| 1. |
- Gustafson, Johan, et al.
(författare)
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Oxygen-induced step bunching and faceting of Rh(553): Experiment and ab initio calculations
- 2006
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Ingår i: Physical Review B (Condensed Matter and Materials Physics). - 1098-0121 .- 1550-235X. ; 74:3
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Tidskriftsartikel (refereegranskat)abstract
- Using a combined experimental and theoretical approach, we show that the initial oxidation of a Rh(553) surface, a surface vicinal to (111), undergoes step bunching when exposed to oxygen, forming lower-index facets. At a pressure of about 10(-6) mbar and a temperature of 380 degrees C this leads to (331) facets with one-dimensional oxide chains along the steps, coexisting with (111) facets. Further increase of the pressure and temperature results in (111) facets only, covered by an O-Rh-O surface oxide. Our density functional theory calculations provide an atomistic understanding of the observed behavior.
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| 2. |
- Gustafson, Johan, et al.
(författare)
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Self-limited growth of a thin oxide layer on Rh(111)
- 2004
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Ingår i: Physical Review Letters. - 1079-7114. ; 92:12
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Tidskriftsartikel (refereegranskat)abstract
- The oxidation of the Rh(111) surface at oxygen pressures from 10(-10) mbar to 0.5 bar and temperatures between 300 and 900 K has been studied on the atomic scale using a multimethod approach of experimental and theoretical techniques. Oxidation starts at the steps, resulting in a trilayer O-Rh-O surface oxide which, although not thermodynamically stable, prevents further oxidation at intermediate pressures. A thick corundum like Rh2O3 bulk oxide is formed only at significantly higher pressures and temperatures.
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| 3. |
- Gustafson, Johan, et al.
(författare)
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Structure and catalytic reactivity of Rh oxides
- 2009
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Ingår i: Catalysis Today. - : Elsevier BV. - 0920-5861. ; 145:3-4, s. 227-235
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Konferensbidrag (refereegranskat)abstract
- Using a combination of experimental and theoretical techniques, we show that a thin RhO2 surface oxide film forms prior to the bulk Rh2O3 corundum oxide on all close-packed single crystal Rh surfaces. Based on previous reports, we argue that the RhO2 surface oxide also forms on vicinal Rh surfaces as well as on Rh nanoparticles. The detailed structure of this film was previously determined using UHV based techniques and density functional theory. In the present paper, we also examine the structure of the bulk Rh2O3 corundum oxide using surface X-ray diffraction. Being armed with this structural information, we have explored the CO oxidation reaction over Rh(1 1 1), Rh(1 0 0) and Pt25Rh75(1 0 0) at realistic pressures using in situ surface X-ray diffraction and online mass spectrometry. In all three cases we find that an increase of the CO2 production coincides with the formation of the thin RhO2 surface oxide film. In the case of Pt25Rh75(1 0 0), our measurements demonstrate that the formation of bulk Rh2O3 corundum oxide poisons the reaction, and argue that this is also valid for all other Rh surfaces. Our study implies that the CO oxidation reaction over Rh surfaces at realistic conditions is insensitive to the exact Rh substrate orientation, but is rather governed by the formation of a specific surface oxide phase. (C) 2008 Elsevier B.V. All rights reserved.
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| 4. |
- Gustafson, Johan, et al.
(författare)
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Structure of a thin oxide film on Rh(100)
- 2005
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Ingår i: Physical Review B (Condensed Matter and Materials Physics). - 1098-0121. ; 71:11
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Tidskriftsartikel (refereegranskat)abstract
- The initial oxidation of Rh(100) has been studied using high resolution core level spectroscopy, low energy electron diffraction, surface x-ray diffraction, scanning tunneling microscopy, and density functional theory. We report a structural study of an oxygen induced structure displaying a c(8x2) periodicity at an oxygen pressure above 10(-5) mbar and using a sample temperature of 700 K. Our experimental and theoretical data demonstrate that this structure is due to the formation of a thin surface oxide with a hexagonal trilayer O-Rh-O structure.
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| 5. |
- Klikovits, J., et al.
(författare)
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Step-Orientation-Dependent Oxidation: From 1D to 2D Oxides
- 2008
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Ingår i: Physical Review Letters. - 1079-7114. ; 101:26
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Tidskriftsartikel (refereegranskat)abstract
- Using scanning tunneling microscopy and density functional theory, we have studied the initial oxidation of Rh(111) surfaces with two types of straight steps, having {100} and {111} microfacets. The one-dimensional (1D) oxide initially formed at the steps acts as a barrier impeding formation of the 2D oxide on the (111) terrace behind it. We demonstrate that the details of the structure of the 1D oxide govern the rate of 2D oxidation and discuss implications for oxidation of nanoparticles.
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| 6. |
- Kohler, L, et al.
