455 research outputs found
Structure and stability of a high-coverage (1x1) oxygen phase on Ru(0001)
The formation of chemisorbed O-phases on Ru(0001) by exposure to O_2 at low
pressures is apparently limited to coverages Theta <= 0.5. Using low-energy
electron diffraction and density functional theory we show that this
restriction is caused by kinetic hindering and that a dense O overlayer (Theta
= 1) can be formed with a (1x1) periodicity. The structural and energetic
properties of this new adsorbate phase are analyzed and discussed in view of
attempts to bridge the so-called "pressure gap" in heterogeneous catalysis. It
is argued that the identified system actuates the unusually high rate of
oxidizing reactions at Ru surfaces under high oxygen pressure conditions.Comment: RevTeX, 6 pages, 3 figures, to appear in Phys. Rev. Let
Towards a first-principles theory of surface thermodynamics and kinetics
Understanding of the complex behavior of particles at surfaces requires
detailed knowledge of both macroscopic and microscopic processes that take
place; also certain processes depend critically on temperature and gas
pressure. To link these processes we combine state-of-the-art microscopic, and
macroscopic phenomenological, theories. We apply our theory to the O/Ru(0001)
system and calculate thermal desorption spectra, heat of adsorption, and the
surface phase diagram. The agreement with experiment provides validity for our
approach which thus identifies the way for a predictive simulation of surface
thermodynamics and kinetics.Comment: 4 pages including 3 figures. Related publications can be found at
http://www.fhi-berlin.mpg.de/th/paper.htm
Anomalous Behavior of Ru for Catalytic Oxidation: A Theoretical Study of the Catalytic Reaction CO + 1/2 O_2 --> CO_2
Recent experiments revealed an anomalous dependence of carbon monoxide
oxidation at Ru(0001) on oxygen pressure and a particularly high reaction rate.
Below we report density functional theory calculations of the energetics and
reaction pathways of the speculated mechanism. We will show that the
exceptionally high rate is actuated by a weakly but nevertheless well bound
(1x1) oxygen adsorbate layer. Furthermore it is found that reactions via
scattering of gas-phase CO at the oxygen covered surface may play an important
role. Our analysis reveals, however, that reactions via adsorbed CO molecules
(the so-called Langmuir-Hinshelwood mechanism) dominate.Comment: 5 pages, 4 figures, Phys. Rev. Letters, Feb. 1997, in prin
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
Half-metallicity and efficient spin injection in AlN/GaN:Cr (0001) heterostructure
First-principles investigations of the structural, electronic and magnetic
properties of Cr-doped AlN/GaN (0001) heterostructures reveal that Cr
segregates into the GaN region, that these interfaces retain their important
half-metallic character and thus yield efficient (100 %) spin polarized
injection from a ferromagnetic GaN:Cr electrode through an AlN tunnel barrier -
whose height and width can be controlled by adjusting the Al concentration in
the graded bandgap engineered Al(1-x)Ga(x)N (0001) layers.Comment: submitted for publicatio
Insights into the function of silver as an oxidation catalyst by ab initio, atomistic thermodynamics
To help understand the high activity of silver as an oxidation catalyst,
e.g., for the oxidation of ethylene to epoxide and the dehydrogenation of
methanol to formaldehyde, the interaction and stability of oxygen species at
the Ag(111) surface has been studied for a wide range of coverages. Through
calculation of the free energy, as obtained from density-functional theory and
taking into account the temperature and pressure via the oxygen chemical
potential, we obtain the phase diagram of O/Ag(111). Our results reveal that a
thin surface-oxide structure is most stable for the temperature and pressure
range of ethylene epoxidation and we propose it (and possibly other similar
structures) contains the species actuating the catalysis. For higher
temperatures, low coverages of chemisorbed oxygen are most stable, which could
also play a role in oxidation reactions. For temperatures greater than about
775 K there are no stable oxygen species, except for the possibility of O atoms
adsorbed at under-coordinated surface sites Our calculations rule out thicker
oxide-like structures, as well as bulk dissolved oxygen and molecular
ozone-like species, as playing a role in the oxidation reactions.Comment: 15 pages including 9 figures, Related publications can be found at
http://www.fhi-berlin.mpg.de/th/paper.htm
Theoretical analysis of the electronic structure of the stable and metastable c(2x2) phases of Na on Al(001): Comparison with angle-resolved ultra-violet photoemission spectra
Using Kohn-Sham wave functions and their energy levels obtained by
density-functional-theory total-energy calculations, the electronic structure
of the two c(2x2) phases of Na on Al(001) are analysed; namely, the metastable
hollow-site structure formed when adsorption takes place at low temperature,
and the stable substitutional structure appearing when the substrate is heated
thereafter above ca. 180K or when adsorption takes place at room temperature
from the beginning. The experimentally obtained two-dimensional band structures
of the surface states or resonances are well reproduced by the calculations.
