Immiscibility in the Fe3O4-FeCr2O4 spinel binary

A recent thermodynamic model of mixing in spinel binaries, based on changes in cation disordering (x) between tetrahedral and octahedral sites [Am. Mineral. 68 (1983) 18, 69 (1984) 733], is investigated for applicability to the Fe₃O₄-FeCr₂O₄ system under conditions where incomplete mixing occurs. Poor agreement with measured consolute solution temperature and solvus [N. Jb. Miner. Abh. 111 (1969) 184] is attributed to neglect of: (1) ordering of magnetic moments of cations in the tetrahedral sublattice antiparallel to the moments of those in the octahedral sublattice and (2) pair-wise electron hopping between octahedral site Fe³⁺ and Fe²⁺ ions. Disordering free energies (ΔG_D), from which free energies of mixing are calculated, are modeled by

     

Immiscibility in the NiFe2O4-NiCr2O4 spinel binary

The solid solution behavior of the Ni(Fe_1−nCr_n)₂O₄ spinel binary is investigated in the temperature range 400-1200 °C. Non-ideal solution behavior, as exhibited by non-linear changes in lattice parameter with changes in n, is observed in a series of single-phase solids air-cooled from 1200 °C. Air-annealing for 1 year at 600 °C resulted in partial phase separation in a spinel binary having n=0.5. Spinel crystals grown from NiO, Fe₂O₃ and Cr₂O₃ reactants, mixed to give NiCrFeO₄, by Ostwald ripening in a molten salt solvent, exhibited single-phase stability down to about 750 °C (the estimated consolute solution temperature, T_cs). A solvus exists below T_cs. The solvus becomes increasingly asymmetric at lower temperatures and extrapolates to n values of 0.2 and 0.7 at 300 °C. The extrapolated solvus is shown to be consistent with that predicted using a primitive regular solution model in which free energies of mixing are determined entirely from changes in configurational entropy at room temperature.     

Electronic structure and chemical bonding of phosphorus-contained sulfides InPS4, TI3PS4, and Sn2P2S6

The electronic structure of phosphorus-contained sulfides InPS₄, Tl₃PS₄, and Sn₂P₂S₆ was investigated experimentally with X-ray spectroscopy and theoretically by quantum mechanical calculations. The partial densities of electron states calculated with the ab initio multiple scattering FEFF8 code correspond well to their experimental analogues—the X-ray K- and L_2,3-spectra of sulfur and phosphorus. The good agreement between theory and experiment was also achieved for K-absorption spectra of S and P in the investigated sulfides. In spite of the difference in the crystallographic structure of InPS₄, TI₃PS₄, and Sn₂P₂S₆ that influence the form of K-absorption spectra, the electronic structure of their valence bands are rather similar. This is due to the strong interaction of the P and S atoms, which are the nearest neighbors in the compounds studied. The electron densities of p- and s-states of phosphorus are shifted by about 3 eV to lower energies in comparison to the analogous electron states of sulfur. This is connected with the greater electro-negativity of sulfur, and is confirmed by the calculated electron charge transfer from P to S.     

Physical properties of the cubic spinel LiMn2O4

We have performed an ab initio study of structural, electronic, magnetic, vibrational and thermal properties of the cubic spinel LiMn₂O₄ by employing the density functional theory, the linear-response formalism, and the plane-wave pseudopotential method. An analysis of the electronic structure with the help of electronic density of states shows that the density of states at the Fermi level (N (E_F)) is found to be governed by the Mn 3d electrons with some contributions from the 2p states of O atoms. It is important to note that the contribution of Mn 3d states to N(_EF)$N\left(E_F\right)$ is as much as 85%. From our phonon calculations, we have obtained that the main contribution to phonon density of states (below 250 cm⁻¹) comes from the coupled motion of Mn and O atoms while phonon modes between 250 cm⁻¹ and 375 cm⁻¹ are characterized by the vibrations of all the three types of atoms. The contribution from Li increases rapidly at higher frequency (above 375 cm⁻¹) due to the light mass of this atom. Finally, the specific heat and the Debye temperature at 300 K are calculated to be 249.29 J/mol K and 820.80 K respectively.     