(författare)
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High-coverage oxygen structures on Rh(111): Adsorbate repulsion and site preference is not enough
- 2004
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Ingår i: Physical Review Letters. - 1079-7114. ; 93:26
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Tidskriftsartikel (refereegranskat)abstract
- A new O induced structure on Rh(111) displaying a (2root3 x 2root3)R30degrees periodicity with an oxygen coverage of 2/3 has been studied by high resolution core level spectroscopy, scanning tunneling microscopy, and density functional theory. Although O favors fcc hollow sites in all other known phases, it occupies both fcc and hcp sites in this structure, which cannot be explained by pairwise adsorbate repulsion only. Both the (22root3 x 2root3)R30degrees and (2x2)-3O structures also exemplify that density-of-states contrast can lead to oxygen adatoms appearing as protrusions in scanning tunneling microscopy images.
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| 7. |
- Kresse, G, et al.
(författare)
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Complex surface reconstructions solved by ab initio molecular dynamics
- 2003
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Ingår i: Applied Physics A: Materials Science & Processing. - : Springer Science and Business Media LLC. - 1432-0630 .- 0947-8396. ; 76:5, s. 701-710
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Tidskriftsartikel (refereegranskat)abstract
- Complex surface reconstructions and surface oxides, in particular, often exhibit complicated atomic arrangements, which are difficult to resolve with traditional experimental methods, such as low energy electron diffraction (LEED), surface X-ray diffraction (SXRD) or scanning tunnelling microscopy (STM) alone. Therefore, ab initio density functional calculations are used as a supplement to the experimental techniques, but even then the structural determination usually relies on a simple trial and error procedure, in which conceivable models are first constructed and then tested for their stability in ab initio calculations. An exhaustive search of the configuration space is usually difficult and requires a significant human effort. Solutions to this problem, such as simulated annealing, have long been known, but are usually considered to be too time-consuming in combination with first principles methods. In this work, we show that ab initio density functional codes are now sufficiently fast to perform extensive finite temperature molecular dynamics. The merits of this approach are exemplified for two cases, for a complex two-dimensional surface oxide on Pd(111), and for the oxygen induced c(6 x 2) reconstruction of V(110).
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| 8. |
- Lundgren, Edvin, et al.
(författare)
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The surface oxide as a source of oxygen on Rh(111)
- 2005
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Ingår i: Journal of Electron Spectroscopy and Related Phenomena. - : Elsevier BV. - 0368-2048 .- 1873-2526. ; 144:SI, s. 367-372
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Tidskriftsartikel (refereegranskat)abstract
- The reduction of a thin surface oxide on the Rh(1 1 1) surface by CO is studied in situ by photoemission spectroscopy, scanning tunneling microscopy, and density functional theory. CO molecules are found not to adsorb on the surface oxide at a sample temperature of 100 K, in contrast to on the clean and chemisorbed oxygen covered surface. Despite this behavior, the surface oxide may still be reduced by CO, albeit in a significantly different fashion as compared to the reduction of a phase containing only chemisorbed on surface oxygen. The experimental observations combined with theoretical considerations concerning the stability of the surface oxide, result in a model of the reduction process at these pressures suggesting that the surface oxide behaves as a source of oxygen for the CO-oxidation reaction.
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| 9. |
- Lundgren, Edvin, et al.
(författare)
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Two-dimensional oxide on Pd(111).
- 2002
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Ingår i: Physical Review Letters. - 1079-7114. ; 88:24, s. 246103-246103
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Tidskriftsartikel (refereegranskat)abstract
- The oxidation of Pd(111) leads to an incommensurate surface oxide, which was studied by the use of scanning tunneling microscopy, surface x-ray diffraction, high resolution core level spectroscopy, and density functional calculations. A combination of these methods reveals a two-dimensional structure having no resemblance to bulk oxides of Pd. Our study also demonstrates how the atomic arrangement of a nontrivial incommensurate surface can be solved by molecular dynamics in a case where experimental techniques alone give no solution.
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| 10. |
- Martin, Natalia, et al.
(författare)
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High-resolution core-level spectroscopy study of the ultrathin aluminum oxide film on NiAl(110)
- 2011
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Ingår i: Physical Review B - Condensed Matter and Materials Physics. - 2469-9950 .- 2469-9969 .- 1098-0121. ; 83:12
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Tidskriftsartikel (refereegranskat)abstract
- We have studied the ultrathin aluminum oxide film on NiAl(110) by a combination of high-resolution core-level spectroscopy and density functional theory calculations. Energy-dependent core-level data from the O 1s and Al 2p levels allows for a distinction between oxygen and aluminum atoms residing at the surface or inside the aluminum oxide film. A comparison to calculated core-level binding energies from the recent model by Kresse et al. [Science 308, 1440 (2005)] reveals good agreement with experiment, and the complex spectroscopic signature of the thin Al oxide on NiAl(110) can be explained. Our assignment of a shifted component in the O 1s spectra to oxygen atoms at the surface with a particular Al and oxygen coordination may have implications for the interpretation of photoelectron-diffraction experiments from similar ultrathin aluminum oxide films.
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