With the help of charge density maps it is found that in both phases, two
pronounced bands appear as the result of a characteristic coupling between the
valence-state band of a free c(2x2)-Na monolayer and the
surface-state/resonance band of the Al surfaces; that is, the clean (001)
surface for the metastable phase and the unstable, reconstructed "vacancy"
structure for the stable phase. The higher-lying band, being Na-derived,
remains metallic for the unstable phase, whereas it lies completely above the
Fermi level for the stable phase, leading to the formation of a
surface-state/resonance band-structure resembling the bulk band-structure of an
ionic crystal.Comment: 11 pages, 11 postscript figures, published in Phys. Rev. B 57, 15251
(1998). Other related publications can be found at
http://www.rz-berlin.mpg.de/th/paper.htm
Quantification of graphene based core/shell quantum dots from first principles
Density functional calculations are performed to study the electronic structure of recently proposed graphene/graphane based core/shell quantum dots, which have a type I band alignment and exhibit quantized carrier energy levels. Strong confinement is robust with shell thickness. The bandgap, band offset, and the number of confined carrier orbitals with different size and geometry are determined. Our findings indicate that these core/shell dots are potentially well suited for the design of advanced diode lasers and room-temperature single electron devices. The proposed method to determine the number of confined orbitals is applicable for other quantum dot systems.We acknowledge the computing resources provided by
the National Computational Infrastructure (Australia) and
support from the Australian Research Council. Support from
AMMRF node at the University of Sydney (ACMM) is
gratefully acknowledged
Sub-surface Oxygen and Surface Oxide Formation at Ag(111): A Density-functional Theory Investigation
To help provide insight into the remarkable catalytic behavior of the
oxygen/silver system for heterogeneous oxidation reactions, purely sub-surface
oxygen, and structures involving both on-surface and sub-surface oxygen, as
well as oxide-like structures at the Ag(111) surface have been studied for a
wide range of coverages and adsorption sites using density-functional theory.
Adsorption on the surface in fcc sites is energetically favorable for low
coverages, while for higher coverage a thin surface-oxide structure is
energetically favorable. This structure has been proposed to correspond to the
experimentally observed (4x4) phase. With increasing O concentrations, thicker
oxide-like structures resembling compressed Ag2O(111) surfaces are
energetically favored. Due to the relatively low thermal stability of these
structures, and the very low sticking probability of O2 at Ag(111), their
formation and observation may require the use of atomic oxygen (or ozone, O3)
and low temperatures. We also investigate diffusion of O into the sub-surface
region at low coverage (0.11 ML), and the effect of surface Ag vacancies in the
adsorption of atomic oxygen and ozone-like species. The present studies,
together with our earlier investigations of on-surface and
surface-substitutional adsorption, provide a comprehensive picture of the
behavior and chemical nature of the interaction of oxygen and Ag(111), as well
as of the initial stages of oxide formation.Comment: 17 pages including 14 figures, Related publications can be found at
http://www.fhi-berlin.mpg.de/th/paper.htm
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
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