Electron surfaces

Chemisorption occurs when the attractive potential well is large so that upon adsorption a strong chemical bond to a surface is fonued. Chemisorption involves changes to both the molecule and surface electronic states. For example, when oxygen adsorbs onto a metal surface, a partially ionic bond is created as charge transfers from the substrate to the oxygen atom. Other chemisorbed species interact in a more covalent maimer by sharing electrons, but this still involves perturbations to the electronic system. 

The surface work fiincdon is fonnally defined as the minimum energy needed m order to remove an electron from a solid. It is often described as being the difference in energy between the Fenni level and the vacuum level of a solid. The work ftmction is a sensitive measure of the surface electronic structure, and can be measured in a number of ways, as described in section B 1.26.4. Many processes, such as catalytic surface reactions or resonant charge transfer between ions and surfaces, are critically dependent on the work ftmction. 

The most popular of the scanning probe tecimiques are STM and atomic force microscopy (AFM). STM and AFM provide images of the outemiost layer of a surface with atomic resolution. STM measures the spatial distribution of the surface electronic density by monitoring the tiumelling of electrons either from the sample to the tip or from the tip to the sample. This provides a map of the density of filled or empty electronic states, respectively. The variations in surface electron density are generally correlated with the atomic positions. 

A DIET process involves tliree steps (1) an initial electronic excitation, (2) an electronic rearrangement to fonn a repulsive state and (3) emission of a particle from the surface. The first step can be a direct excitation to an antibondmg state, but more frequently it is simply the removal of a bound electron. In the second step, the surface electronic structure rearranges itself to fonn a repulsive state. This rearrangement could be, for example, the decay of a valence band electron to fill a hole created in step (1). The repulsive state must have a sufficiently long lifetime that the products can desorb from the surface before the state decays. Finally, during the emission step, the particle can interact with the surface in ways that perturb its trajectory. 

Flamers R J, Tromp R M and Demuth J M 1986 Surface electronic structure of Si(111)-7 7 resolved in real space Phys. Rev. Lett. 56 1972... 

Many of the fiindamental physical and chemical processes at surfaces and interfaces occur on extremely fast time scales. For example, atomic and molecular motions take place on time scales as short as 100 fs, while surface electronic states may have lifetimes as short as 10 fs. With the dramatic recent advances in laser tecluiology, however, such time scales have become increasingly accessible. Surface nonlinear optics provides an attractive approach to capture such events directly in the time domain. Some examples of application of the method include probing the dynamics of melting on the time scale of phonon vibrations [82], photoisomerization of molecules [88], molecular dynamics of adsorbates [89, 90], interfacial solvent dynamics [91], transient band-flattening in semiconductors [92] and laser-induced desorption [93]. A review article discussing such time-resolved studies in metals can be found in... 

Figure Bl.25.12. Excitation mechanisms in electron energy loss spectroscopy for a simple adsorbate system Dipole scattering excites only the vibration perpendicular to the surface (v ) in which a dipole moment nonnal to the surface changes the electron wave is reflected by the surface into the specular direction. Impact scattering excites also the bending mode v- in which the atom moves parallel to the surface electrons are scattered over a wide range of angles. The EELS spectra show the higlily intense elastic peak and the relatively weak loss peaks. Off-specular loss peaks are in general one to two orders of magnitude weaker than specular loss peaks.

Wlien photons of sufiBciently high frequency v are directed onto a metal surface, electrons are emitted in a process known as photoelectron emission [ ]. The threshold frequency Vq is related to the work fimction by the expression... 

Surface electron charge density can be described in tenus of the work fiinction and the surface dipole moment can be calculated from it ( equatiou (Bl.26.30) and equation (B1.26.31)). Likewise, changes in the chemical or physical state of the surface, such as adsorption or geometric reconstruction, can be observed through a work-fimction modification. For studies related to cathodes, the work fiinction may be the most important surface parameter to be detenuined [52]. 

Krasovskll E E and Schattke W 1997 Surface electronic structure with the linear methods of band theory Phys. Rev. B 56 12 874... 

Whitten J L and Pakkanen T A 1980 Chemisorption theory for metallic surfaces Electron localization and the description of surface interactions Phys. Rev. B 21 4357-67... 

Inglesfield J E and Benesh G A 1988 Surface electronic structure embedded self-consistent calculations Phys. Rev. 

Aers G C and Inglesfield J E 1989 Electric field and Ag(OOI) surface electronic structure Surf. Sc/. 217 367 Colbourn E A and Inglesfield J E 1991 Effective charges and surface stability of O on Cu(OOI) Phys. Rev. Lett. 66 2006... 

Figure C1.5.12.(A) Fluorescence decay of a single molecule of cresyl violet on an indium tin oxide (ITO) surface measured by time-correlated single photon counting. The solid line is tire fitted decay, a single exponential of 480 5 ps convolved witli tire instmment response function of 160 ps fwiim. The decay, which is considerably faster tlian tire natural fluorescence lifetime of cresyl violet, is due to electron transfer from tire excited cresyl violet (D ) to tire conduction band or energetically accessible surface electronic states of ITO. (B) Distribution of lifetimes for 40 different single molecules showing a broad distribution of electron transfer rates. Reprinted witli pennission from Lu andXie [1381. Copyright 1997 American Chemical Society.

If photons of light of a suitable wavelength (usually ultraviolet or x-rays) impinge on a metal surface, electrons are emitted. This effect is photoelectric (or photovoltaic) and can be used to start a flow of electrons in a discharge tube. 

