800 research outputs found
Electronic correlations and crystal structure distortions in BaBiO3
BaBiO3 is a material where formally Bi4+ ions with the half-filled 6s-states
form the alternating set of Bi3+ and Bi5+ ions resulting in a charge ordered
insulator. The charge ordering is accompanied by the breathing distortion of
the BiO6 octahedra (extension and contraction of the Bi-O bond lengths).
Standard Density Functional Theory (DFT) calculations fail to obtain the
crystal structure instability caused by the pure breathing distortions.
Combining effects of the breathing distortions and tilting of the BiO6
octahedra allows DFT to reproduce qualitatively experimentally observed
insulator with monoclinic crystal structure but gives strongly underestimate
breathing distortion parameter and energy gap values. In the present work we
reexamine the BaBiO3 problem within the GGA+U method using a Wannier functions
basis set for the Bi 6s-band. Due to high oxidation state of bismuth in this
material the Bi 6s-symmetry Wannier function is predominantly extended
spatially on surrounding oxygen ions and hence differs strongly from a pure
atomic 6s-orbital. That is in sharp contrast to transition metal oxides (with
exclusion of high oxidation state compounds) where the major part a of d-band
Wannier function is concentrated on metal ion and a pure atomic d-orbital can
serve as a good approximation. The GGA+U calculation results agree well with
experimental data, in particular with experimental crystal structure parameters
and energy gap values. Moreover, the GGA+U method allows one to reproduce the
crystal structure instability due to the pure breathing distortions without
octahedra tilting
Wannier functions and exchange integrals: The example of LiCuO
Starting from a single band Hubbard model in the Wannier function basis, we
revisit the problem of the ligand contribution to exchange and derive explicit
formulae for the exchange integrals in metal oxide compounds in terms of atomic
parameters that can be calculated with constrained LDA and LDA+U. The analysis
is applied to the investigation of the isotropic exchange interactions of
LiCuO, a compound where the Cu-O-Cu angle of the dominant exchange
path is close to 90. Our results show that the magnetic moments are
localized in Wannier orbitals which have strong contribution from oxygen atomic
orbitals, leading to exchange integrals that considerably differ from the
estimates based on kinetic exchange only. Using LSDA+U approach, we also
perform a direct {\it ab-initio} determination of the exchange integrals
LiCuO. The results agree well with those obtained from the Wannier
function approach, a clear indication that this modelization captures the
essential physics of exchange. A comparison with experimental results is also
included, with the conclusion that a very precise determination of the Wannier
function is crucial to reach quantitative estimates.Comment: 8 pages, 8 figure
Transition state method and Wannier functions
We propose a computational scheme for materials where standard Local Density
Approximation (LDA) fails to produce a satisfactory description of excitation
energies. The method uses Slater's "transition state" approximation and Wannier
functions basis set. We define a correction to LDA functional in such a way
that its variation produces one-electron energies for Wannier functions equal
to the energies obtained in "transition state" constrained LDA calculations. In
the result eigenvalues of the proposed functional could be interpreted as
excitation energies of the system under consideration. The method was applied
to MgO, Si, NiO and BaBiO and gave an improved agreement with experimental
data of energy gap values comparing with LDA.Comment: 13 pages, 6 figures, 1 tabl
Thermodynamics of oxygen in CaMnO3-δ
The experimental data for equilibrium oxygen content were used in order to extract increments of partial molar thermodynamic functions of oxygen with changes of oxygen stoichiometry in calcium manganite CaMnO3-δ. It is shown that along with the oxygen exchange reaction, thermal excitation of Mn4+ cations plays an important role in equilibration of charged manganese species that appear in response to the loss of oxygen at heating. The interrelation of partial molar enthalpy and entropy of oxygen with electron and ion defect formation parameters is obtained in approximation of the point defect model. The nearly linear changes of oxygen partial molar enthalpy are shown to directly reflect thermally driven changes in concentration of Mn3+ cations. © Springer-Verlag Berlin Heidelberg 2013
Electron transport in CaMnO3 - δ at elevated temperatures: A mobility analysis
The drift mobility of electron charge carriers in oxygen non-stoichiometric manganite CaMnO3 - δ was calculated by combining the total electrical conductivity and oxygen non-stoichiometry data at 700-950 ° C and oxygen partial pressure varying between 10-6 and 1 atm. The carrier concentration changes with pressure and temperature were obtained with the help of the earlier-developed defect model involving reactions of oxygen exchange and thermal excitation of manganese sites. The activation energy for mobility is found to increase with oxygen non-stoichiometry. High-temperature electron transport properties of the manganite CaMnO3 - δ can be explained in terms of activated jumps of n-type small polarons in adiabatic regime. The relatively small mobility of charge carriers is explained by strong localization of polarons on manganese sites. © 2013 Springer-Verlag Berlin Heidelberg
Condensation of Silica Nanoparticles on a Phospholipid Membrane
The structure of the transient layer at the interface between air and the
aqueous solution of silica nanoparticles with the size distribution of
particles that has been determined from small-angle scattering has been studied
by the X-ray reflectometry method. The reconstructed depth profile of the
polarizability of the substance indicates the presence of a structure
consisting of several layers of nanoparticles with the thickness that is more
than twice as large as the thickness of the previously described structure. The
adsorption of 1,2-distearoyl-sn-glycero-3-phosphocholine molecules at the
hydrosol/air interface is accompanied by the condensation of anion silica
nanoparticles at the interface. This phenomenon can be qualitatively explained
by the formation of the positive surface potential due to the penetration and
accumulation of Na+ cations in the phospholipid membrane.Comment: 7 pages, 5 figure
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