6.8. Hexagonal close-packed surface

Fig. 6.9. Corrugation amplitudes of a hexagonal close-packed surface. Solid curve, theoretical corrugation amplitude for an s and a d,- tip state, on a close-packed metal surface with a=2.88 A and 4>=3.5 eV. The orbitals on each metal atom on the sample is assumed to be 1 i-type. Measured STM corrugation amplitudes are from the data of Wintterlin et al. (1989). The first-principle calculation of Al(lll) is taken from Mednick and Kleinman (1980). The corrugation amplitude for a 4-wave tip state is more than one order of magnitude smaller then the experimental corrugation. (Reproduced from Chen, 1991, with permission.)...

Ordered strain relief patterns with a large period are most often formed on hexagonally close-packed surfaces since they have a small corrugation of the substrate potential, and the overlayer is relatively stiff since it is... 

Fig. 9a - c. Possible domain wall structures for strain relief on hexagonally close packed surfaces (a) unidirectional compression or expansion along the close packed atomic rows. For isotropic strain relief on a mesoscopic scale often two of the three possible rotational domains alternate leading to a herringbone pattern, (b) and (c) trigonal networks with wall crossings [97Bru]. 

Co(OOOl) is a kind of hexagonal close packed surface, being a model system since it is relatively stable and simple. The typical adsorption configuration of CO adsorption on Co(OOOl) is shown in Fig. 3. As listed in Table 1, the adsorption of CO on Co(OOOl) prefers on top sites with an adsorption energy of 1.60 1.90 eV, which is 0.3 0.6eV higher than the experimental results of 1.35 eV and 1.32 0.13 eV. This divergence comes from the inaccurate description of the chemical bond of adsorbed CO molecule by DFT methods. 

Single-crystal surfaces of other noble metals, including Rh and Pd, have also been used as substrates for EC-STM. As with Au and Pt, these metals possess electrochemical windows and surface characteristics suitable for EC-STM studies of adsorbed species.i i Similar to Au, the most frequently employed crystal faces for Rh and Pd electrodes have been the (111) faces, which present a hexagonally close-packed surface structure. 

W. (2002) Anomalous surface lattice dynamics of a simple hexagonally close-packed surface. Phys. Rev. B,... 

Figure Bl.21.1. Atomic hard-ball models of low-Miller-index bulk-temiinated surfaces of simple metals with face-centred close-packed (fee), hexagonal close-packed (licp) and body-centred cubic (bcc) lattices (a) fee (lll)-(l X 1) (b)fcc(lO -(l X l) (c)fcc(110)-(l X 1) (d)hcp(0001)-(l x 1) (e) hcp(l0-10)-(l X 1), usually written as hcp(l010)-(l x 1) (f) bcc(l 10)-(1 x ]) (g) bcc(100)-(l x 1) and (li) bcc(l 11)-(1 x 1). The atomic spheres are drawn with radii that are smaller than touching-sphere radii, in order to give better depth views. The arrows are unit cell vectors. These figures were produced by the software program BALSAC [35]-...

Figure Bl.21.1 shows a number of other clean umeconstnicted low-Miller-index surfaces. Most surfaces studied in surface science have low Miller indices, like (111), (110) and (100). These planes correspond to relatively close-packed surfaces that are atomically rather smooth. With fee materials, the (111) surface is the densest and smoothest, followed by the (100) surface the (110) surface is somewhat more open , in the sense that an additional atom with the same or smaller diameter can bond directly to an atom in the second substrate layer. For the hexagonal close-packed (licp) materials, the (0001) surface is very similar to the fee (111) surface the difference only occurs deeper into the surface, namely in the fashion of stacking of the hexagonal close-packed monolayers onto each other (ABABAB.. . versus ABCABC.. ., in the convenient layerstacking notation). The hep (1010) surface resembles the fee (110) surface to some extent, in that it also...

It is well known that the 0 of a metal depends on the surface crystallographic orientation.6,65,66 In particular, it is well established that 0 increases with the surface atomic density as a consequence of an increase in the surface potential M. More specifically, for metals crystallizing in the face-centered cubic (fee) system, 0 increases in the sequence (110) <(100) <(111) for those crystallizing in the body-centered cubic (bcc) system, in the sequence (111) < (100) <(110) and for the hexagonal close-packed (hep) system, (1120) < (1010) < (0001). 

A freshly prepared flame-annealed Au(100) surface has been found to be reconstmcted188,487,534,538 and the surface atoms exhibit a hexagonal close-packed structure to yield the (hex)-stmcture. One-directional long-range corrugation of 1.45 nm periodicity and 0.05 nm height has been found on the Au( 100) surface.188,488 When the reconstruction is lifted due to specific adsorption of SO - anions at more positive , the surface changes to a (1 x 1) structure.538... 

Zinc crystallizes in the hexagonal close-packed system its electronic structure is 4s2 and the melting point is 693 K. Since the zinc dissolution takes place at potentials very close to ffa0 the differential capacitance curves in the region of Ea=c in pure surface-inactive electrolyte solutions (KC1, pH = 3.7) can be determined directly for the Zn(llJO) face only... 

