Adsorbed atoms

The coverage of adsorbates on a given substrate is usually reported in monolayers (ML). Most often, 1 ML is defined as the number of atoms in the outemiost atomic layer of the umeconstmcted, i.e. bulk-tenuinated, substrate. Sometimes, however, 1 ML is defined as the maximum iiumber of adsorbate atoms that can stick to a particular surface, which is temied the saturation coverage. The saturation coverage can be much smaller... 

Adsorbed atoms and molecules can also diflfiise across terraces from one adsorption site to another [33]. On a perfect terrace, adatom diflfiision could be considered as a random walk between adsorption sites, with a diflfiisivity that depends on the barrier height between neighbouring sites and the surface temperature [29]. The diflfiision of adsorbates has been studied with FIM [14], STM [34, 35] and laser-mduced themial desorption [36]. 

Tseng T T 1988 Experimental studies of the behaviour of single adsorbed atoms on solid surfaces Rep. Prog. Phys. 51 759... 

Elkowitz A B, McCreery J H and Wolken G 1976 Dynamics of atom-adsorbed atom collisions Hydrogen on tungsten Chem. Phys. 17 423... 

Bradshaw A M 1982 Vibrational speotrosoopy of adsorbed atoms and moleoules App/. Surf. Sci. 11/12 712-29... 

The electron density, pj, of the embedded cluster/adsorbate atoms is calculated using quantum chemistry methods (HF, PT, multireference SCF, or Cl). The initial step in this iterative procedure sets to zero,... 

Ultimately, the surface energy is used to produce a cohesive body during sintering. As such, surface energy, which is also referred to as surface tension, y, is obviously very important in ceramic powder processing. Surface tension causes liquids to fonn spherical drops, and allows solids to preferentially adsorb atoms to lower tire free energy of tire system. Also, surface tension creates pressure differences and chemical potential differences across curved surfaces tlrat cause matter to move. 

A study of Table 1.1 reveals interesting features as to the mobility of the adsorbed atoms. Thus, for an argon atom on the (100) face, the easiest path from one preferred site S to the next is over the saddle point P, so that the energy barrier which must be surmounted is (1251 — 855) or 396 X 10 J/molecule. Since the mean thermal energy kT at 78 K is only 108 J/molecule, the argon molecule will have severely limited mobility at this temperature and will spend nearly all of its time in the close vicinity of site S its adsorption will be localized. On the other hand, for helium on the... 

Fig. 1.7 Variation of the value of (pg as the centre of the adsorbed atom moves along a straight line parallel to the surface of a solid and distant Co from it. (---------) For a real surface (-----) for an ideal surface.

Fig. 4. Atom manipulation by the scanning tunneling microscope (STM). Once the STM tip has located the adsorbate atom, the tip is lowered such that the attractive interaction between the tip and the adsorbate is sufficient to keep the adsorbate "tethered" to the tip. The tip is then moved to the desired location on the surface and withdrawn, leaving the adsorbate atom bound to the surface at a new location. The figure schematically depicts the use of this process in the formation of a "quantum corral" of 48 Fe atoms arranged in a circle of about 14.3 nm diameter on a Cu(lll) surface at 4 K.

The second class of atomic manipulations, the perpendicular processes, involves transfer of an adsorbate atom or molecule from the STM tip to the surface or vice versa. The tip is moved toward the surface until the adsorption potential wells on the tip and the surface coalesce, with the result that the adsorbate, which was previously bound either to the tip or the surface, may now be considered to be bound to both. For successful transfer, one of the adsorbate bonds (either with the tip or with the surface, depending on the desired direction of transfer) must be broken. The fate of the adsorbate depends on the nature of its interaction with the tip and the surface, and the materials of the tip and surface. Directional adatom transfer is possible with the apphcation of suitable junction biases. Also, thermally-activated field evaporation of positive or negative ions over the Schottky barrier formed by lowering the potential energy outside a conductor (either the surface or the tip) by the apphcation of an electric field is possible. FIectromigration, the migration of minority elements (ie, impurities, defects) through the bulk soHd under the influence of current flow, is another process by which an atom may be moved between the surface and the tip of an STM. 

