285 research outputs found
Forces and atomic relaxations in the pSIC approach with ultrasoft pseudopotentials
We present the scheme that allows for efficient calculations of forces in the
framework of pseudopotential self-interaction corrected (pSIC) formulation of
the density functional theory. The scheme works with norm conserving and also
with ultrasoft pseudopotentials and has been implemented in the plane-wave
basis code {\sc quantum espresso}. We have performed tests of the internal
consistency of the derived expressions for forces considering ZnO and CeO
crystals. Further, we have performed calculations of equilibrium geometry for
LaTiO, YTiO, and LaMnO perovskites and also for Re and Mn pairs in
silicon. Comparison with standard DFT and DFT+U approaches shows that in the
cases where spurious self-interaction matters, the pSIC approach predicts
different geometry, very often closer to the experimental data.Comment: 11 pages, 2 figure
Exceptionally strong magnetism in 4d perovskites RTcO3 (R=Ca,Sr,Ba)
The evolution of the magnetic ordering temperature of the 4d3 perovskites
RTcO3 (R=Ca,Sr,Ba) and its relation with its electronic and structural
properties has been studied by means of hybrid density functional theory and
Monte Carlo simulations. When compared to the most widely studied 3d
perovskites the large spatial extent of the 4d shells and their relatively
strong hybridization with oxygen weaken the tendency to form Jahn-Teller like
orbital ordering. This strengthens the superexchange interaction. The resulting
insulating G-type antiferromagnetic ground state is characterized by large
superexchange coupling constants (26-35 meV) and Neel temperatures (750-1200
K). These monotonically increase as a function of the R ionic radius due to the
progressive enhancement of the volume and the associated decrease of the
cooperative rotation of the TcO6 octahedra.Comment: 4 pages, 3 figure
Correlative Microscopy of Morphology and Luminescence of Cu porphyrin aggregates
Transfer of energy and information through molecule aggregates requires as
one important building block anisotropic, cable-like structures. Knowledge on
the spatial correlation of luminescence and morphology represents a
prerequisite in the understanding of internal processes and will be important
for architecting suitable landscapes. In this context we study the morphology,
fluorescence and phosphorescence of molecule aggregate structures on surfaces
in a spatially correlative way. We consider as two morphologies, lengthy
strands and isotropic islands. It turns out that phosphorescence is quite
strong compared to fluorescence and the spatial variation of the observed
intensities is largely in line with the amount of dye. However in proportion,
the strands exhibit more fluorescence than the isotropic islands suggesting
weaker non-radiative channels. The ratio fluorescence to phosphorescence
appears to be correlated with the degree of aggregation or internal order. The
heights at which luminescence saturates is explained in the context of
attenuation and emission multireflection, inside the dye. This is supported by
correlative photoemission electron microscopy which is more sensitive to the
surface region. The lengthy structures exhibit a pronounced polarization
dependence of the luminescence with a relative dichroism up to about 60%,
revealing substantial perpendicular orientation preference of the molecules
with respect to the substrate and parallel with respect to the strands
Computation of correlation-induced atomic displacements and structural transformations in paramagnetic KCuF3 and LaMnO3
We present a computational scheme for ab initio total-energy calculations of
materials with strongly interacting electrons using a plane-wave basis set. It
combines ab initio band structure and dynamical mean-field theory and is
implemented in terms of plane-wave pseudopotentials. The present approach
allows us to investigate complex materials with strongly interacting electrons
and is able to treat atomic displacements, and hence structural
transformations, caused by electronic correlations. Here it is employed to
investigate two prototypical Jahn-Teller materials, KCuF3 and LaMnO3, in their
paramagnetic phases. The computed equilibrium Jahn-Teller distortion and
antiferro-orbital order agree well with experiment, and the structural
optimization performed for paramagnetic KCuF3 yields the correct lattice
constant, equilibrium Jahn-Teller distortion and tetragonal compression of the
unit cell. Most importantly, the present approach is able to determine
correlation-induced structural transformations, equilibrium atomic positions
and lattice structure in both strongly and weakly correlated solids in their
paramagnetic phases as well as in phases with long-range magnetic order.Comment: 27 pages, 11 figure
Double Exchange Alone Does Not Explain the Resistivity of
The system with has
traditionally been modelled with a ``double exchange'' Hamiltonian, in which it
