ L even at 500 K followed by dissociation at higher exposures. These results are also supported by Auger spectroscopic studies.     

Semiclassical dynamics of electron transfer at metal surfaces

In this Letter, we demonstrate that nonadiabatic dynamics of molecular scattering from metal surfaces can be efficiently simulated by semiclassical Gaussian wave packet propagation on a local complex potential. The method relies on the wideband limit decoupling of the nuclear equations of motion on different electronic states. If the continuum diabatic potential surfaces are assumed to be parallel, the number of Gaussian wave packets spawned scales at most linearly with propagation time, allowing efficient propagation of nuclear dynamics.