Quantum-chemical simulation of N-doped Co3O4

Calculations were performed using the DFT method as implemented in the computer code VASP 5.4[1]. Core electrons were substituted with the US potentials with the PAW method [2]. Exchange-correlation described by the PBE functional [3]. The Hubbard correction U-J=3eV [4] was applied to d-electrons of Cotet as well as Cooct atoms [5]. For defects modeling cubic 56-atom supercell model has been used. For Brillouine zone [6] was sampled with the 2x2x2 Monkhorst- Pack scheme

First principles calculations of the atomic and electronic structure of F centers in bulk and on the (001) surface of SrTiO3

The atomic and electronic structure, formation energy, and the energy barriers for migration have been calculated for the neutral O vacancy point defect F center in cubic SrTiO3 employing various implementations of density functional theory DFT. Both bulk and TiO2-terminated 001 surface F centers have been considered. Supercells of different shapes containing up to 320 atoms have been employed. The limit of an isolated single oxygen vacancy in the bulk corresponds to a 270-atom supercell, in contrast to commonly used supercells containing 40–80 atoms. Calculations carried out with the hybrid B3PW functional show that the F center level approaches the conduction band bottom to within 0.5 eV, as the supercell size increases up to 320 atoms. The analysis of the electronic density maps indicates, however, that this remains a small-radius center with the two electrons left by the missing O ion being redistributed mainly between the vacancy and the 3d z2 atomic orbitals of the two nearest Ti ions. As for the dynamical properties, the calculated migration energy barrier in the low oxygen depletion regime is predicted to be 0.4 eV. In contrast, the surface F center exhibits a more delocalized character, which leads to significantly reduced ionization and migration energies. Results obtained are compared with available experimental data

Comparative density-functional LCAO and plane-wave calculations of LaMnO3 surfaces

We compare two approaches to the atomic, electronic, and magnetic structures of LaMnO3 bulk and the (001), (110) surfaces—hybrid B3PW with optimized LCAO basis set (CRYSTAL-2003 code) and GGA-PW91 with plane-wave basis set (VASP 4.6 code). Combining our calculations with those available in the literature, we demonstrate that combination of nonlocal exchange and correlation used in hybrid functionals allows to reproduce the experimental magnetic coupling constants Jab and Jc as well as the optical gap. Surface calculations performed by both methods using slab models show that the antiferromagnetic (AF) and ferromagnetic (FM) (001) surfaces have lower surface energies than the FM (110) surface. Both the (001) and (110) surfaces reveal considerable atomic relaxations, up to the fourth plane from the surface, which reduce the surface energy by about a factor of 2, being typically one order of magnitude larger than the energy difference between different magnetic structures. The calculated (Mulliken and Bader) effective atomic charges and the electron density maps indicate a considerable reduction of the Mn and O atom ionicity on the surface

Quantum-chemical simulation of N-doped Co3O4

Calculations were performed using the DFT method as implemented in the computer code VASP 5.4[1]. Core electrons were substituted with the US potentials with the PAW method [2]. Exchange-correlation described by the PBE functional [3]. The Hubbard correction U-J=3eV [4] was applied to d-electrons of Cotet as well as Cooct atoms [5]. For defects modeling cubic 56-atom supercell model has been used. For Brillouine zone [6] was sampled with the 2x2x2 Monkhorst- Pack scheme

Interaction of carbon with microstructural defects in a W-Re matrix: An ab initio assessment

The interaction of carbon atoms with point defects and the core of edge and screw dislocations with Burgers vector a0/2⟨111⟩ in W and a W-Re matrix is studied by means of ab initio calculations. The structure and energetics of the ground-state atomic configurations are presented and rationalized. It is found that di-vacancies, which are thermally unstable in pure W according to the state-of-the-art ab initio calculations, can nucleate at C and Re-C complexes, which fill the gap in the explanation of the emergence of nanovoids observed experimentally under irradiation. Also, on the basis of the recent experimental evidence and our calculations, the temperature ranges for the manifestation of the yield drop phenomenon, which is related to the obstruction of dislocation motion due to their decoration by impurities such as carbon, are revealed

First principles calculations of the atomic and electronic structure of F centers in bulk and on the (001) surface of SrTiO3

The atomic and electronic structure, formation energy, and the energy barriers for migration have been calculated for the neutral O vacancy point defect F center in cubic SrTiO3 employing various implementations of density functional theory DFT. Both bulk and TiO2-terminated 001 surface F centers have been considered. Supercells of different shapes containing up to 320 atoms have been employed. The limit of an isolated single oxygen vacancy in the bulk corresponds to a 270-atom supercell, in contrast to commonly used supercells containing 40–80 atoms. Calculations carried out with the hybrid B3PW functional show that the F center level approaches the conduction band bottom to within 0.5 eV, as the supercell size increases up to 320 atoms. The analysis of the electronic density maps indicates, however, that this remains a small-radius center with the two electrons left by the missing O ion being redistributed mainly between the vacancy and the 3d z2 atomic orbitals of the two nearest Ti ions. As for the dynamical properties, the calculated migration energy barrier in the low oxygen depletion regime is predicted to be 0.4 eV. In contrast, the surface F center exhibits a more delocalized character, which leads to significantly reduced ionization and migration energies. Results obtained are compared with available experimental data