1,495 research outputs found
Density functional theory study of Na at Al(111) and O at Ru(0001)
The success of density functional theory for the description of the
adsorption of atoms on surfaces is well established, and based on recent
calculations using gradient corrections, it has been shown that it also
describes well the dissociative adsorption of molecules at surfaces -
admittedly however, the data base for reactions at surfaces is still somewhat
small. In the present paper the power of density functional theory calculations
is demonstrated by investigations for two different adsorption systems, namely,
one with a strongly electropositive adsorbate [Na on Al(111)] and one with a
strongly electronegative adsorbate [O on Ru(0001)]. In each case, new hitherto
not expected adsorbate phases have been predicted by the theory: For Na on
Al(111) the stability of a "four-layer" surface alloy was identified while for
O on Ru(0001) it was predicted that the formation of a (1 x 1)-O adlayer should
be possible which implies that the apparent saturation coverage of 1/2 is due
to kinetic hindering.Comment: RevTeX, 24 pages, 6 figures in uufiles for
Theory of Adsorption on Metal Substrates
Contents:
5.1 Introduction
5.2 Concepts and definitions
5.3 The tight-binding picture of bonding
5.4 Adsorption of isolated adatoms
5.5 Alkali-metal adsorption: the traditional picture of on-surface adsorption
5.6 Substitutional adsorption and formation of surface alloys
5.7 Adsorption of CO on transition-metal surfaces - a model system for a
simple molecular adsorbate
5.8 Co-adsorption [the example CO plus O on Ru(0001)]
5.9 Chemical reactions at metal surfaces
5.10 The catalytic oxidation of CO
5.11 Summary outline of main pointsComment: 73 pages including 44 figures. A version with high-resolution figures
and related publications can be found at
http://www.fhi-berlin.mpg.de/th/paper.htm
Theory of alkali metal adsorption on close-packed metal surfaces
Results of recent density functional theory calculations for alkali metal
adsorbates on close-packed metal surfaces are discussed. Single adatoms on the
(111) surface of Al and Cu are studied with the self-consistent surface
Green-function method by which the pure adsorbate-substrate interaction may be
analyzed. Higher coverage ordered adlayers of K on Al(111), Na on Al(111), and
Na on Al(001) are treated using the ab-initio pseudopotential plane
wave method which affords the prediction of coverage dependent stable and
metastable adsorbate geometries and phase transitions of the adsorbate layers.
Together, these studies give insight and understanding into current key issues
in alkali metal adsorption, namely, the nature of the adsorbate-substrate bond
at low coverage and the occurrence of hitherto unanticipated adsorbate
geometries, and the associated electronic properties.Comment: to be published in Surface Reviews and Letters, 18 pages, 18 figure
Coadsorption of CO and O on Ru(0001): A structural analysis by density functional theory
Knowledge of the atomic geometry of a surface is a prerequisite for any
detailed understanding of the surface's electronic structure and chemical
properties. Previous studies have convincingly demonstrated that density
functional theory (DFT) yields accurate surface atomic geometries and that
reliable predictions concerning stable and metastable phases can be made on the
basis of the calculated energetics. In the present work we use DFT to
investigate the atomic structure of four ordered coadsorbate phases of carbon
monoxide and oxygen on Ru(0001). All of the structures have a (2x2) periodicity
with differing concentrations of CO molecules and O atoms. For two of these
phases dynamical low-energy electron diffraction (LEED) intensity analyses have
been performed and the agreement between our DFT- and the LEED-determined
structures is found to be very good. We predict the atomic geometry of the
third phase for which no structural determination based on experiments has been
made to date. We also predict the stability of a new ordered mixed phase.Comment: 6 pages, 1 figure, submitted to Israel Journal of Chemistry (June 29,
1998). Other related publications can be found at
http://www.rz-berlin.mpg.de/th/paper.htm
Study of CO Oxidation over Ru(0001) at High Gas Pressures
Experiments performed at high gas partial pressures have demonstrated that
the kinetics of the CO oxidation reaction at Ru(0001) is different and somewhat
anomalous compared to that over other transition metal surfaces and, in
particular, the turnover rate is exceptionally high. In order to gain insight
into the underlying reasons for this behavior, we performed density functional
theory calculations using the generalized gradient approximation for the
exchange-correlation functional. We find that the high rate is due to a weakly,
but nevertheless well bound, (1x1) oxygen adsorbate layer which may form for
high O_2 pressures but not under usual ultra high vacuum conditions. The
calculations indicate that reaction to CO_2 occurs both via scattering of
gas-phase CO molecules as well as by CO molecules weakly adsorbed at vacancies
in the oxygen adlayer, where the latter mechanism dominates the rate.Comment: 13 pages, 4 figures. Surface Science, in press (submitted July 1996
Mechanism of efficient carbon monoxide oxidation at Ru(0001)
We performed density-functional theory calculations using the generalized
gradient approximation for the exhange-correlation functional to investigate
the unusual catalytic behavior of Ru under elevated gas pressure conditions for
the carbon monoxide oxidation reaction, which includes a particularly high CO_2
turnover. Our calculations indicate that a full monolayer of adsorbed oxygen
actuates the high rate, enabling CO_2 formation via both scattering of
gas-phase CO molecules as well as by CO molecules adsorbed at oxygen vacancies
in the adlayer, where the latter mechanism is expected to be very efficient due
to the relatively weak adsorption energy of both CO and O, as well as the close
proximity of these reactants. In the present paper we analyse the bonding and
electronic properties associated with the reaction pathway for CO_2 production
via the scattering reaction. We find that the identified ``bent'' transition
state is due to electron transfer into the unoccupied 2 pi orbitals of the CO
molecule which reduces the Pauli repulsion between the impinging CO and the
O-covered surface. Bond formation to CO_2 then proceeds by electron transfer
back from the CO 2 pi orbitals into the bonding region between CO and the
adsorbed O atom.Comment: 20 pages, 7 figures. J. Vac. Sci. and Techn., in press (submitted
September 1996
First-principles prediction of phonon-mediated superconductivity in XBC (X= Mg, Ca, Sr, Ba)
From first-principles calculations, we predict four new intercalated
hexagonal BC (=Mg, Ca, Sr, Ba) compounds to be dynamically stable and
phonon-mediated superconductors. These compounds form a LiBC like structure but
are metallic. The calculated superconducting critical temperature, , of
MgBC is 51 K. The strong attractive interaction between -bonding
electrons and the B phonon mode gives rise to a larger electron-phonon
coupling constant (1.135) and hence high ; notably, higher than that of
MgB. The other compounds have a low superconducting critical temperature
(4-17 K) due to the interaction between -bonding electrons and low
energy phonons (E modes). Due to their energetic and dynamic
stability, we envisage that these compounds can be synthesized experimentally.Comment: 7 pages, 6 figure
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