361 research outputs found
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
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
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
The structure ofAl(111)-K−(√3 × √3)R30° determined by LEED: stable and metastable adsorption sites
It is found that the adsorption of potassium on Al(111) at 90 K and at 300 K both result in a (√3 × √3)R0° structure. Through a detailed LEED analysis it is revealed that at 300 K the adatoms occupy substitutional sites and at 90 K the adatoms occupy on-top sites; both geometries have hitherto been considered as very unusual. The relationship between bond length and coordination is discussed with respect to the present results, and with respect to other quantitative studies of alkali-metal/metal adsorption systems
Oxygen adsorption on the Ru (10 bar 1 0) surface: Anomalous coverage dependence
Oxygen adsorption onto Ru (10 bar 1 0) results in the formation of two
ordered overlayers, i.e. a c(2 times 4)-2O and a (2 times 1)pg-2O phase, which
were analyzed by low-energy electron diffraction (LEED) and density functional
theory (DFT) calculation. In addition, the vibrational properties of these
overlayers were studied by high-resolution electron loss spectroscopy. In both
phases, oxygen occupies the threefold coordinated hcp site along the densely
packed rows on an otherwise unreconstructed surface, i.e. the O atoms are
attached to two atoms in the first Ru layer Ru(1) and to one Ru atom in the
second layer Ru(2), forming zigzag chains along the troughs. While in the
low-coverage c(2 times 4)-O phase, the bond lengths of O to Ru(1) and Ru(2) are
2.08 A and 2.03 A, respectively, corresponding bond lengths in the
high-coverage (2 times 1)-2O phase are 2.01 A and 2.04 A (LEED). Although the
adsorption energy decreases by 220 meV with O coverage (DFT calculations), we
observe experimentally a shortening of the Ru(1)-O bond length with O coverage.
This effect could not be reconciled with the present DFT-GGA calculations. The
nu(Ru-O) stretch mode is found at 67 meV [c(2 times 4)-2O] and 64 meV [(2 times
1)pg-2O].Comment: 10 pages, figures are available as hardcopies on request by mailing
[email protected], submitted to Phys. Rev. B (8. Aug. 97), other related
publications can be found at http://www.rz-berlin.mpg.de/th/paper.htm
Bioreactor and scaffold design for the mechanical stimulation of anterior cruciate ligament grafts
First-principles investigation of Ag-Cu alloy surfaces in an oxidizing environment
In this paper we investigate by means of first-principles density functional
theory calculations the (111) surface of the Ag-Cu alloy under varying
conditions of pressure of the surrounding oxygen atmosphere and temperature.
This alloy has been recently proposed as a catalyst with improved selectivity
for ethylene epoxidation with respect to pure silver, the catalyst commonly
used in industrial applications. Here we show that the presence of oxygen leads
to copper segregation to the surface. Considering the surface free energy as a
function of the surface composition, we construct the convex hull to
investigate the stability of various surface structures. By including the
dependence of the free surface energy on the oxygen chemical potential, we are
able compute the phase diagram of the alloy as a function of temperature,
pressure and surface composition. We find that, at temperature and pressure
typically used in ethylene epoxidation, a number of structures can be present
on the surface of the alloy, including clean Ag(111), thin layers of copper
oxide and thick oxide-like structures. These results are consistent with, and
help explain, recent experimental results.Comment: 10 pages, 6 figure
Electronic structure of wurtzite and zinc-blende AlN
The electronic structure of AlN in wurtzite and zinc-blende phases is studied
experimentally and theoretically. By using x-ray emission spectroscopy, the Al
3p, Al 3s and N 2p spectral densities are obtained. The corresponding local and
partial theoretical densities of states (DOS), as well as the total DOS and the
band structure, are calculated by using the full potential linearized augmented
plane wave method, within the framework of the density functional theory. There
is a relatively good agreement between the experimental spectra and the
theoretical DOS, showing a large hybridization of the valence states all along
the valence band. The discrepancies between the experimental and theoretical
DOS, appearing towards the high binding energies, are ascribed to an
underestimation of the valence band width in the calculations. Differences
between the wurtzite and zinc-blende phases are small and reflect the slight
variations between the atomic arrangements of both phases
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
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