5,053 research outputs found
The role of different negatively charged layers in Ca10(Fe1-xPtxAs)10(Pt3+yAs8) and superconductivity at 30 K in electron-doped (Ca0.8La0.2)10(FeAs)10(Pt3As8)
The recently discovered compounds Ca10(Fe1-xPtxAs)10(Pt3+yAs8) exhibit
superconductivity up to 38 K, and contain iron arsenide (FeAs) and platinum
arsenide (Pt3+yAs8) layers separated by layers of Ca atoms. We show that high
Tc's above 15 K only emerge if the iron-arsenide layers are at most free of
platinum-substitution (x \rightarrow 0) in contrast to recent reports. In fact
Pt-substitution is detrimental to higher Tc, which increases up to 38 K only by
charge doping of pure FeAs layers. We point out, that two different negatively
charged layers [(FeAs)10]n- and (Pt3+yAs8)m- compete for the electrons provided
by the Ca2+ ions, which is unique in the field of iron-based superconductors.
In the parent compound Ca10(FeAs)10(Pt3As8), no excess charge dopes the
FeAs-layer, and superconductivity has to be induced by Pt-substitution, albeit
below 15 K. In contrast, the additional Pt-atom in the Pt4As8layer shifts the
charge balance between the layers equivalent to charge doping by 0.2 electrons
per FeAs. Only in this case Tc raises to 38 K, but decreases again if
additionally platinum is substituted for iron. This charge doping scenario is
supported by our discovery of superconductivity at 30 K in the electron-doped
La-1038 compound (Ca0.8La0.2)10(FeAs)10(Pt3As8) without significant
Pt-substitution.Comment: 4 pages, 4 figure
Surface properties of the clean and Au/Pd covered FeO(111): a DFT and DFT+ study
The spin-density functional theory (DFT) and DFT+ with Hubbard term
accounting for on-site Coulomb interactions were applied to investigate
structure, stability, and electronic properties of different terminations of
the FeO(111) surface. All terminations of the ferrimagnetic
FeO(111) surface exhibit very large (up to 90%) relaxations of the
first four interlayer distances, decreasing with the oxide layer depth. Our
calculations predict the iron terminated surface to be most stable in a wide
range of the accessible values of the oxygen chemical potential. The adsorption
of Au and Pd on two stable Fe- and O-terminated surfaces is studied. Our
results show that Pd binds stronger than Au both to the Fe- and O-terminated
surface. DFT+ gives stronger bonding than DFT. The bonding of both
adsorbates to the O-terminated magnetite surface is by 1.5-2.5 eV stronger than
to the Fe-terminated surface
Ideal strengths and bonding properties of PuO2 under tension
We perform a first-principles computational tensile test on PuO based
on density-functional theory within local density approximation (LDA)+\emph{U}
formalism to investigate its structural, mechanical, magnetic, and intrinsic
bonding properties in the four representative directions: [001], [100], [110],
and [111]. The stress-strain relations show that the ideal tensile strengths in
the four directions are 81.2, 80.5, 28.3, and 16.8 GPa at strains of 0.36,
0.36, 0.22, and 0.18, respectively. The [001] and [100] directions are
prominently stronger than other two directions since that more PuO bonds
participate in the pulling process. Through charge and density of states
analysis along the [001] direction, we find that the strong mixed
ionic/covalent character of PuO bond is weakened by tensile strain and
PuO will exhibit an insulator-to-metal transition after tensile stress
exceeds about 79 GPa.Comment: 11 pages, 6 figure
First-principles Calculations of Engineered Surface Spin Structures
The engineered spin structures recently built and measured in scanning
tunneling microscope experiments are calculated using density functional
theory. By determining the precise local structure around the surface
impurities, we find the Mn atoms can form molecular structures with the binding
surface, behaving like surface molecular magnets. The spin structures are
confirmed to be antiferromagnetic, and the exchange couplings are calculated
within 8% of the experimental values simply by collinear-spin GGA+U
calculations. We can also explain why the exchange couplings significantly
change with different impurity binding sites from the determined local
structure. The bond polarity is studied by calculating the atomic charges with
and without the Mn adatoms
Electronic structure of copper intercalated transition metal dichalcogenides: First-principles calculations
We report first principles calculations, within density functional theory, of
copper intercalated titanium diselenides, CuxTiSe2, for values of x ranging
from 0 to 0.11. The effect of intercalation on the energy bands and densities
of states of the host material is studied in order to better understand the
cause of the superconductivity that was recently observed in these structures.
We find that charge transfer from the copper atoms to the metal dichalcogenide
host layers causes a gradual reduction in the number of holes in the otherwise
semi-metallic pristine TiSe2, thus suppressing the charge density wave
transition at low temperatures, and a corresponding increase in the density of
states at the Fermi level. These effects are probably what drive the
superconducting transition in the intercalated systems.Comment: 8 pages, 6 figure
Kinetic Energy Density Study of Some Representative Semilocal Kinetic Energy Functionals
There is a number of explicit kinetic energy density functionals for
non-interacting electron systems that are obtained in terms of the electron
density and its derivatives. These semilocal functionals have been widely used
in the literature. In this work we present a comparative study of the kinetic
energy density of these semilocal functionals, stressing the importance of the
local behavior to assess the quality of the functionals. We propose a quality
factor that measures the local differences between the usual orbital-based
kinetic energy density distributions and the approximated ones, allowing to
ensure if the good results obtained for the total kinetic energies with these
semilocal functionals are due to their correct local performance or to error
cancellations. We have also included contributions coming from the laplacian of
the electron density to work with an infinite set of kinetic energy densities.