Among MC lattice models of the double layer, it is also worth mentioning the work of Nazmutdinov et al. (1988), who used a lattice model involving two mono-layers of water molecules on the surface of an electrode, forming a hexagonal close-packed array. The interaction of each water molecule in contact with the metal surface (assumed to be Hg) was taken from quantum-mechanical calculations. Information was obtained concerning the relative numbers of molecules with different numbers of hydrogen bonds, and it was concluded that the hypothesis of an icelike state of water in a monolayer on Hg is rather unlikely. 

Mono- or single-crystal materials are undoubtedly the most straightforward to handle conceptually, however, and we start our consideration of electrochemistry by examining some simple substances to show how the surface structure follows immediately from the bulk structure we will need this information in chapter 2, since modern single-crystal studies have shed considerable light on the mechanism of many prototypical electrochemical reactions. The great majority of electrode materials are either elemental metals or metal alloys, most of which have a face-centred or body-centred cubic structure, or one based on a hexagonal close-packed array of atoms. 

Figure 1,2 Atomic arrangement on various clean metal surfaces. In each of the sketches (a) to (h) the upper and lower diagrams represent top and side views, respectively. Atoms drawn with dashed lines lie behind the plane of those drawn with thick lines, Atoms in unrelaxed positions (i.e. in the positions they occupy in the bulk) are shown as dotted lines. From G.A. Somorjai, Chemistry in Two Dimensions, Cornell University Press, London, 1981, p. 133, For the Miller index convention in hexagonal close-packed structures, see also G.A. Somorjai loc. cit, Used by permission of Cornell University Press,...

The most important metals for catalysis are those of Groups VIII and I-B of the periodic system. Three crystal structures are important, face-centered cubic (fee Ni, Cu, Rh, Pd, Ag, Ir, Pt, Au), hexagonal close-packed (hep Co, Ru, Os) and body-centered cubic (bcc Fe) [9, 10]. Before discussing the surfaces that these lattices expose, we mention a few general properties. 

The surfaces are labeled according to the lattice plane that is exposed. The (111), (100) and (110) surfaces are perpendicular to the < 111 >, <100> and <1I0> directions in the crystal. The close-packed surface of the hep lattice, the (001) plane, [or strictly speaking the (0001) plane, because four coordinates are used for hexagonal lattices], has the same structure as the fee (111) plane [11]. 

Figure 9. Simplified model of the (111) surface of the corundum-type structure, (a) A view of the surface from a direction slightly shifted from <111>. Only metal ions of the zeroth, first, and second layers are shown, (b) A section of the surface along the arrows depicted in part a. Hexagonally close-packed oxide ion layers are shown with lines. Surface protons are not shown, (c) A divalent Co-57 or pentavalent Sb-119 ion on the zeroth metal ion layer, (d) Aquo or hydroxyl complex of divalent Co-57 or pentavalent Sb-119 hydrogen-bonded to the surface oxide ion layers of hematite.

The first first direct experimental evidence for a roughening transition was reported in 1979. Several groups have studied the thermal behavior of the basal plane of a hexagonal close-packed He crystal. In a beautiful experiment Balibar and Casting obtained for this surface a roughening temperature of Tk 1.2K. 

Fig. 6-1. TVo-dimensional atomic structure on the (100) plane of platinum crystals (1x1) = cubic close-packed surface plane identical with the (100) plane (5 x 20) = hexagonal dose-packed surface plane reconstructed finm the original (100) plane. [From Kolb, 1993.]...

It is noteworthy that prior to the advent of scanning probe microscopy electrochemically driven reconstruction phenomena had been identified and studied using traditional macroscopic electrochemical measurements [210,211], However, STM studies have provided insight as to the various atomistic processes involved in the phase transition between the reconstructed and unreconstructed state and promise to provide an understanding of the macroscopically observed kinetics. An excellent example is provided by the structural evolution of the Au(lOO) surface as a function of potential and sample history [210,211,216-223], Flame annealing of a freshly elec-tropolished surface results in the thermally induced formation of a dense hexagonal close-packed reconstructed phase referred to as Au(100)-(hex). For carefully annealed crystals a single domain of the reconstructed phase... 

Some metal surfaces reconstruct either in the clean state or in the presence of adsorbed gases. Platinum, iridium, and gold (100) surfaces, which have square symmetry, all reconstruct to hexagonal close-packed (111) surfaces... 

Any study of colloidal crystals requires the preparation of monodisperse colloidal particles that are uniform in size, shape, composition, and surface properties. Monodisperse spherical colloids of various sizes, composition, and surface properties have been prepared via numerous synthetic strategies [67]. However, the direct preparation of crystal phases from spherical particles usually leads to a rather limited set of close-packed structures (hexagonal close packed, face-centered cubic, or body-centered cubic structures). Relatively few studies exist on the preparation of monodisperse nonspherical colloids. In general, direct synthetic methods are restricted to particles with simple shapes such as rods, spheroids, or plates [68]. An alternative route for the preparation of uniform particles with a more complex structure might consist of the formation of discrete uniform aggregates of self-organized spherical particles. The use of colloidal clusters with a given number of particles, with controlled shape and dimension, could lead to colloidal crystals with unusual symmetries [69]. 

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