Structure determination of the (3sqrt{3}x3sqrt{3}) reconstructed alpha-Al_2O_3(0001)

Grazing-incidence X-ray diffraction data are combined with energy-minimization calculations to analyse the atomic structure of the Al-rich (3sqrt{3} x 3sqrt{3})R 30 deg reconstructed surface of sapphire alpha-Al_2O_3(0001). The experiments on the BM32 beamline of the ESRF provide the non-integer-order diffraction intensities and, after Fourier transform, an incomplete Patterson map. The computer simulations are implemented to obtain structural information from this map. In the simulations, the interactions between the Al overlayer atoms were described with the Sutton-Chen potential and the interactions between the overlayer and the sapphire substrate with a laterally modulated Lennard-Jones potential. We have shown that the hexagonal reconstructed unit cell is composed of triangles where the two layers of Al adatoms are FCC(111) ordered whereas between the triangles the stacking is FCC(001).Comment: 9 pages, incl. 4 figures; submitted to Surface Science Letter

A leed analysis of the (2×1)H-Ni(110) structure

A monolayer of H atoms adsorbed on Ni(110) below 180 K forms a (2×1) structure. The unit cell exhibits a glide symmetry plane and contains two adsorbed atoms. Based on a quantitative comparison between experimental and calculated LEED I/V spectra using standard R-factors the following structure was derived: On the clean Ni(110) surface the separation between the first two atomic layers, d12, is contracted by 8.5%±1.5% with respect to the bulk value; those between the second and third and the third and fourth layer, d23 and d34, are expanded by 3.5%±1.5% and 1%±1.5%, respectively—in agreement with recent other results. In the presence of the H adlayer the contraction of d12 is reduced to 4.5%±1.5%, while the expansion of d23 is not affected within the limits of accuracy. The third interlayer spacing d34 returns to its bulk value. The H atoms occupy threefold-coordinated sites formed by two Ni atoms from the first layer and one Ni atom from the second layer which confirms previous more qualitative conclusions based on He diffraction and vibrational spectroscopy. The bond lengths between H and its neighbouring Ni atoms were determined to be equal, namely 1.72±0.1 Å

Reconstruction and subsurface lattice distortions in the (2 × 1)O-Ni(110) structure: A LEED analysis

LEED analysis of the reconstructed (2 × 1)O-Ni(110) system clearly favors the “missing row” structure over the “saw-tooth” and “buckled row” models. By using a novel computational procedure 8 structural parameters could be refined simultaneously, leading to excellent R-factors (RZJ = 0.09, RP = 0.18). The adsorbed O atoms are located 0.2 Å above the long bridge sites in [001] direction, presumably with a slight displacement ( 0.1 Å) in [1 0] direction to an asymmetric adsorption site. The nearest-neighbor Ni---O bond lengths (1.77 Å) are rather short. The separation between the topmost two Ni layers is expanded to 1.30 Å (bulk value 1.25 Å), while that between the second and third layer is slightly contracted to 1.23 Å. The third layer is, in addition, slightly buckled (±0.05 Å). The results are discussed on the basis of our present general knowledge about the structure of adsorbate covered metallic surfaces

Segregation and ordering at the (1×2) reconstructed Pt80Fe20(110) surface determined by low-energy electron diffraction

