226 research outputs found
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
Infrared and Reflected Solar Radiation Measurements from the TIROS 2 Meteorological Satellite
TIROS II contains instrumentation for measuring infrared and reflected solar radiation from the earth and its atmosphere. A medium resolution scanning radiometer and a low resolution non-scanning radiometer are employed. The satellite's spin provides the scan line of the medium resolution radiometer which is then advanced by the orbital motion. The spatial resolution is about 40 miles square when the earth directly beneath the satellite is viewed. The five channels employ bolometer detectors and filters to limit the spectral responses to five bands: 6 to 6.5 microns, 8 to 12 microns, 0.2 to 6 microns, 8 to 30 microns, and 0.55 to 0.75 microns. These five bands study, respectively: radiation in the water vapor absorption band; day and nighttime cloud cover; albedo; thermal radiation; and visual maps for comparison with satellite vidicon pictures. The low resolution non-scanning radiometer measures the earth's black-body temperature and albedo. Its field when viewing directly below is a circle of 450 miles diameter, covering part of each frame from the wide-field television camera. This radiometer consists of two thermistors, each in the apex of a reflective cone which provides optical gain. One thermistor is black and responds to both thermal and reflected solar radiation. The second responds to thermal but reflects solar radiation. The design, calibration, performance, and data reduction for both systems are discussed herein
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
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
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
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
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
First-principles prediction of structure, energetics, formation enthalpy, elastic constants, polarization, and piezoelectric constants of AlN, GaN, and InN: comparison of local and gradient-corrected density-functional theory
A number of diverse bulk properties of the zincblende and wurtzite III-V
nitrides AlN, GaN, and InN, are predicted from first principles within density
functional theory using the plane-wave ultrasoft pseudopotential method, within
both the LDA (local density) and GGA (generalized gradient) approximations to
the exchange-correlation functional. Besides structure and cohesion, we study
formation enthalpies (a key ingredient in predicting defect solubilities and
surface stability), spontaneous polarizations and piezoelectric constants
(central parameters for nanostructure modeling), and elastic constants. Our
study bears out the relative merits of the two density functional approaches in
describing diverse properties of the III-V nitrides (and of the parent species
N, Al, Ga, and In), and leads us to conclude that the GGA approximation,
associated with high-accuracy techniques such as multiprojector ultrasoft
pseudopotentials or modern all-electron methods, is to be preferred in the
study of III-V nitrides.Comment: RevTeX 6 pages, 12 tables, 0 figure
Surface relaxation and ferromagnetism of Rh(001)
The significant discrepancy between first-principles calculations and
experimental analyses for the relaxation of the (001) surface of rhodium has
been a puzzle for some years. In this paper we present density functional
theory calculations using the local-density approximation and the generalized
gradient approximation of the exchange-correlation functional. We investigate
the thermal expansion of the surface and the possibility of surface magnetism.
The results throw light on several, hitherto overlooked, aspects of metal
surfaces. We find, that, when the free energy is considered, density-functional
theory provides results in good agreement with experiments.Comment: 6 pages, 4 figures, submitted to Phys. Rev. Lett. (April 28, 1996
Ab initio atomistic thermodynamics and statistical mechanics of surface properties and functions
Previous and present "academic" research aiming at atomic scale understanding
is mainly concerned with the study of individual molecular processes possibly
underlying materials science applications. Appealing properties of an
individual process are then frequently discussed in terms of their direct
importance for the envisioned material function, or reciprocally, the function
of materials is somehow believed to be understandable by essentially one
prominent elementary process only. What is often overlooked in this approach is
that in macroscopic systems of technological relevance typically a large number
of distinct atomic scale processes take place. Which of them are decisive for
observable system properties and functions is then not only determined by the
detailed individual properties of each process alone, but in many, if not most
cases also the interplay of all processes, i.e. how they act together, plays a
crucial role. For a "predictive materials science modeling with microscopic
understanding", a description that treats the statistical interplay of a large
number of microscopically well-described elementary processes must therefore be
applied. Modern electronic structure theory methods such as DFT have become a
standard tool for the accurate description of individual molecular processes.
Here, we discuss the present status of emerging methodologies which attempt to
achieve a (hopefully seamless) match of DFT with concepts from statistical
mechanics or thermodynamics, in order to also address the interplay of the
various molecular processes. The new quality of, and the novel insights that
can be gained by, such techniques is illustrated by how they allow the
description of crystal surfaces in contact with realistic gas-phase
environments.Comment: 24 pages including 17 figures, related publications can be found at
http://www.fhi-berlin.mpg.de/th/paper.htm
- …