640 research outputs found
Ab initio study on the effects of transition metal doping of Mg2NiH4
Mg2NiH4 is a promising hydrogen storage material with fast (de)hydrogenation
kinetics. Its hydrogen desorption enthalpy, however, is too large for practical
applications. In this paper we study the effects of transition metal doping by
first-principles density functional theory calculations. We show that the
hydrogen desorption enthalpy can be reduced by ~0.1 eV/H2 if one in eight Ni
atoms is replaced by Cu or Fe. Replacing Ni by Co atoms, however, increases the
hydrogen desorption enthalpy. We study the thermodynamic stability of the
dopants in the hydrogenated and dehydrogenated phases. Doping with Co or Cu
leads to marginally stable compounds, whereas doping with Fe leads to an
unstable compound. The optical response of Mg2NiH4 is also substantially
affected by doping. The optical gap in Mg2NiH4 is ~1.7 eV. Doping with Co, Fe
or Cu leads to impurity bands that reduce the optical gap by up to 0.5 eV.Comment: 8 pages, 4 figure
Band gaps in pseudopotential self-consistent GW calculations
For materials which are incorrectly predicted by density functional theory to
be metallic, an iterative procedure must be adopted in order to perform GW
calculations. In this paper we test two iterative schemes based on the
quasi-particle and pseudopotential approximations for a number of inorganic
semiconductors whose electronic structures are well known from experiment.
Iterating just the quasi-particle energies yields a systematic, but modest
overestimate of the band gaps, confirming conclusions drawn earlier for CaB_6
and YH_3. Iterating the quasi-particle wave functions as well gives rise to an
imbalance between the Hartree and Fock potentials and results in bandgaps in
far poorer agreement with experiment.Comment: 5 pages, 2 figures, 2 table
Work functions of self-assembled monolayers on metal surfaces
Using first-principles calculations we show that the work function of noble
metals can be decreased or increased by up to 2 eV upon the adsorption of
self-assembled monolayers of organic molecules. We identify the contributions
to these changes for several (fluorinated) thiolate molecules adsorbed on
Ag(111), Au(111) and Pt(111) surfaces. The work function of the clean metal
surfaces increases in this order, but adsorption of the monolayers reverses the
order completely. Bonds between the thiolate molecules and the metal surfaces
generate an interface dipole, whose size is a function of the metal, but it is
relatively independent of the molecules. The molecular and bond dipoles can
then be added to determine the overall work function.Comment: 5 pages, 2 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
Ab initio study of magnesium alanate, Mg(AlH4)2
Magnesium alanate Mg(AlH4)2 has recently raised interest as a potential
material for hydrogen storage. We apply ab initio calculations to characterize
structural, electronic and energetic properties of Mg(AlH4)2. Density
functional theory calculations within the generalized gradient approximation
(GGA) are used to optimize the geometry and obtain the electronic structure.
The latter is also studied by quasi-particle calculations at the GW level.
Mg(AlH4)2 is a large band gap insulator with a fundamental band gap of 6.5 eV.
The hydrogen atoms are bonded in AlH4 complexes, whose states dominate both the
valence and the conduction bands. On the basis of total energies, the formation
enthalpy of Mg(AlH4)2 with respect to bulk magnesium, bulk aluminum and
hydrogen gas is 0.17 eV/H2 (at T = 0). Including corrections due to the zero
point vibrations of the hydrogen atoms this number decreases to 0.10 eV/H2. The
enthalpy of the dehydrogenation reaction Mg(AlH4)2 -> MgH2 +2Al+3H2(g) is close
to zero, which impairs the potential usefulness of magnesium alanate as a
hydrogen storage material.Comment: 5 pages, 3 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
Surface Dipoles and Work Functions of Alkylthiolates and Fluorinated Alkylthiolates on Au(111)
We study the dipole formation at the surface formed by -CH3 and -CF3
terminated shortchain alkyl-thiolate monolayers on Au(111). In particular, we
monitor the change in work function upon chemisorption using density functional
theory calculations. We separate the surface dipole into two contributions,
resulting from the gold-adsorbate interaction and the intrinsic dipole of the
adsorbate layer, respectively. The two contributions turn out to be
approximately additive. Adsorbate dipoles are defined by calculating dipole
densities of free-standing molecular monolayers. The gold-adsorbate interaction
is to a good degree determined by the Au-S bond only. This bond is nearly
apolar and its contribution to the surface dipole is relatively small. The
surface dipole of the self-assembled monolayer is then dominated by the
intrinsic dipole of the thiolate molecules. Alkyl-thiolates increase the work
function of Au(111), whereas fluorinated alkyl-thiolates decrease it.Comment: 24 pages, 5 figures, 4 table
First-principles study of the interaction and charge transfer between graphene and metals
Measuring the transport of electrons through a graphene sheet necessarily
involves contacting it with metal electrodes. We study the adsorption of
graphene on metal substrates using first-principles calculations at the level
of density functional theory. The bonding of graphene to Al, Ag, Cu, Au and
Pt(111) surfaces is so weak that its unique "ultrarelativistic" electronic
structure is preserved. The interaction does, however, lead to a charge
transfer that shifts the Fermi level by up to 0.5 eV with respect to the
conical points. The crossover from p-type to n-type doping occurs for a metal
with a work function ~5.4 eV, a value much larger than the work function of
free-standing graphene, 4.5 eV. We develop a simple analytical model that
describes the Fermi level shift in graphene in terms of the metal substrate
work function. Graphene interacts with and binds more strongly to Co, Ni, Pd
and Ti. This chemisorption involves hybridization between graphene -states
and metal d-states that opens a band gap in graphene. The graphene work
function is as a result reduced considerably. In a current-in-plane device
geometry this should lead to n-type doping of graphene.Comment: 12 pages, 9 figure
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