21 research outputs found
Semiempirical Hartree-Fock calculations for KNbO3
In applying the semiempirical intermediate neglect of differential overlap
(INDO) method based on the Hartree-Fock formalism to a cubic perovskite-based
ferroelectric material KNbO3, it was demonstrated that the accuracy of the
method is sufficient for adequately describing the small energy differences
related to the ferroelectric instability. The choice of INDO parameters has
been done for a system containing Nb. Based on the parametrization proposed,
the electronic structure, equilibrium ground state structure of the
orthorhombic and rhombohedral phases, and Gamma-TO phonon frequencies in cubic
and rhombohedral phases of KNbO3 were calculated and found to be in good
agreement with the experimental data and with the first-principles calculations
available.Comment: 7 pages, 2 Postscript figures, uses psfig.tex. To be published in
Phys.Rev.B 54, No.4 (1996
Vacancy ordering and electronic structure of gamma-Fe2O3 (maghemite): a theoretical investigation
The crystal structure of the iron oxide gamma-Fe2O3 is usually reported in
either the cubic system (space group P4332) with partial Fe vacancy disorder or
in the tetragonal system (space group P41212) with full site ordering and
c/a\approx 3. Using a supercell of the cubic structure, we obtain the spectrum
of energies of all the ordered configurations which contribute to the partially
disordered P4332 cubic structure. Our results show that the configuration with
space group P41212 is indeed much more stable than the others, and that this
stability arises from a favourable electrostatic contribution, as this
configuration exhibits the maximum possible homogeneity in the distribution of
iron cations and vacancies. Maghemite is therefore expected to be fully ordered
in equilibrium, and deviations from this behaviour should be associated with
metastable growth, extended anti-site defects and surface effects in the case
of small nanoparticles. The confirmation of the ordered tetragonal structure
allows us to investigate the electronic structure of the material using density
functional theory (DFT) calculations. The inclusion of a Hubbard (DFT+U)
correction allows the calculation of a band gap in good agreement with
experiment. The value of the gap is dependent on the electron spin, which is
the basis for the spin-filtering properties of maghemite.Comment: 19 pages, 2 tables, 5 figures. To appear in the Journal of Physics -
Condensed Matter (2010)
Electronic structure of a neutral oxygen vacancy in SrTiO3
The electronic structure of an isolated oxygen vacancy in SrTiO3 has been investigated with a variety of ab initio quantum mechanical approaches. In particular we compared pure density functional theory (DFT) approaches with the Hartree-Fock method, and with hybrid methods where the exchange term is treated in a mixed way. Both local cluster models and periodic calculations with large supercells containing up to 80 atoms have been performed. Both diamagnetic (singlet state) and paramagnetic (triplet state) solutions have been considered. We found that the formation of an O vacancy is accompanied by the transfer of two electrons to the 3d(z2) orbitals of the two Ti atoms along the Ti-Vac-Ti axis. The two electrons are spin coupled and the ground state is diamagnetic. New states associated with the defect center appear in the gap just below the conduction band edge. The formation energy computed with respect to an isolated oxygen atom in the triplet state is 9.4 eV
Electronic structure of a neutral oxygen vacancy in SrTiO3
The electronic structure of an isolated oxygen vacancy in SrTiO3 has been investigated with a variety of ab initio quantum mechanical approaches. In particular we compared pure density functional theory (DFT) approaches with the Hartree-Fock method, and with hybrid methods where the exchange term is treated in a mixed way. Both local cluster models and periodic calculations with large supercells containing up to 80 atoms have been performed. Both diamagnetic (singlet state) and paramagnetic (triplet state) solutions have been considered. We found that the formation of an O vacancy is accompanied by the transfer of two electrons to the 3d(z2) orbitals of the two Ti atoms along the Ti-Vac-Ti axis. The two electrons are spin coupled and the ground state is diamagnetic. New states associated with the defect center appear in the gap just below the conduction band edge. The formation energy computed with respect to an isolated oxygen atom in the triplet state is 9.4 eV