The surface of an ordered Pt80Fe20(110) crystal exhibits (1×2) and (1×3) reconstructions depending on the annealing treatment after ion bombardment. The (1×3) structure occurs after annealing in the range 750 to 900 K. Annealing above 1000 K leads to the (1×2) structure, which is, from the present result, unambiguously attributed to the same geometrical reconstruction as Pt(110) but with smaller relaxation amplitudes: a detailed low-energy electron-diffraction analysis concludes to a missing-row structure with row pairing in layers 2 and 4 accompanied by a buckling in layers 3 and 5. The top layer spacing is contracted by 13%, and further relaxations are detectable down to the fifth layer. The specific diffraction spots associated with the bulk chemical ordering along the dense [1¯10] rows are very weak: The I(V) analysis shows that this chemical ordering is absent in the outermost ‘‘visible’’ rows but gradually recovers over five to six layers deep. General Pt enrichment is found in the surface ‘‘visible’’ rows (in layers 1–3), but segregation and order yield a subtle redistribution of Pt and Fe atoms in deeper rows: For example, in layer 2, the visible row is Pt rich, whereas the other row (buried under layer 1) is enriched with Fe. Because of the many parameters considered, a fit procedure was applied to a large data basis to solve the structure; the results were confirmed and illustrated subsequently by a standard I(V) analysis for the most relevant parameters. The final r factors are RDE=0.36, RP=0.34, and RZJ=0.14 for two beam sets at normal and oblique incidence consisting of 26 and 21 beams, respectively

New reactor dedicated to in operando studies of model catalysts by means of surface x-ray diffraction and grazing incidence small angle x-ray scattering

International audienceA new experimental setup has been developed to enable in situ studies of catalyst surfaces during chemical reactions by means of surface x-ray diffraction (SXRD) and grazing incidence small angle x-ray scattering. The x-ray reactor chamber was designed for both ultrahigh-vacuum (UHV) and reactive gas environments. A laser beam heating of the sample was implemented; the sample temperature reaches 1100 K in UHV and 600 K in the presence of reactive gases. The reactor equipment allows dynamical observations of the surface with various, perfectly mixed gases at controlled partial pressures. It can run in two modes: as a bath reactor in the pressure range of 1-1000 mbars and as a continuous flow cell for pressure lower than 10−3 mbar. The reactor is connected to an UHV preparation chamber also equipped with low energy electron diffraction and Auger spectroscopy. This setup is thus perfectly well suited to extend in situ studies to more complex surfaces, such as epitaxial films or supported nanoparticles. It offers the possibility to follow the chemically induced changes of the morphology, the structure, the composition, and growth processes of the model catalyst surface during exposure to reactive gases. As an example the Pd8Ni92(110) surface structure was followed by SXRD under a few millibars of hydrogen and during butadiene hydrogenation while the reaction was monitored by quadrupole mass spectrometry. This experiment evidenced the great sensitivity of the diffracted intensity to the subtle interaction between the surface atoms and the gas molecules

FAUT-IL UNE THÉORIE DYNAMIQUE DE LA D. E. L. POUR ACCÉDER AUX VIBRATIONS DES ATOMES DE SURFACE ?

Les premières expériences faites par Germer et Mac Rae sur le Nickel, montrent une anisotropie de la composante u// de l'amplitude de vibration atomique en surface, ainsi qu'une variation avec l'énergie des électrons incidents de la température de Debye effective E eff(V). Ces résultats ont été prévus qualitativement par des calculs théoriques ; la D. E. L. est-elle donc un outil idéal pour l'étude de la dynamique des surfaces des monocristaux ? Dans ce cadre, nous avons repris une étude faite par Jones, McKinney et Webb sur la face (111) de l'Argent, mais avec une technique plus précise. Nos résultats montrent qu'une théorie pseudo-cinématique comme celle qu'ont employée Jones et alii ne peut expliquer les courbes expérimentales Eeff(V), si l'on veut conserver des valeurs raisonnables pour le mouvement des atomes proches de la surface.First experiments, by Germer and Mac Rae on Nickel, show an anisotropic component u// of the root mean square displacements of the surface atoms, and a dependence of the effective Debye temperature Eeff(V) on the energy of the incident electrons. These results being qualitatively predicted by theoretical calculations, is L. E. E. D. an ideal tool for studying the dynamics of monocrystal surfaces ? On this basis, we have undertaken a similar study as that done by Jones, McKinney and Webb on the (111) face of Silver, but with a more precise technique. Our results show that such a pseudokinematical theory as that used by Jones and alii cannot explain the experimental Eeff(V) curves, if reasonable values of the atomic displacement near the surface are to be used

The (110) surface of the disordered Pt25Co75 alloy: a sandwich of almost pure monoatomic layers

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