186 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
Geometric, electronic and magnetic structure of FeO clusters
Correlation between geometry, electronic structure and magnetism of solids is
both intriguing and elusive. This is particularly strongly manifested in small
clusters, where a vast number of unusual structures appear. Here, we employ
density functional theory in combination with a genetic search algorithm,
GGA and a hybrid functional to determine the structure of gas phase
FeO clusters. For FeO cation clusters we also
calculate the corresponding vibration spectra and compare them with
experiments. We successfully identify FeO, FeO,
FeO, FeO and propose structures for
FeO. Within the triangular geometric structure of
FeO a non-collinear, ferrimagnetic and ferromagnetic state are
comparable in energy. FeO and FeO are
ferrimagnetic with a residual magnetic moment of 1~\muB{} due to ionization.
FeO is ferrimagnetic due to the odd number of Fe atoms. We
compare the electronic structure with bulk magnetite and find
FeO, FeO, FeO to be mixed
valence clusters. In contrast, in FeO and FeO
all Fe are found to be trivalent.Comment: 14 pages, 21 figure
Interactions of adsorbed CO on water ice at low temperatures
We present a computational study into the adsorption properties of CO on
amorphous and crystalline water surfaces under astrophysically relevant
conditions. Water and carbon dioxide are two of the most dominant species in
the icy mantles of interstellar dust grains and a thorough understanding of
their solid phase interactions at low temperatures is crucial for understanding
the structural evolution of the ices due to thermal segregation. In this paper,
a new HO-CO interaction potential is proposed and used to model the
ballistic deposition of CO layers on water ice surfaces, and to study the
individual binding sites at low coverages. Contrary to recent experimental
results, we do not observe CO island formation on any type of water
substrate. Additionally, density functional theory calculations are performed
to assess the importance of induced electrostatic interactions.Comment: Accepted for publication in Physical Chemistry Chemical Physic
Low work function of the (1000) Ca2N surface
Polymer diodes require cathodes that do not corrode the polymer but do have
low work function to minimize the electron injection barrier. First-principles
calculations demonstrate that the work function of the (1000) surface of the
compound Ca2N is half an eV lower than that of the elemental metal Ca (2.35 vs.
2.87 eV). Moreover its reactivity is expected to be smaller. This makes Ca2N an
interesting candidate to replace calcium as cathode material for polymer light
emitting diode devices.Comment: 3 pages, 4 figures, accepted by J. Appl. Phy
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
NMR shieldings from density functional perturbation theory: GIPAW versus all-electron calculations
We present a benchmark of the density functional linear response calculation
of NMR shieldings within the Gauge-Including Projector-Augmented-Wave method
against all-electron Augmented-Plane-Wavelocal-orbital and uncontracted
Gaussian basis set results for NMR shieldings in molecular and solid state
systems. In general, excellent agreement between the aforementioned methods is
obtained. Scalar relativistic effects are shown to be quite large for nuclei in
molecules in the deshielded limit. The small component makes up a substantial
part of the relativistic corrections.Comment: 3 figures, supplementary material include
Interrelation of work function and surface stability: the case of BaAl4
The relationship between the work function (Phi) and the surface stability of
compounds is, to our knowledge, unknown, but very important for applications
such as organic light-emitting diodes. This relation is studied using
first-principles calculations on various surfaces of BaAl4. The most stable
surface [Ba terminated (001)] has the lowest Phi (1.95 eV), which is lower than
that of any elemental metal including Ba. Adding barium to this surface neither
increases its stability nor lowers its work function. BaAl4 is also strongly
bound. These results run counter to the common perception that stability and a
low Phi are incompatible. Furthermore, a large anisotropy and a stable
low-work-function surface are predicted for intermetallic compounds with polar
surfaces.Comment: 4 pages, 5 figures, to be published in Chem. Ma
Band Offsets at the Interface between Crystalline and Amorphous Silicon from First Principles
The band offsets between crystalline and hydrogenated amorphous silicon
(a-Si:H) are key parameters governing the charge transport in modern silicon
hetrojunction solar cells. They are an important input for macroscopic
simulators that are used to further optimize the solar cell. Past experimental
studies, using X-ray photoelectron spectroscopy (XPS) and capacitance-voltage
measurements, have yielded conflicting results on the band offset. Here we
present a computational study on the band offsets. It is based on atomistic
models and density-functional theory (DFT). The amorphous part of the interface
is obtained by relatively long DFT first-principles molecular-dynamics (MD)
runs at an elevated temperature on 30 statistically independent samples. In
order to obtain a realistic conduction band position the electronic structure
of the interface is calculated with a hybrid functional. We find a slight
asymmetry in the band offsets, where the offset in the valence band (0.30 eV)
is larger than in the conduction band (0.17 eV). Our results are in agreement
with the latest XPS measurements that report a valence band offset of 0.3 eV
[M. Liebhaber et al., Appl. Phys. Lett. 106, 031601 (2015)]
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