490 research outputs found
CO adsorption on Pt induced Ge nanowires
Using density functional theory, we investigate the possible adsorption sites
of CO molecules on the recently discovered Pt induced Ge nanowires on Ge(001).
Calculated STM images are compared to experimental STM images to identify the
experimentally observed adsorption sites. The CO molecules are found to adsorb
preferably onto the Pt atoms between the Ge nanowire dimer segments. This
adsorption site places the CO in between two nanowire dimers, pushing them
outward, blocking the nearest equivalent adsorption sites. This explains the
observed long-range repulsive interaction between CO molecules on these Pt
induced nanowires.Comment: 12 pages, 10 figure
Tunable Hydrogen Storage in Magnesium - Transition Metal Compounds
Magnesium dihydride (\mgh) stores 7.7 weight % hydrogen, but it suffers
from a high thermodynamic stability and slow (de)hydrogenation kinetics.
Alloying Mg with lightweight transition metals (TM = Sc, Ti, V, Cr) aims at
improving the thermodynamic and kinetic properties. We study the structure and
stability of MgTMH compounds, -1], by first-principles
calculations at the level of density functional theory. We find that the
experimentally observed sharp decrease in hydrogenation rates for
correlates with a phase transition of MgTMH from a fluorite to
a rutile phase. The stability of these compounds decreases along the series Sc,
Ti, V, Cr. Varying the transition metal (TM) and the composition , the
formation enthalpy of MgTMH can be tuned over the substantial
range 0-2 eV/f.u. Assuming however that the alloy MgTM does not
decompose upon dehydrogenation, the enthalpy associated with reversible
hydrogenation of compounds with a high magnesium content () is close to
that of pure Mg.Comment: 8 pages, 5 figure
Structural studies of phosphorus induced dimers on Si(001)
Renewed focus on the P-Si system due to its potential application in quantum
computing and self-directed growth of molecular wires, has led us to study
structural changes induced by P upon placement on Si(001)-. Using
first-principles density functional theory (DFT) based pseudopotential method,
we have performed calculations for P-Si(001) system, starting from an isolated
P atom on the surface, and systematically increasing the coverage up to a full
monolayer. An isolated P atom can favorably be placed on an {\bf M} site
between two atoms of adjacent Si dimers belonging to the same Si dimer row. But
being incorporated in the surface is even more energetically beneficial due to
the participation of the {\bf M} site as a receptor for the ejected Si. Our
calculations show that up to 1/8 monolayer coverage, hetero-dimer structure
resulting from replacement of surface Si atoms with P is energetically
favorable. Recently observed zig-zag features in STM are found to be consistent
with this replacement process. As coverage increases, the hetero-dimers give
way to P-P ortho-dimers on the Si dimer rows. This behavior is similar to that
of Si-Si d-dimers but are to be contrasted with the Al-Al dimers, which are
found between adjacent Si dimers rows and in a para-dimer arrangement. Unlike
Al-Si system P-Si does not show any para to ortho transition. For both systems,
the surface reconstruction is lifted at about one monolayer coverage. These
calculations help us in understanding the experimental data obtained using
scanning tunneling microscope.Comment: To appear in PR
Stability of conductance oscillations in monatomic sodium wires
We study the stability of conductance oscillations in monatomic sodium wires
with respect to structural variations. The geometry, the electronic structure
and the electronic potential of sodium wires suspended between two sodium
electrodes are obtained from self-consistent density functional theory
calculations. The conductance is calculated within the framework of the
Landauer-B\"utttiker formalism, using the mode-matching technique as formulated
recently in a real-space finite-difference scheme [Phys. Rev. B \textbf{70},
195402 (2004)]. We find a regular even-odd conductance oscillation as a
function of the wire length, where wires comprising an odd number of atoms have
a conductance close to the quantum unit , and even-numbered
wires have a lower conductance. The conductance of odd-numbered wires is stable
with respect to geometry changes in the wire or in the contacts between the
wire and the electrodes; the conductance of even-numbered wires is more
sensitive. Geometry changes affect the spacing and widths of the wire
resonances. In the case of odd-numbered wires the transmission is on-resonance,
and hardly affected by the resonance shapes, whereas for even-numbered wires
the transmission is off-resonance and sensitive to the resonance shapes.
