Surface chemical bond

What is the nature of surface chemical bonds, and what are their energies ... 

Chemisoq)tion bonding to metal and metal oxide surfaces has been treated extensively by quantum-mechanical methods. Somoijai and Bent [153] give a general discussion of the surface chemical bond, and some specific theoretical treatments are found in Refs. 154-157 see also a review by Hoffman [158]. One approach uses the variation method (see physical chemistry textbooks) ... 

T. N. Rhodin and G. Ertl, The Nature of the Surface Chemical Bond, North-Holland, Amsterdam, 1979. 

Surfaces that do not have strong surface chemical bonds that were broken tend to be nonpolar and are not readily wetted. Substances such as graphite and talc are examples that can be broken along weakly bonded layer planes without rupturing strong chemical bonds. These solids are naturally floatable. Also, polymeric particles possess... 

Of these, the most extensive use is to identify adsorbed molecules and molecular intermediates on metal single-crystal surfaces. On these well-defined surfaces, a wealth of information can be gained about adlayers, including the nature of the surface chemical bond, molecular structural determination and geometrical orientation, evidence for surface-site specificity, and lateral (adsorbate-adsorbate) interactions. Adsorption and reaction processes in model studies relevant to heterogeneous catalysis, materials science, electrochemistry, and microelectronics device failure and fabrication have been studied by this technique. 

Gas phase transition metal cluster chemistry lies along critical connecting paths between different fields of chemistry and physics. For example, from the physicist s point of view, studies of clusters as they grow into metals will present new tests of the theory of metals. Questions like How itinerant are the bonding electrons in these systems and Is there a metal to non-metal phase transition as a function of size are frequently addressed. On the other hand from a chemist point of view very similar questions are asked but using different terminology How localized is the surface chemical bond and What is the difference between surface chemistry and small cluster chemistry Cluster science is filling the void between these different perspectives with a new set of materials and measurements of physical and chemical properties. 

When an atom or molecule is adsorbed on a surface new electronic states are formed due to the bonding to the surface. The nature of the surface chemical bond will determine the properties and reactivity of the adsorbed molecule. In the case of physisorption, the bond is rather weak, of the order of 0.3 eV. The overlap of the wave functions of the molecule and the substrate is rather small and no major change in the electronic structure is usually observed. On the contrary, when the interaction energy is substantially higher, there are rearrangements of the valence levels of the molecule, a process often denoted chemisorption. The discrete molecular orbitals interact with the substrate to produce a new set of electronic levels, which are usually broadened and shifted with respect to the gas phase species. In some cases completely new electronic levels emerge which have no resemblance to the original orbitals of the free molecule. 

The electronic structure of the surface chemical bond is discussed in depth in the present chapter for a number of example systems taken from the five categories of bonding types (i) atomic radical, (ii) diatomics with unsaturated -systems (Blyholder model), (iii) unsaturated hydrocarbons (Dewar-Chatt-Duncanson model), (iv) lone pair interactions, and (v) saturated hydrocarbons (physisorption). 

The measured electronic structure, occupied or unoccupied, provides the fullest information when also combined with theory. Electronic structure calculations in surface chemistry have advanced immensely in the past decades and have now reached a level of accuracy and predictive power so as to provide a very strong complement to experiment. Indeed, the type of theoretical modeling that will be employed and presented here can be likened to computer experiments, where it can be assumed that spectra can be computed reliably and thus computed spectra for different models of the surface adsorption used to determine which structural model is the most likely. In the present chapter, we will thus consistently use the interplay between experiment and theory in our analysis of the interaction between adsorbate and substrate. Before discussing what quantities are of interest to compute in the analysis of the surface chemical bond, we will briefly discuss and justify our choice of Density Functional Theory (DFT) as approach to spectrum and chemisorption calculations. 

XAS, on the other hand has a core-excited final state for which the effect of the core-hole must be taken into account. To obtain the full spectrum, i.e., valence, Rydberg and continuum excitations, we use the Slater transition-state approach [22,23] with a half-occupied core-hole. This provides a balanced description of both initial and final states allowing the same orbitals to be used to describe both initial and final states and all transitions are obtained in one calculation [23,24]. Details of the computational procedure can be found in the original papers as referenced in the following sections. In the present chapter, the focus is on the surface chemical bond and the spectra, measured or calculated, will mainly be used to obtain the required information on the electronic structure. 