Electroresistance effect in La1−xCaxMnO3 (0<x<1) ceramics

Electroresistance (ER) effects were investigated for a full series of manganite ceramics La_1−xCa_xMnO₃ (0<x<1), synthesized by solid state reaction. The results indicate that while the ER effects are large only in the presence of electrically active, high E-field boundaries, the equilibrium or metastable electronic-magnetic states in the adjoining domains are also significant, as a large ER occurs only at x=0.51 and x=0.17; those compositions are both near a two-phase coexistence region, i.e. close to a compositional regime where equilibrium insulating/metallic phase domains and interfaces would occur spontaneously.     

First-principles study on electronic structure of Sr2Bi2O5 crystal

The electronic structure of Sr₂Bi₂O₅ is calculated by the GGA approach. Both of the valence band maximum and the conduction band minimum are located at Γ-point. This means that Sr₂Bi₂O₅ is a direct band-gap material. The wide energy-band dispersions near the valence band maximum and the conduction band minimum predict that holes and electrons generated by band gap excitation have a high mobility. The conduction band is composed of Bi 6p, Sr 4d and O 2p energy states. On the other hand, the valence band can be divided into two energy regions ranging from −9.5 to −7.9 eV (lower valence band) and from −4.13 to 0 eV (upper valence band). The former mainly consists of Bi 6s states hybridizing with O 2s and O 2p states, and the latter is mainly constructed from O 2p states strongly interacting with Bi 6s and Bi 6p states.     

Thermochemical studies on RE2O2CO3 (RE=Gd, Nd) decomposition

Thermochemistry in the decomposition of gadolinium di-oxycarbonate, Gd₂O₂CO₃(s) and neodymium di-oxycarbonate, Nd₂O₂CO₃(s) was studied over the temperature region of 774-952 K and 775-1105 K, respectively. The equilibrium properties of the decomposition reactions were obtained by tensimetric measurement of the CO₂(g) pressure over the biphasic mixture of RE₂O₂CO₃(s) and RE₂O₃(s) at different temperatures (RE=Gd, Nd) and also by thermogravimetric analysis of the decomposition temperature at different CO₂ pressures. The temperature dependence of the equilibrium pressure of CO₂ thus measured could be given by

ln p_CO2/Pa (±0.13)=−22599.1/T+35.21 (774≤T (K)≤952) for Gd₂O₂CO₃ decomposition and

ln p_CO2/Pa (±0.19)=−23824.7/T+33.14 (775≤T (K)≤1105) for Nd₂O₂CO₃ decomposition.

From the above vapor pressure expressions, the median enthalpy and entropy of the decomposition of the oxycarbonates were calculated by the second law analysis and their thermodynamic stabilities were derived. The results are discussed in the light of available thermochemical data of the compounds.     

Electronic structure and electric-field-gradients distribution in Y3Al5O12: An ab initio study

The periodic Hartree-Fock method has been applied to calculate the electronic structure of the yttrium aluminium garnet. We report on the results of the density of state calculations, the population analysis, as well as the electric-field-gradient distribution. A comparative analysis with the related structure α-Al₂O₃ was done. The calculations show that the Y₃Al₅O₁₂ crystal is more ionic than α-Al₂O₃.     

O-vacancy and surface on CeO2: A first-principles study

Atomic and electronic structures of CeO₂ (1 1 1), (1 1 0) and (1 0 0) surfaces are investigated using the first-principles density functional theory taking into account the on-site Coulomb interaction. Both the stoichiometric and O-deficient surfaces are examined in order to clarify the overall features. The CeO₂ (1 1 1) is found to be the most stable surface, followed by the (1 1 0) and (1 0 0) surfaces, consistent with experimental observations. Three surfaces exhibit different features of relaxation. Large relaxations are found at the (1 1 0) and (1 0 0) surfaces, while very small changes are observed at the (1 1 1) surface. It is found that the O-vacancy occurs more readily at the (1 1 0) surface as compared with the (1 1 1) surface. Furthermore, the formation energies of the O-vacancy in the surfaces are lower than that in the bulk. The energetically favorable O-vacancy locates in the second O-atomic layer for the (1 1 1) while at the surface layer for the (1 1 0). The excess electrons left with the removal of the O atom are distributed in the first two layers with certain (a considerable) fraction filling the Ce-4f states.     

