Local surface electronic properties

The chemical bond of H to the surface of a metal is, of course, of electronic nature. A strong perturbation of the substrate valence band and of the H Is wave function takes place. So called H induced states are formed, comparable to the H induced band in the electronic structure of metal hydrides. Accordingly, surface electronic properties such as local density of states, work function, surface magnetization, and possibly valency are affected by the adsorption of H. 

Wachutka G, Fleszar A, Maca F and Scheffler M 1992 Self-consistent Green-function method for the calculation of electronic properties of localized defects at surfaces and in the bulk J. Phys. Condens Matter A 2831 Bormet J, Neugebauer J and Scheffler M 1994 Chemical trends and bonding mechanisms for isolated adsorbates on Al(111) Phys. Rev. B 49 17 242... 

In this contribution it is shown that local density functional (LDF) theory accurately predicts structural and electronic properties of metallic systems (such as W and its (001) surface) and covalently bonded systems (such as graphite and the ethylene and fluorine molecules). Furthermore, electron density related quantities such as the spin density compare excellently with experiment as illustrated for the di-phenyl-picryl-hydrazyl (DPPH) radical. Finally, the capabilities of this approach are demonstrated for the bonding of Cu and Ag on a Si(lll) surface as related to their catalytic activities. Thus, LDF theory provides a unified approach to the electronic structures of metals, covalendy bonded molecules, as well as semiconductor surfaces. 

The similarity of the results obtained for finite elusters and the infinite slab allows to eonclude in favour of the validity of the eluster model of adequate size (6 or 8 molybdenum atoms). In addition to the chemisorption of organic molecules on solid surfaces which is generally considered as a localized phenomenon, the interaction between molybdenum oxide and an adsorbate can also be represented by a loeal eomplex formed by a finite eluster and the adsorbed molecule. Indeed, the study of the evolution of the electronic properties as a funetion of the cluster size shows that, for a eluster eontaining 6 or 8 molybdenum atoms, most of the electronic properties converge towards limit values. This eonvergence is sensitive to the direction of the cluster growth. On the other hand, the electronic properties of the (001), (010) and (100) faces are not identieal, the type of surface atoms being different these results allow to predict that the characteristics of the chemisorption step will depend on the particular face on which it takes place. 

In the conductance image, a dark color represents high electronic conductance, whereas a white color corresponds to areas of low or zero electronic conductance. Taking into account that the tip is in physical contact with the oxide, the magnitude of the current is determined by the local electronic properties of the electrode and the tip, and the tip-sample voltage difference. The surface conductance image of the cathode from the fresh cell... 

These studies indicate that the charge transfer at the metal-oxide interface alters the electronic structure of the metal thin film, which in turn affects the adsorption of molecules to these surfaces. Understanding the effect that an oxide support has on molecular adsorption can give insight into how local environmental factors control the reactivity at the metal surface, presenting new avenues for tuning the properties of metal thin films and nanoparticles. Coupled with the knowledge of how particle size and shape modify the metal s electronic properties, these results can be used to predict how local structure and environment influence the reactivity at the metal surface. 

Various astoichiometric components (hydrogen, carbon, and others, for example, silicium and aluminum) present may interact with localized and nearly free electrons to differing extents. According to the localized free electron interplay model of metal catalysts developed by Knor 163, 164) the ratio of the two types of electrons may influence the catalytic properties considerably. For example, a subsurface proton attracts nearly free electrons and thus uncovers some localized orbitals. Carbon may interact first with localized electrons 164). This may be one of the reasons why their effects are of opposite character. The collective efforts of catalytic and surface chemists are necessary to bring some clarity to the multitude of problems arising here. 

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