Effect of the surface model on the theoretical description of the chemisorption of atomic hydrogen on Cu(001)

Adsorption at surfaces can be modelled using a periodic supercell approach or using finite clusters. For many systems and properties these models are complementary and often the most productive way to work is to use a combination of these techniques. If reliable data is to be obtained it is essential that convergence is achieved with respect to the size of supercell and cluster. This work discusses the convergence of chemisorption properties of H on Cu(001) with respect to the cluster size. To this end calculations of the H binding energy and equilibrium distance, are reported for cluster models of increasing size containing up to 77 metal atoms. Likewise, periodic slab model calculations are used to provide the corresponding values towards which the cluster approach should converge. In many previous studies of a wide variety of systems it has been established that computed equilibrium distances converge rapidly with respect to cluster size. Here, a systematic study of the dependence on cluster size shows that, for adsorption in the 4-fold site, convergence is not achieved even for very large clusters. The reason for this poor convergence is seen to be the inability of the cluster model to reproduce accurately the charge density and electrostatic potential of the crystalline surface

The structure of epitaxial V2O3 films and their surfaces : a medium energy ion scattering study

Medium energy ion scattering, using 100 keV H+ incident ions, has been used to investigate the growth of epitaxial films, up to thicknesses of ~200 Å, of V2O3 on both Pd(111) and Au(111). Scattered-ion energy spectra provide a measure of the average film thickness and the variations in this thickness, and show that, with suitable annealing, the crystalline quality is good. Plots of the scattering yield as a function of scattering angle, so-called blocking curves, have been measured for two different incidence directions and have been used to determine the surface structure. Specifically, scattering simulations for a range of different model structures show poor agreement with experiment for half-metal (….V’O3V) and vanadyl (….V’O3V=O) terminations, with and without surface interlayer relaxations. However, good agreement with experiment is found for the modified oxygen-termination structure, first proposed by Kresse et al., in which a subsurface V half-metal layer is moved up into the outermost V buckled metal layer to produce a VO2 overlayer on the underlying V2O3, with an associated layer structure of ….O3VV’’V’O3

Metastable precursors during the oxidation of the Ru(0001) surface

Using density-functional theory, we predict that the oxidation of the Ru(0001) surface proceeds via the accumulation of sub-surface oxygen in two-dimensional islands between the first and second substrate layer. This leads locally to a decoupling of an O-Ru-O trilayer from the underlying metal. Continued oxidation results in the formation and stacking of more of these trilayers, which unfold into the RuO_2(110) rutile structure once a critical film thickness is exceeded. Along this oxidation pathway, we identify various metastable configurations. These are found to be rather close in energy, indicating a likely lively dynamics between them at elevated temperatures, which will affect the surface chemical and mechanical properties of the material.Comment: 11 pages including 9 figures. Submitted to Phys. Rev. B. Related publications can be found at http://www.fhi-berlin.mpg.de/th/paper.htm

Adlayer core-level shifts of random metal overlayers on transition-metal substrates

We calculate the difference of the ionization energies of a core-electron of a surface alloy, i.e., a B-atom in a A_(1-x) B_x overlayer on a fcc-B(001)-substrate, and a core-electron of the clean fcc-B(001) surface using density-functional-theory. We analyze the initial-state contributions and the screening effects induced by the core hole, and study the influence of the alloy composition for a number of noble metal-transition metal systems. Data are presented for Cu_(1-x)Pd_x/Pd(001), Ag_(1-x) Pd_x/Pd(001), Pd_(1-x) Cu_x/Cu(001), and Pd_(1-x) Ag_x/Ag(001), changing x from 0 to 100 %. Our analysis clearly indicates the importance of final-state screening effects for the interpretation of measured core-level shifts. Calculated deviations from the initial-state trends are explained in terms of the change of inter- and intra-atomic screening upon alloying. A possible role of alloying on the chemical reactivity of metal surfaces is discussed.Comment: 4 pages, 2 figures, Phys. Rev. Letters, to appear in Feb. 199

Stability of sub-surface oxygen at Rh(111)

Using density-functional theory (DFT) we investigate the incorporation of oxygen directly below the Rh(111) surface. We show that oxygen incorporation will only commence after nearly completion of a dense O adlayer (\theta_tot = 1.0 monolayer) with O in the fcc on-surface sites. The experimentally suggested octahedral sub-surface site occupancy, inducing a site-switch of the on-surface species from fcc to hcp sites, is indeed found to be a rather low energy structure. Our results indicate that at even higher coverages oxygen incorporation is followed by oxygen agglomeration in two-dimensional sub-surface islands directly below the first metal layer. Inside these islands, the metastable hcp/octahedral (on-surface/sub-surface) site combination will undergo a barrierless displacement, introducing a stacking fault of the first metal layer with respect to the underlying substrate and leading to a stable fcc/tetrahedral site occupation. We suggest that these elementary steps, namely, oxygen incorporation, aggregation into sub-surface islands and destabilization of the metal surface may be more general and precede the formation of a surface oxide at close-packed late transition metal surfaces.Comment: 9 pages including 9 figure files. Submitted to Phys. Rev. B. Related publications can be found at http://www.fhi-berlin.mpg.de/th/paper.htm

Potential, core-level and d band shifts at transition metal surfaces

We have extended the validity of the correlation between the surface 3d-core-level shift (SCLS) and the surface d band shift (SDBS) to the entire 4d transition metal series and to the neighboring elements Sr and Ag via accurate first-principles calculations. We find that the correlation is quasilinear and robust with respect to the differencies both between initial and final-state calculations of the SCLS's and two distinct measures of the SDBS's. We show that despite the complex spatial dependence of the surface potential shift (SPS) and the location of the 3d and 4d orbitals in different regions of space, the correlation exists because the sampling of the SPS by the 3d and 4d orbitals remains similar. We show further that the sign change of the SCLS's across the transition series does indeed arise from the d band-narrowing mechanism previously proposed. However, while in the heavier transition metals the predicted increase of d electrons in the surface layer relative to the bulk arises primarily from transfers from s and p states to d states within the surface layer, in the lighter transition metals the predicted decrease of surface d electrons arises primarily from flow out into the vacuum.Comment: RevTex, 22 pages, 5 figures in uufiles form, to appear in Phys.Rev.

Surface Core Level Shifts of Clean and Oxygen Covered Ru(0001)

We have performed high resolution XPS experiments of the Ru(0001) surface, both clean and covered with well-defined amounts of oxygen up to 1 ML coverage. For the clean surface we detected two distinct components in the Ru 3d_{5/2} core level spectra, for which a definite assignment was made using the high resolution Angle-Scan Photoelectron Diffraction approach. For the p(2x2), p(2x1), (2x2)-3O and (1x1)-O oxygen structures we found Ru 3d_{5/2} core level peaks which are shifted up to 1 eV to higher binding energies. Very good agreement with density functional theory calculations of these Surface Core Level Shifts (SCLS) is reported. The overriding parameter for the resulting Ru SCLSs turns out to be the number of directly coordinated O atoms. Since the calculations permit the separation of initial and final state effects, our results give valuable information for the understanding of bonding and screening at the surface, otherwise not accessible in the measurement of the core level energies alone.Comment: 16 pages including 10 figures. Submitted to Phys. Rev. B. Related publications can be found at http://www.fhi-berlin.mpg.de/th/paper.htm