Predicting the amplitude of the conductance oscillation requires a
first-principles calculation based upon a realistic structure of the wire and
the leads. A simple tight-binding model is introduced to clarify these results.Comment: 16 pages, 20 figure
Real space finite difference method for conductance calculations
We present a general method for calculating coherent electronic transport in
quantum wires and tunnel junctions. It is based upon a real space high order
finite difference representation of the single particle Hamiltonian and wave
functions. Landauer's formula is used to express the conductance as a
scattering problem. Dividing space into a scattering region and left and right
ideal electrode regions, this problem is solved by wave function matching (WFM)
in the boundary zones connecting these regions. The method is tested on a model
tunnel junction and applied to sodium atomic wires. In particular, we show that
using a high order finite difference approximation of the kinetic energy
operator leads to a high accuracy at moderate computational costs.Comment: 13 pages, 10 figure
First principles modelling of magnesium titanium hydrides
Mixing Mg with Ti leads to a hydride Mg(x)Ti(1-x)H2 with markedly improved
(de)hydrogenation properties for x < 0.8, as compared to MgH2. Optically, thin
films of Mg(x)Ti(1-x)H2 have a black appearance, which is remarkable for a
hydride material. In this paper we study the structure and stability of
Mg(x)Ti(1-x)H2, x= 0-1 by first-principles calculations at the level of density
functional theory. We give evidence for a fluorite to rutile phase transition
at a critical composition x(c)= 0.8-0.9, which correlates with the
experimentally observed sharp decrease in (de)hydrogenation rates at this
composition. The densities of states of Mg(x)Ti(1-x)H2 have a peak at the Fermi
level, composed of Ti d states. Disorder in the positions of the Ti atoms
easily destroys the metallic plasma, however, which suppresses the optical
reflection. Interband transitions result in a featureless optical absorption
over a large energy range, causing the black appearance of Mg(x)Ti(1-x)H2.Comment: 22 pages, 9 figures, 4 table
Hydrogen storage in magnesium-transition metal compounds: a first-principles study
Uncertainty analysis for large-scale model studies is a challenging activity that requires a different approach to uncertainty analysis at a smaller scale. However, in river basin studies, the practice of uncertainty analysis at a large scale is mostly derived from practice at a small scale. The limitations and inherent subjectivity of some current practices and assumptions are identified, based on the results of a quantitative uncertainty analysis exploring the effects of input data and parameter uncertainty on surface water nutrient concentration. We show that: (i) although the results from small- scale sensitivity analysis are often applied at larger scales, this is not always valid; (ii) the current restriction of the uncertainty assessment to uncertainty types with a strong evidence base gives structurally conservative estimates; (iii) uncertainty due to bias is usually not assessed, but it may easily outweigh the effects of variability; (iv) the uncertainty bandwidth may increase for higher aggregation levels, although the opposite is the standard assumption
Identification of a methylase required for 2-methylhopanoid production and implications for the interpretation of sedimentary hopanes
The rise of atmospheric oxygen has driven environmental change and biological evolution throughout much of Earth’s history and was enabled by the evolution of oxygenic photosynthesis in the cyanobacteria. Dating this metabolic innovation using inorganic proxies from sedimentary rocks has been difficult and one important approach has been to study the distributions of fossil lipids, such as steranes and 2-methylhopanes, as biomarkers for this process. 2-methylhopanes arise from degradation of 2-methylbacteriohopanepolyols (2-MeBHPs), lipids thought to be synthesized primarily by cyanobacteria. The discovery that 2-MeBHPs are produced by an anoxygenic phototroph, however, challenged both their taxonomic link with cyanobacteria and their functional link with oxygenic photosynthesis. Here, we identify a radical SAM methylase encoded by the hpnP gene that is required for methylation at the C-2 position in hopanoids. This gene is found in several, but not all, cyanobacteria and also in α -proteobacteria and acidobacteria. Thus, one cannot extrapolate from the presence of 2-methylhopanes alone, in modern environments or ancient sedimentary rocks, to a particular taxonomic group or metabolism. To understand the origin of this gene, we reconstructed the evolutionary history of HpnP. HpnP proteins from cyanobacteria, Methylobacterium species, and other α-proteobacteria form distinct phylogenetic clusters, but the branching order of these clades could not be confidently resolved. Hence,it is unclear whether HpnP, and 2-methylhopanoids, originated first in the cyanobacteria. In summary, existing evidence does not support the use of 2-methylhopanes as biomarkers for oxygenic photosynthesis
Ab-initio calculation of the electronic and optical excitations in polythiophene: effects of intra- and interchain screening
We present an calculation of the electronic and optical excitations of an
isolated polythiophene chain as well as of bulk polythiophene. We use the GW
approximation for the electronic self-energy and include excitonic effects by
solving the electron-hole Bethe-Salpeter equation. The inclusion of interchain
screening in the case of bulk polythiophene drastically reduces both the
quasi-particle band gap and the exciton binding energies, but the optical gap
is hardly affected. This finding is relevant for conjugated polymers in
general.Comment: 4 pages, 1 figur
Ab-initio prediction of the electronic and optical excitations in polythiophene: isolated chains versus bulk polymer
We calculate the electronic and optical excitations of polythiophene using
the GW approximation for the electronic self-energy, and include excitonic
effects by solving the electron-hole Bethe-Salpeter equation. Two different
situations are studied: excitations on isolated chains and excitations on
chains in crystalline polythiophene. The dielectric tensor for the crystalline
situation is obtained by modeling the polymer chains as polarizable line
objects, with a long-wavelength polarizability tensor obtained from the
ab-initio polarizability function of the isolated chain. With this model
dielectric tensor we construct a screened interaction for the crystalline case,
including both intra- and interchain screening. In the crystalline situation
both the quasi-particle band gap and the exciton binding energies are
drastically reduced in comparison with the isolated chain. However, the optical
gap is hardly affected. We expect this result to be relevant for conjugated
polymers in general.Comment: 15 pages including 4 figures; to appear in Phys. Rev. B, 6/15/200
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