Doping-induced spin-manipulation in complex trimer system Ca3Cu3(PO4)4: A density functional investigation

Doping induced spin-manipulation with magnetic (Ni) and non-magnetic (Mg) dopants constitutes the experimental attempts to obtain a singlet ground state system from the linear chain Heisenberg antiferromagnetic Cu-based d⁹ spin-1/2 trimer compound Ca³Cu³(PO⁴)⁴ with doublet ground state. The present study is a density-functional investigation of the effects of such doping on the spin-exchange mechanism and electronic structure of the parent compound. Site-selective doping with zero-spin dopants like Mg is proved to be more efficient than an integral spin dopant Ni in obtaining a spin-gap system with singlet ground state, as also observed in the experimental studies. Doping induced dimerized state is found to be the lowest in ground-state energy. Calculated spin exchange couplings along various possible pathways are observed to attain good agreement with earlier experimental results with suitable optimization of Coulomb repulsion (U) and exchange (J) parameters.     

Lattice dynamics of cubic SrZrO3

Using density functional perturbation theory, the optical dielectric constant, Born effective charges and phonon dispersion curves of cubic SrZrO₃ have been calculated. The obtained dispersion curves show a soft phonon branch spreading from R to M points of the cubic Brillouin zone. An analysis based on the symmetry relationships indicates that the experimentally observed low-symmetry phases of SrZrO₃ can be considered as results of the soft mode condensation at R and M points.     

Dielectric and AC conductivity behavior of BaBi2Nb2O9 ceramics

The complex dielectric and AC conductivity response of BaBi₂Nb₂O₉ relaxor ferroelectric ceramics were studied as a function of frequency (100 Hz-10 MHz) at various temperatures. The observed dielectric behavior was characterized by two types of relaxation processes which were described by the ‘universal relaxation law’. The frequency dependence of conductivity which showed a classical relaxor behavior followed the Jonscher's universal law σ(ω)=σ₀+Aωⁿ. The exponent n exhibited a minimum in the vicinity of temperatures of dielectric anomaly while the pre-factor A showed a maximum. The temperature dependence of n followed the Vogel-Fulcher relation with activation energy of about 0.14 eV.     

Oxygen non-stoichiometry and defect thermodynamics in La2Ni0.9Fe0.1O4+δ

The oxygen hyperstoichiometry of K₂NiF₄-type La₂Ni_0.9Fe_0.1O_4+δ, studied by thermogravimetric analysis and coulometric titration in the oxygen partial pressure range 6×10⁻⁵-0.7 atm at 923-1223 K, is considerably higher than that of undoped lanthanum nickelate. The p(O₂)-T-δ diagram of iron-doped lanthanum nickelate can be adequately described by introducing point-defect interaction energy in the concentration-dependent part of defect chemical potentials and accounting for the site-exclusion effects. The critical factors affecting the equilibrium oxygen incorporation process include coulombic repulsion of interstitial anions, trapping of the p-type electronic charge carriers by iron, and interaction between Fe³⁺ and holes localized on nickel cations. Due to low chemical expansion of La₂Ni_0.9Fe_0.1O_4+δ lattice, the thermodynamic functions governing oxygen intercalation, site-blocking factors and hole mobility are all independent of the defect concentrations. The predominant 3+ state of iron cations under oxidizing conditions was confirmed by the Mössbauer spectroscopy. The stability of La₂NiO₄-based phase in reducing atmospheres is essentially unaffected by doping.     

First-principles calculations of electronic, optical and elastic properties of ZnAl2S4 and ZnGa2O4

The optimized crystal structures, band structures, partial and total densities of states (DOS), dielectric functions, refractive indexes and elastic constants for ZnAl₂S₄ and ZnGa₂O₄ were calculated using the CASTEP module of Materials Studio package. Pressure effects were modeled by performing these calculations for different values of external hydrostatic pressure up to 50 GPa. Obtained dependencies of the unit cell volume on pressure were fitted by the Murnaghan equation of state, and the relative changes of different chemical bond lengths were approximated by quadratic functions of pressure. Variations of applied pressure were shown to produce considerable re-distribution of the electron densities around ions in both crystals, which is evidenced in different trends for the effective Mulliken charges of the constituting ions and changes of contour plots of the charge densities. The longitudinal and transverse sound velocities and Debye temperatures for both compounds were also estimated using the calculated elastic constants.     