is assumed that the only relevant physics is the tendency of carrier hopping to
line up neighboring spins. We present a solution of the double exchange model,
show it is incompatible with many aspects of the resistivity data, and propose
that a strong electron-phonon interaction arising from a Jahn-Teller splitting
of the outer Mn d-level plays a crucial role.Comment: Figure available via concentional mail. Contact
[email protected]
Measurement of the local Jahn-Teller distortion in LaMnO_3.006
The atomic pair distribution function (PDF) of stoichiometric LaMnO_3 has
been measured. This has been fit with a structural model to extract the local
Jahn-Teller distortion for an ideal Mn(3+)O_6 octahedron. These results are
compared to Rietveld refinements of the same data which give the average
structure. Since the local structure is being measured in the PDF there is no
assumption of long-range orbital order and the real, local, Jahn-Teller
distortion is measured directly. We find good agreement both with published
crystallographic results and our own Rietveld refinements suggesting that in an
accurately stoichiometric material there is long range orbital order as
expected. The local Jahn-Teller distortion has 2 short, 2 medium and 2 long
bonds.Comment: 5 pages, 3 postscript figures, minor change
Two-Dimensional Molecular Patterning by Surface-Enhanced Zn-Porphyrin Coordination
In this contribution, we show how zinc-5,10,15,20-meso-tetradodecylporphyrins (Zn-TDPs) self-assemble into stable organized arrays on the surface of graphite, thus positioning their metal center at regular distances from each other, creating a molecular pattern, while retaining the possibility to coordinate additional ligands. We also demonstrate that Zn-TDPs coordinated to 3-nitropyridine display a higher tendency to be adsorbed at the surface of highly oriented pyrolytic graphite (HOPG) than noncoordinated ones. In order to investigate the two-dimensional (2D) self-assembly of coordinated Zn-TDPs, solutions with different relative concentrations of 3-nitropyridine and Zn-TDP were prepared and deposited on the surface of HOPG. STM measurements at the liquid-solid interface reveal that the ratio of coordinated Zn-TDPs over noncoordinated Zn-TDPs is higher at the n-tetradecane/HOPG interface than in n-tetradecane solution. This enhanced binding of the axial ligand at the liquid/solid interface is likely related to the fact that physisorbed Zn-TDPs are better binding sites for nitropyridines.
Double exchange-driven spin pairing at the (001) surface of manganites
The (001) surface of La_{1-x}Ca_xMnO_3 system in various magnetic orderings
is studied by first principle calculations. A general occurrence is that z^2
dangling bond charge -- which is ``invisible'' in the formal valence picture --
is promoted to the bulk gap/Fermi level region. This drives a
double-exchange-like process that serves to align the surface Mn spin with its
subsurface neighbor, regardless of the bulk magnetic order. For heavy doping,
the locally ``ferromagnetic'' coupling is very strong and the moment enhanced
by as much as 30% over the bulk value.Comment: 6 pages, 4 figure
Charge Ordering and Phase Competition in the Layered Perovskite Lasr2mn2o7
Charge-lattice fluctuations are observed in the layered perovskite manganite
LaSr2Mn2O7 by Raman spectroscopy as high as 340 K and with decreasing
temperature they become static and form a charge ordered (CO) phase below
TCO=210 K. In the static regime, superlattice reflections are observed through
neutron and x-ray diffraction with a propagation vector (h+1/4,k-1/4,l).
Crystallographic analysis of the CO state demonstrates that the degree of
charge and orbital ordering in this manganite is weaker than the charge
ordering in three dimensional perovskite manganites. A TN=170K a type-A
antiferromagnetism (AF) develops and competes with the charge ordering, that
eventually melts below T*=100K. High resolution diffraction measurements
suggest that that CO- and AF-states do not coincide within the same region in
the material but rather co-exist as separate phases. The transition to type-A
antiferromagnetism at lower temperatures is characterized by the competition
between these two phases.Comment: 9 pages, 6 figure
Pre-K-Edge Structure on Anomalous X-Ray Scattering in LaMnO3
We study the pre-K-edge structure of the resonant X-ray scattering for
forbidden reflections (anomalous scattering) in LaMnO3, using the band
calculation based on the local density approximation. We find a two-peak
structure with an intensity approximately 1/100 of that of the main peak. This
originates from a mixing of 4p states of Mn to 3d states of neighboring Mn
sites. The effect is enhanced by an interference with the tail of the main
peak. The effect of the quadrupole transition is found to be one order of
magnitude smaller than that of the dipole transition, modifying slightly the
azimuthal-angle dependence.Comment: 4 pages, 5 figures, submitted to J. Phys. Soc. Jp
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