We will now compare the N2 system to the much more studied isoelectronic CO molecule adsorbed on Ni(100). Like N2, CO adsorbs in a c(2 x 2) overlayer structure on Ni(100), occupying on-top sites with the carbon end down with a C—Ni distance of 1.73 A, see Chapter 1 for details. However, the adsorption energy of 1.2 eV [63] is much higher in comparison to that of N2. It is therefore very interesting to see how the difference in electronegativity of the carbon and oxygen atoms influences the surface-chemical bond in comparison to the isoelectronic N2. 

The chemical bonding to the surface is achieved via orbitals of ax symmetry. The adsorbate-substrate hybrid levels exhibiting mainly metal character are represented by the a, states. It has been shown that backdonation into the previously unoccupied ammonia 4at orbital, and a simultaneous 3a, donation into the substrate, plays an important role in the surface chemical bond [112]. 

In this section, a number of electrocatalytic processes will be discussed where surface chemical bonding plays a central role in the reaction mechanism. The selection of reactions is far from complete and not representative of the wide range of technologically important electrocatalytic processes. The selection is biased towards the areas of electrochemical energy conversion and fuel cell electrochemistry, which have been catalyzing a renewed interest in the field of electrochemistry. 

Figure 6.16. Illustration of the d-band model governing surface chemical bonding on transition metal surfaces. As the d-band center of a catalytic surface shifts downward more antibonding orbitals become occupied and the surface bond energy of an adsorbate (here an oxygen atom) decreases. An upward shift in the d-band center predicts strengthening of the surface bond.

The ideal surface for contact with human blood is the surface of blood vessels, and the immediate surface contains heparinoid complexes. Heparin, a negatively charged polysaccharide, has been bonded to silicon rubber and other polymers. In one procedure, a quaternary ammonium compound is first adsorbed on die polymer substrate and heparin is 111 turn adsorbed on the positively charged surface. Chemical bonding of heparin has also been achieved. Such surfaces do not cause clotting of contacted blood. 

Over the past 10 years a multitude of new techniques has been developed to permit characterization of catalyst surfaces on the atomic scale. Low-energy electron diffraction (LEED) can determine the atomic surface structure of the topmost layer of the clean catalyst or of the adsorbed intermediate (7). Auger electron spectroscopy (2) (AES) and other electron spectroscopy techniques (X-ray photoelectron, ultraviolet photoelectron, electron loss spectroscopies, etc.) can be used to determine the chemical composition of the surface with the sensitivity of 1% of a monolayer (approximately 1013 atoms/cm2). In addition to qualitative and quantitative chemical analysis of the surface layer, electron spectroscopy can also be utilized to determine the valency of surface atoms and the nature of the surface chemical bond. These are static techniques, but by using a suitable apparatus, which will be described later, one can monitor the atomic structure and composition during catalytic reactions at low pressures (< 10-4 Torr). As a result, we can determine reaction rates and product distributions in catalytic surface reactions as a function of surface structure and surface chemical composition. These relations permit the exploration of the mechanistic details of catalysis on the molecular level to optimize catalyst preparation and to build new catalyst systems by employing the knowledge gained. 

Over the past several years the surface structures of several clean monatomic solid surfaces and a variety of adsorbed atoms on solid surfaces have been determined by LEED (7). This field of study is now called surface crystallography and is one of the most rapidly growing fields of surface science. By studying the atomic surface structure of clean surfaces and adsorbed molecules, the nature of the surface chemical bond can be explored in a systematic manner. 

The theoretical chemical application of surface chemical bonding theory, highlighted next, is related to formal chemisorption theory as developed in surface physics, but concentrates on quantum chemical concepts as the electron distribution over bonding and antibonding orbital fragments [5, 6]. It will be seen that both approaches complement each other. The notion of a surface molecule relates to the surface physicists concept of surface state. 

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