Bonding adatoms

The general conclusion from Eqs. (9)—(14) is that the molecular heat of chemisorption ( AB rapidly decreases as the gas-phase dissociation (total bond) energy DAB increases. The values of QAB are smaller than QA(QB), typically by a factor of 5-10 but sometimes even 15-20. For this reason, the periodic changes in QAB for molecules such as CO, NH3, NO, H20, C2H4, and C2H2 are expected to be small and potentially irregular, unlike the large and systematic variations in QA observed for the relevant multiply bonded adatoms A. 

Figure Al.7.6. Schematic diagrams of the DAS model of the Si(l 11)-(7 x 7) surface structure. There are 12 adatoms per unit cell in the outennost layer, which each have one dangling bond perpendicular to the surface. The second layer, called the rest layer, also has six rest atoms per unit cell, each with a perpendicular dangling bond. The comer holes at the edges of the nnit cells also contain one atom with a dangling bond.

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. 

This is illustrated in Figure 1.6 for the dissociation of CO [3]. As a consequence of the high value of a, the proportionality constant of recombination is usually approximately 0.2, reflecting a weakening of the adatom surface bonds in transition state by this small amount. It implies that typically one of the six surface bonds is broken in the transition state compared to the adsorption state of the two atoms before recombination. 

The overall reaction pathway is probably similar to what has been presented for the reaction of SnBu4 with Pt particles, that is first hydrogenolysis of the As-C bond to form Nis[AsPh2] , species, which rapidly evolves into Nis[AsPh]jy, Nis[As]jy to give finally an alloy by migration of the As adatoms into the Ni lattice as evidenced by the formation of Nickeline (NiAs) according to XRD studies (Scheme 36). 

Further studies were carried out on the Pd/Mo(l 1 0), Pd/Ru(0001), and Cu/Mo(l 10) systems. The shifts in core-level binding energies indicate that adatoms in a monolayer of Cu or Pd are electronically perturbed with respect to surface atoms of Cu(lOO) or Pd(lOO). By comparing these results with those previously presented in the literature for adlayers of Pd or Cu, a simple theory is developed that explains the nature of electron donor-electron acceptor interactions in metal overlayer formation of surface metal-metal bonds leads to a gain in electrons by the element initially having the larger fraction of empty states in its valence band. This behavior indicates that the electro-negativities of the surface atoms are substantially different from those of the bulk [65]. 

It is observed that higher potential values for the adatom redox process are correlated with a lower energy of the M—O bond, i.e., lower (less negative) enthalpy of formation of the adatom oxygenated species. In this regard, the discrepant behavior of Ge-Pt(lOO) may be related to the dilute nature of this adlayer, with a maximum coverage of only 0.25. 

It has been often stressed that low eoordinated atoms (defeets, steps, and kink sites) play an important role in surfaee ehemistry. The existenee of dangling bonds makes steps and kinks espeeially reaetive, favoring the adsorption of intermediate species on these sites. Moreover, smdies of single-crystal surfaces with a eomplex geometry have been demonstrated very valuable to link the gap between fundamental studies of the basal planes [Pt( 111), Pt( 100), and Pt(l 10)] and applied studies of nanoparticle eatalysts and polycrystalline materials. In this context, it is relevant to mention results obtained with adatom-modified Pt stepped surfaces, prior to discussing the effect of adatom modification on electrocatalysis. 

In the presence of Bi or Te, the C=0 bond is weakened, as concluded from the displacement of the CO stretching band to lower wavenumbers. There is also a change in the dependence of the band frequency on electrode potential, with the slope dv/dE increasing for the adatom-modified surfaces. These changes indicate that the adatom alters the electronic properties of the surface, increasing the amount of electronic backdonation and stabilizing the adsorbed CO molecule. No catalytic enhancement is expected from this effect. 

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