Another phenomenon that was inexplicable in classical terms was the photoelectric effect discovered by Hertz in f 887. When ultraviolet light falls on an alkali metal surface, electrons are ejected from the surface only when the frequency of the radiation reaches the threshold... 

Fig. 4. Schematic of a multisequence biosensor in which the target glucose is first converted to glucose-6-phosphate, G6P, in the test solution by hexokinase. G6P then reacts selectively with glucose-6-phosphate dehydrogenase immobilized on the quartz crystal surface. Electrons released in the reaction then chemically reduce the Pmssian blue film (see Fig. 3), forcing an uptake of potassium ions. The resulting mass increase is manifested as a...

Low-temperature adsorption of weak CH proton-donating molecules such as CHFj, acetylene and its derivatives or HCN, enables one to chai acterize the basicity of surface electron-donating sites. 

Fine structure extending several hundred eV in kinetic energy below a CEELS peak, analogous to EXAFS, have been observed in REELS. Bond lengths of adsorbed species can be determined from Surface Electron Energy-Loss Fine Structure (SEELFS) using a modified EXAFS formalism. 

M. De Crescenzi. Phys. Rev. Letts. 30,1949,1987. Use of surface electron energy-loss fine structure (SEELFS) to determine oxygen-nickel bond length changes for oxygen absorbed on Ni (100) on a function of coverage from 0 to 1.0 monolayer. 

X-ray photoelectron spectroscopy (XPS) is currently the most widely used surface-analytical technique, and is therefore described here in more detail than any of the other techniques. At its inception hy Sieghahn and coworkers [2.1] it was called ESCA (electron spectroscopy for chemical analysis), hut the name ESCA is now considered too general, because many surface-electron spectroscopies exist, and the name given to each one must be precise. The name ESCA is, nevertheless, still used in many places, particularly in industrial laboratories and their publications. Briefly, the reasons for the popularity of XPS are the exceptional combination of compositional and chemical information that it provides, its ease of operation, and the ready availability of commercial equipment. 

Spin Density Surfaces. Electrons have a property called spin that allows them to exist in either of two spin states spin up or spin down . Almost all of the molecules that you will encounter will involve each spin-up electron paired to a spin down electron. Thus, the number of spin up and spin down electrons will be the same, and the electron clouds due to each spin will be identical. 

Figure 1.2 A schematic view of an atom. The dense, positively charged nucleus contains most of the atom s mass and is surrounded by negatively charged electrons. The three-dimensional view on the right shows calculated electron-density surfaces. Electron density increases steadily toward the nucleus and is 40 times greater at the blue solid surface than at the gray mesh surface.

Let us see now what happens in a similar linear scan voltammetric experiment, but utilizing a stirred solution. Under these conditions, the bulk concentration (C0(b, t)) is maintained at a distance S by the stilling. It is not influenced by the surface electron transfer reaction (as long as the ratio of electrode area to solution volume is small). The slope of the concentration-distance profile [(CQ(b, t) — Co(0, /))/r)] is thus determined solely by the change in the surface concentration (Co(0, /)). Hence, the decrease in Co(0, t) duiing the potential scan (around E°) results in a sharp rise in the current. When a potential more negative than E by 118 mV is reached, Co(0, t) approaches zero, and a limiting current (if) is achieved ... 

Local breakdown of passive film results from a localized increase in the film dissolution rate at the anion adsorption sites that are attacked by chloride ions, as will be discussed later, in the same manner as substrate metal dissolution. Such acceleration of the dissolution rate was ascribed to the formation of metal chlorides24 or the local degeneration of film surface by the formation of surface electron levels.7... 

Electronegative adatoms cause significant changes in the metal surface electronic stmcture, manifest as changes in the surface work function. In general electronegative additives increase the work function of the metal substrate. Typical examples are shown in Figures 2.9 and 2.10 for the adsorption of Cl and coadsorption of Cl and O on the work function of... 

FIGURE 15.50 The images show four stages in the construction of a ring of iron atoms on a copper substrate. The scientists used top-down" techniques to place 48 iron atoms into a ring. The circular waves seen in the final image show the density of the surface electrons inside the ring, whit h acts as a "i orral" lor the pint trons. 

Whether they are called surfaces or interfaces, when the zones between parts of a structure are "thin"— from a fraction of a micrometer (the limit of the ordinary microscope) down to molecular dimensions—the matter in them assumes a character that is somewhat different from that seen when the same matter is in bulk form. This special character of a molecular population arranged as an interfacial zone is manifested in such phenomena as surface tension, surface electronic states, surface reactivity, and the ubiquitous phenomena of surface adsorption and segregation. And the stmcturing of multiple interfaces may be so fine that no part of the resulting material has properties characteristic of any bulk material the whole is exclusively made up of transition zones of one kind or another. 

The electron charge on the magnetic head was measured by a Guzik instrument. The parameter is chosen to judge the level of the surface electron charge of magnetic heads. When the value is close to 1, the electron charge on... 

Single slab. A number of recent calculations of surface electronic structures have shown that the essential electronic and structural features of the bulk material are recovered only a few atomic layers beneath a metal surface. Thus, it is possible to model a surface by a single slab consisting of 5-15 atomic layers with two-dimensional translational symmetry parallel to the surface and vacuum above and below the slab. Using the two-dimensional periodicity of the slab (or thin film), a band-structure approach with two-dimensional periodic boundary conditions can be applied to the surface electronic structure. 

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