For all the functionals but one we have found that their success in the
evaluation of the total kinetic energy are due to global error cancellations,
whereas the local behavior of their kinetic energy density becomes worse than
that corresponding to the Thomas-Fermi functional.Comment: 12 pages, 3 figure
The atomic orbitals of the topological atom
The effective atomic orbitals have been realized in the framework of Bader’s atoms in molecules theory for a general wavefunction. This formalism can be used to retrieve from any type of calculation a
proper set of orthonormalized numerical atomic orbitals, with occupation numbers that sum up to the
respective Quantum Theory of Atoms in Molecules (QTAIM) atomic populations. Experience shows
that only a limited number of effective atomic orbitals exhibit significant occupation numbers. These
correspond to atomic hybrids that closely resemble the core and valence shells of the atom. The
occupation numbers of the remaining effective orbitals are almost negligible, except for atoms with
hypervalent character. In addition, the molecular orbitals of a calculation can be exactly expressed
as a linear combination of this orthonormalized set of numerical atomic orbitals, and the Mulliken
population analysis carried out on this basis set exactly reproduces the original QTAIM atomic populations of the atoms. Approximate expansion of the molecular orbitals over a much reduced set of
orthogonal atomic basis functions can also be accomplished to a very good accuracy with a singular
value decomposition procedure
Polarization and Charge Transfer in the Hydration of Chloride Ions
A theoretical study of the structural and electronic properties of the
chloride ion and water molecules in the first hydration shell is presented. The
calculations are performed on an ensemble of configurations obtained from
molecular dynamics simulations of a single chloride ion in bulk water. The
simulations utilize the polarizable AMOEBA force field for trajectory
generation, and MP2-level calculations are performed to examine the electronic
structure properties of the ions and surrounding waters in the external field
of more distant waters. The ChelpG method is employed to explore the effective
charges and dipoles on the chloride ions and first-shell waters. The Quantum
Theory of Atoms in Molecules (QTAIM) is further utilized to examine charge
transfer from the anion to surrounding water molecules.
From the QTAIM analysis, 0.2 elementary charges are transferred from the ion
to the first-shell water molecules. The default AMOEBA model overestimates the
average dipole moment magnitude of the ion compared with the estimated quantum
mechanical value. The average magnitude of the dipole moment of the water
molecules in the first shell treated at the MP2 level, with the more distant
waters handled with an AMOEBA effective charge model, is 2.67 D. This value is
close to the AMOEBA result for first-shell waters (2.72 D) and is slightly
reduced from the bulk AMOEBA value (2.78 D). The magnitude of the dipole moment
of the water molecules in the first solvation shell is most strongly affected
by the local water-water interactions and hydrogen bonds with the second
solvation shell, rather than by interactions with the ion.Comment: Slight revision, in press at J. Chem. Phy
Exploring water adsorption on isoelectronically doped graphene using alchemical derivatives
The design and production of novel 2-dimensional materials has seen great
progress in the last decade, prompting further exploration of the chemistry of
such materials. Doping and hydrogenating graphene is an experimentally realised
method of changing its surface chemistry, but there is still a great deal to be
understood on how doping impacts on the adsorption of molecules. Developing
this understanding is key to unlocking the potential applications of these
materials. High throughput screening methods can provide particularly effective
ways to explore vast chemical compositions of materials. Here, alchemical
derivatives are used as a method to screen the dissociative adsorption energy
of water molecules on various BN doped topologies of hydrogenated graphene. The
predictions from alchemical derivatives are assessed by comparison to density
functional theory. This screening method is found to predict dissociative
adsorption energies that span a range of more than 2 eV, with a mean absolute
error eV. In addition, we show that the quality of such predictions can
be readily assessed by examination of the Kohn-Sham highest occupied molecular
orbital in the initial states. In this way, the root mean square error in the
dissociative adsorption energies of water is reduced by almost an order of
magnitude (down to eV) after filtering out poor predictions. The
findings point the way towards a reliable use of first order alchemical
derivatives for efficient screening procedures
Structure and binding in crystals of cage-like molecules: hexamine and platonic hydrocarbons
In this paper, we show that first-principle calculations using a van der
Waals density functional (vdW-DF), [Phys. Rev. Lett. , 246401
(2004)] permits determination of molecular crystal structure. We study the
crystal structures of hexamine and the platonic hydrocarbons (cubane and
dodecahedrane). The calculated lattice parameters and cohesion energy agree
well with experiments. Further, we examine the asymptotic accounts of the van
der Waals forces by comparing full vdW-DF with asymptotic atom-based pair
potentials extracted from vdW-DF. The character of the binding differ in the
two cases, with vdW-DF giving a significant enhancement at intermediate and
relevant binding separations. We analyze consequences of this result for
methods such as DFT-D, and question DFT-D's transferability over the full range
of separations
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