High-temperature crystal structure and electronic properties of cesium niobate Cs2Nb4O11

The antiferroelectric material Cs₂Nb₄O₁₁ transforms at 165 °C from a low-temperature, antiferroelectric phase in space group Pnna to a high-temperature, paraelectric phase in space group Imma; the latter structure has been determined by single-crystal X-ray diffraction. The high-temperature lattice is comprised of niobium-centered tetrahedra and octahedra connected through shared vertices and edges; cesium atoms occupy channels afforded by the three-dimensional polyhedral network. Calculated band structures for both phases predict a bandgap of 3.1-3.2 eV, which is similar to that found experimentally through photoluminescence. The calculated band structure is also conducive to its observed photocatalytic properties.     

Band structure calculations on the layered compounds FeGa2S4 and NiGa2S4

For the compounds FeGa₂S₄ and NiGa₂S₄ band structure calculations have been performed by the ab initio plane wave pseudo-potential method. The valence charge density distribution points to an ionic type of chemical bonding between the transition metal atoms and the ligand atoms. Two models for the pseudo-potentials are used to calculate the band structures: (a) only s and p electrons and (b) also the d-shells of the transition metal atoms are included in the pseudo-potentials. The differences between these two cases of band structures are discussed. Energy gap formation peculiarities are analysed for both crystals. Zak's elementary energy band concept is demonstrated for the energy spectra of the considered crystals.     

On the mechanism of the zircon-reidite pressure induced transformation

We report first principles results of a detailed investigation directed to elucidate mechanistic aspects of the zircon-reidite phase transition in ZrSiO₄. The calculated thermodynamic boundary is located around 5 GPa, and the corresponding thermal barrier, estimated from temperatures at which the transition is observed at zero and high pressure, is 133 kJ/mol. Under a martensitic perspective, we examine two different transition pathways at the thermodynamic transition pressure. First, the direct, displacive-like, tetragonal I4₁/a energetic profile is computed using the c/a ratio as the transformation parameter, and yields a very high activation barrier (236 kJ/mol). Second, a quasi-monoclinic unit cell allows us to characterize a transition path from zircon (β=90^°) to reidite (β=114.51^°) with an activation barrier of around 80 kJ/mol at β=104^°. This energy is somewhat lower than our previous estimation and supports the reconstructive nature of the transformation at the thermodynamic transition pressure.     

Molecular dynamics simulation of phase transition in AgNO3

Structural phase transition in AgNO₃ at high temperature is simulated by molecular dynamics. The simulations are based on the potentials calculated from the Gordon-Kim modified electron-gas formalism extended to molecular ionic crystals. AgNO₃ transforms into rhombohedral structure at high temperature and the phase transition is associated with the rotations of the NO₃ ions and displacements of the NO₃ and Ag ions.     

A first-principles theoretical simulation on the electronic structures and optical absorption properties for O vacancy and Ni impurity in TiO2 photocatalysts

The band structures and optical absorption spectra of O vacancy and Ni ion doped anatase TiO₂ were successfully calculated and simulated by a plane wave pseudopotential method based on density functional theory (DFT). From the calculated results, a phenomenon of “impurity compensation” was found: the lower formation energy for O vacancy than Ni impurity indicated that introducing the intrinsic defect of O vacancy into Ni ion doped TiO₂ sample was very possible; the positive binding energy for the combination of O vacancy and Ni impurity indicated that two defects were apt to bind to each other; While Ni impurity produced the donor levels in the forbidden band of TiO₂, Ni impurity with O vacancy produced the acceptor levels upon which the excitation led to the photogenerated electrons with high energy and transferability. The combination of absorption spectra for O vacancy and Ni impurity with O vacancy models could reproduce the experimental measurement very well.     

Pressure effect on the electronic and optical properties of the alkali antimonide semiconductors Cs3Sb, KCs2Sb, CsK2Sb and K3Sb: Ab initio study

We present first principles calculations of the effect of pressure on the electronic and optical properties of the alkali antimonides semiconductors K₃Sb, K₂CsSb, KCs₂Sb and Cs₃Sb by means of the full-potential linearized augmented plane wave method within the generalized gradient approximation. The band gap variation is not linear. The crossover pressure values are determined for K₃Sb and K₂CsSb. Under pressure the structures in the optical spectra shift towards higher energies for K₃Sb and KCs₂Sb whereas the threshold energy is lowered for K₂CsSb and Cs₃Sb. The electronic dielectric constant decreases with pressure for K₃Sb while it increases for the other three compounds. Our results indicate that the absorption becomes strong in the UV region for KCs₂Sb and Cs₃Sb.