CO oxidation catalysis is understood in depth because potential surface contaminants such as carbon or sulfur are burned off under reaction conditions and because the rate of CO oxidation is almost independent of pressure over a wide range. Thus ultrahigh vacuum surface science experiments could be done in conjunction with measurements of reaction kinetics (71). The results show that at very low surface coverages, both reactants are adsorbed randomly on the surface CO is adsorbed intact and O2 is dissociated and adsorbed atomically. When the coverage by CO is more than 1/3 of a monolayer, chemisorption of oxygen is blocked. When CO is adsorbed at somewhat less than a monolayer, oxygen is adsorbed, and the two are present in separate domains. The reaction that forms CO2 on the surface then takes place at the domain boundaries. 

Another special case of weak heterogeneity is found in the systems with stepped surfaces [97,142-145], shown schematically in Fig. 3. Assuming that each terrace has the lattice structure of the exposed crystal plane, the potential field experienced by the adsorbate atom changes periodically across the terrace but exhibits nonuniformities close to the terrace edges [146,147]. Thus, we have here another example of geometrically induced energetical heterogeneity. Adsorption on stepped surfaces has been studied experimentally [95,97,148] as well as with the help of both Monte Carlo [92-94,98,99,149-152] and molecular dynamics [153,154] computer simulation methods. 

If the step is initially prepared to be straight, it relaxes to its fluctuating shape in the due course of time. This time evolution of step width depends on the relaxation kinetics, and can be used to determine the values of various kinetic coefficients [3,16-18,64-66], For example, if the attachment and detachment kinetics of adsorbed atoms at a step is rate limiting, the step width increases as [65]... 

In addition to these direct long-range forces there may also exist effective long-range forces, produced by some medium or substrate. An especially drastic effect is expected for epitaxial growth on a semiconductor. If adsorbate atoms are different from the substrate, the adsorbed layers have a lattice constant different from that of the substrate. In the case of thick adsorbate layers, an instability then appears on the surface of the crystal such that the surface undergoes wavy deformation, which might even lead to... 

Afterwards, kinetic effects determine whether many small islands are formed on a new layer, or only a few large islands develop there [12,19,81,94]. One must take into account many different length and time scales for the interface processes. The typical residential time of an adsorbed atom on the surface might be... 

An analysis of the rate of release of adsorbed atoms from sites with a continuous energy spectrum for the case of an arbitrary distribution function of initial site populations was given by Carter (32). The rate equation for the t th desorption process with x = 1 and negligible readsorption is... 

Adsorbed Atomic Species as Intermediates in Heterogeneous Catalysis Carl Wagner... 

C. Wagner, Adsorbed Atomic Species as Intermediates in Heterogeneous Catalysis, in Adv. Catal., (1970), pp. 323-381. 

The adsorption of C02 on metal surfaces is rather weak, with the exception of Fe, and no molecular or dissociative adsorption takes place at room temperature on clean metal surfaces. At low temperatures, lower than 180 to 300 K, a chemisorbed COf" species has been observed by UPS6 on Fe(lll) and Ni(110) surfaces, which acts as a precursor for further dissociation to CO and adsorbed atomic oxygen. A further step of CO dissociation takes place on Fe(l 11) above 300 to 390 K. 

Figure 2,40. Schematic of the two extreme conformations of adsorbed atomic oxygen on Ag covalently bonded electrophilic oxygen (a-) and ionically bonded oxygen (P-).98 Reprinted with permission from Academic Press.

H. Ohtani, C.-T. Kao, M.A.V. Hove, and G. Somorjai, A tabulation and classification of the stmctures of clean solid surfaces and of adsorbed atomic and molecular monolayes as determined from low energy electron diffraction patterns, Progress in Surface Science 23(2,3), 155-316 (1986) and reference therein. 

Figure 2. The BeisXe D3/1 cluster used to model chemisorption into the four-fold hollows. The Be 13X3 cluster used to model chemisorption into the three-fold hollows is generated by a 60° rotation of the six adsorbate atoms about the vertical axis. The D3d metal cluster is formed by rotating the bottom three metal atoms by 180° about the vertical axis.

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