Structural and vibrational properties of two-dimensional MnxOy\rm Mn_xO_y nanolayers on Pd(100)

Using different experimental techniques combined with density functional based theoretical methods we have explored the formation of interface-stabilized manganese oxide structures grown on Pd(100) at (sub)monolayer coverage. Amongst the multitude of phases experimentally observed we focus our attention on four structures which can be classified into two distinct regimes, characterized by different building blocks. Two oxygen-rich phases are described in terms of MnO(111)-like O-Mn-O trilayers, whereas the other two have a lower oxygen content and are based on a MnO(100)-like monolayer structure. The excellent agreement between calculated and experimental scanning tunneling microscopy images and vibrational electron energy loss spectra allows for a detailed atomic description of the explored models.Comment: 14 pages, 11 figure

Density functional study of the polar MnO(111) surface

By application of a density functional approach within the PBE and PBE+U approximations we investigate the ground state terminations of the polar MnO(111) surface being in thermodynamic equilibrium with an oxygen reservoir. In the allowed range of the oxygen chemical potential and for realistic oxygen partial pressures the surface is found to undergo different structural transitions. In the oxygen-poor regime the most stable phases are the O- and Mn-terminated octopolar structures, which are almost degenerate in energy. For oxygen-rich conditions we observe a competition between the O-terminated unreconstructed bulk face and a stripes structure. We show that the stabilization of the polar surface in the thermodynamic equilibrium with the oxygen environment is due to remarkable changes of the geometrical structure (i.e., reconstruction and relaxation) and of the electronic structure (i.e., metallization)

Density functional study of the polar MnO(111) surface

By application of a density functional approach within the PBE and PBE+U approximations we investigate the ground state terminations of the polar MnO(111) surface being in thermodynamic equilibrium with an oxygen reservoir. In the allowed range of the oxygen chemical potential and for realistic oxygen partial pressures the surface is found to undergo different structural transitions. In the oxygen-poor regime the most stable phases are the O- and Mn-terminated octopolar structures, which are almost degenerate in energy. For oxygen-rich conditions we observe a competition between the O-terminated unreconstructed bulk face and a stripes structure. We show that the stabilization of the polar surface in the thermodynamic equilibrium with the oxygen environment is due to remarkable changes of the geometrical structure (i.e., reconstruction and relaxation) and of the electronic structure (i.e., metallization)

Two-dimensional manganese oxide nanolayers on Pd(100): the surface phase diagram

Two-dimensional manganese oxide layers have been grown on Pd(100) and have been characterized by means of scanning tunnelling microscopy, low energy electron diffraction and x-ray photoelectron spectroscopy (XPS). The complex surface phase diagram of MnO(x) on Pd(100) is reported, where nine different novel Mn oxide phases have been detected as a function of the chemical potential of oxygen mu(O). Three regions of the chemical potential of oxygen can be identified, in which structurally related oxide phases are formed, often in coexistence at the surface. The different regions of mu(O) are reflected in the oxidation states of the respective Mn oxide nanolayers as revealed by the Mn 2p and O 1s XPS binding energies. The MnO(x) nanolayers form two-dimensional wetting layers and it is speculated that they mediate the epitaxial growth of MnO on Pd(100) by providing structurally graded interfaces

Strained c(4 x 2) CoO(100)-like monolayer on Pd(100): Experiment and theory

We report on an interface-stabilized strained c(4 x 2) phase formed by cobalt oxide on Pd(100). The structural details and electronic properties of this oxide monolayer are elucidated by combination of scanning tunneling microscopy data, high resolution electron energy loss spectroscopy measurements and density functional theory. The c(4 x 2) periodicity is shown to arise from a rhombic array of Co vacancies, which form in a pseudomorphic CoO(100) monolayer to partially compensate for the compressive strain associated with the large lattice mismatch (similar to 9.5%) between cobalt monoxide and the substrate. Deviation from the perfect 1:1 stoichiometry thus appears to offer a common and stable mechanism for strain release in Pd(100) supported monolayers of transition metal rocksalt monoxides of the first transition series, as very similar metal-deficient c(4 x 2) structures have been previously found for nickel and manganese oxides on the same substrate. (C) 2009 Elsevier B.V. All rights reserved

Silver nanostructures on a c(4x2)-NiOx/Pd(100) monolayer

The growth, morphology and epitaxial relationship of Ag nanostructures deposited onto the c(4 × 2)-NiOx/Pd(1 0 0) surface have been investigated by photoemission (both core and valence levels), scanning tunneling microscopy and angle-scanned photoelectron diffraction. Small Ag nanoparticles are obtained on the terraces, whereas the tendency of Ag to decorate the step edges can lead to the formation of extended nanowire-like features. The Ag nanoparticles adopt a fcc structure epitaxially related to the substrate according to the following relationship: Ag(1 0 0)[0 0 1]//Pd(1 0 0)[0 0 1], while by means of STM we have found that the shape of the islands is typically rectangular with the edges running along the [0 1 1] directions. According to the reported data, the NiOx ML is locally disrupted in the vicinity of the Ag nanoparticles so that the c(4 × 2)-NiOx/Pd(1 0 0) surface cannot be considered as an efficient template to stabilize metal nanoparticles against Ostwald ripening phenomena

Adsorption and Dissociation of CO on Bare and Ni-Decorated Stepped Rh(553) Surfaces

The adsorption and dissociation of carbon monoxide were studied with plane-wave density functional theory on flat Rh(111), stepped and kinked Rh(553), and Ni-decorated Rh(553) surfaces. The theoretical results were compared to high-resolution X-ray photoelectron spectroscopy (HR-XPS) experiments. The most favorable CO adsorption sites for low coverages were identified by a systematic calculation of the adsorption energies, and their sequence of occupation as a function of CO exposure was determined experimentally in C 1s HR-XPS spectra via their characteristic surface core-level shifts. On the clean, stepped (553) surface, molecular CO is adsorbed more strongly on low-coordinated top sites at the step edge, but on the Ni-decorated surface, the binding is stronger at the terrace sites. The barrier for dissociation with respect to the gas phase is about 1 eV lower on the stepped Rh(553) surface than on the flat Rh(111) surface, implying a substantially higher reaction rate. The presence of kinks at the clean Rh(553) surface does not lead to a significant additional decrease of the dissociation barriers, resulting in dissociation energies just above the desorption threshold for both stepped and kinked surfaces, whereas the barrier can be additionally lowered by about 0.1 eV by decorating the step edges with Ni stripes. Whereas no dissociation of CO was observed by HR-XPS on the clean Rh(553) surface, a minor amount of CO dissociation was found on the Ni-decorated Rh surface, in agreement with the theoretical predictions

Cobalt oxide nanolayers on Pd(100): The thickness-dependent structural evolution

The growth of interface-stabilized cobalt oxide (CoOx) nanolayers on Pd(100) has been investigated and their structures are reported as a function of coverage. Several different phases have been observed by LEED and STM experiments, and they have been characterized spectroscopically by photoemission and X-ray absorption. The data indicate that in the low coverage regime (up to \u398Co 48 2\u20133 ML) rock-salt CoO type phases are formed (defective in the single layer regime, and stoichiometric in multilayers) with (100) or (111) termination. At higher coverage (\u398Co 48 10\u201320 ML) spinel Co3O4(111) and CoO(100) layers have been detected, in ratios dependent on the preparation conditions. The observed structures are discussed in relation to similar structures reported recently for CoOx films on Ir(100) [W. Meyer et al., J. Phys.: Condens. Matter 20 (2008) 265011