Structure instability of A2Al2B2O7 (A=K, Na) crystals

A theoretical study on the stabilities of the crystal structures of K₂Al₂B₂O₇ (KABO) and Na₂Al₂B₂O₇ (NABO) has been carried out using density functional theory with generalized-gradient corrections. All structures have been optimized by minimizing the total energies with respect to lattice constants and to the atomic coordinates within the unit cell. In the case of KABO, the structure with space group P321 always takes energy advantage over the whole volume range studied, whereas on both volume expansion and contraction, the original NABO structure becomes unstable, taking a structure transition from its space group to the P321 space group of KABO structure. The theoretical predictions were well realized in the experimental results on the structure changes of the (K_1−xNa_x)₂Al₂B₂O₇ solid solution system.     

Crystal-chemistry from XPS analysis of carbide-derived Mn+1AXn (n=1) nano-laminate compounds

The M_n+1AX_n layered carbide/nitride-derived phases, where M is an early transition metal, A is an A-group element and X is N or C, have an unusual combination of mechanical, electrical and thermal properties. The surface and crystal-chemistries of several recently synthesized n=1 members have been investigated by X-ray photoelectron spectroscopy. The results show that the constituent species are characterized by low binding energies, sometimes exceptionally so. The C 1s energies are in the lower end of the range for carbides, at 281.1-282.0 eV. The M-species—Ti, V, Nb and Hf—have binding energies at or below those corresponding to the elemental metallic state. The binding energies of the A-species in apparent planar coordination—In, Ge, As and Al—are quite exceptional, being 0.5-2 eV below those corresponding to the elemental state. Those results suggest that screening of the A-group species is derived from out-of-plane interactions, while the XPS signatures of the species associated with the MX blocks are reminiscent of those obtained from the relevant carbide phases.     

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.     

Topological analysis of real space properties for the solid-state full-potential APW DFT method

For the solid-state density functional program Elk a module was developed that enables to interface the crystal orbitals data into the DGrid package. Within DGrid the real-space electronic properties, like the electron density and its gradient or Laplacian, kinetic energy density, electron localizability indicator, etc., are computed. The properties can be searched for critical points as well as for the interconnection lines between them. Additionally, the basins can be evaluated and the property integrals can be calculated. The results of topological analysis for fcc Al, MgB₂, CaTiO₃, and urea molecular crystal are discussed and compared with the experimental data. The role of certain computation parameters of (L)APW method is also analyzed.     

Ab initio band structure calculations of the low-temperature phases of Ag2Se, Ag2Te and Ag3AuSe2

Ab initio band structure calculations were performed for the low-temperature modifications of the silver chalcogenides β-Ag₂Se, β-Ag₂Te and the ternary compound β-Ag₃AuSe₂ by the local spherical wave (LSW) method. Coordinates of the atoms of β-Ag₂Se and β-Ag₃AuSe₂ were obtained from refinements using X-ray powder data. The structures are characterized by three, four and five coordinations of silver by the chalcogen, a linear coordination of gold by Se, and by metal-metal distances only slightly larger than in the metals. The band structure calculations show that β-Ag₃AuSe₂ is a semiconductor, while β-Ag₂Se and β-Ag₂Te are semimetals with an overlap of about 0.1-0.2 eV. The Ag 4d and Au 5d states are strongly hybridized with the chalcogen p states all over the valence bands. β-Ag₂Se and β-Ag₂Te have a very low DOS in the energy range from about −0.1 to +0.5 eV. The calculated effective mass β-Ag₂Se is about 0.1-0.3 m_e for electrons and 0.75 m_e for holes, respectively.     

Position and momentum densities. Complementarity at work: refining a quantum model from different data sets

Although Bragg and Compton scattering are well-established techniques, only very few attempts to simultaneously combine information originating from these two experiments have been made so far. This remark also holds for Bragg neutron magnetic combined with X-ray scattering. We propose a quite general procedure to refine a quantum model from different data sets using basic Bayesian probability theory. As an illustration, a qualitative preliminary study to extract chemical information such as charge transfer in ionic-covalent compounds is reported.     

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.     

Electrostatic potential and interaction energies of molecular entities occluded in the AlPO4-15 molecular sieve: determination from X-ray charge density analysis

Electrostatic interaction energies of water molecules, hydroxyl and ammonium ions occluded in AlPO₄-15 molecular sieve are estimated from the modeling of the experimental X-ray charge density by numerical integration using a partitioning of the density based on multipolar pseudo-atoms.     

On the nature of the SO4/Ag(111) and SO4/Au(111) surface bonding

The nature of sulfate-Ag(111) and sulfate-Au(111) surface bonding has been investigated at the SCF + MP2 level of theory. Convergence of binding energy with cluster size is investigated and, unlike neutral adsorbates, large clusters are required in order to obtain reliable binding energies. In the most stable adsorption mode, sulfate binds to the surface via three oxygen atoms (C_3v symmetry) with a binding energy of 159.3 kcal/mol on Ag(111) and 143.9 kcal/mol on Au(111). The geometry of adsorbed sulfate was optimized at the SCF level. While the bond length between sulfur and the oxygens coordinated to the surface increases, the sulfur-uncoordinated oxygen bond length decreases. This weakening and strengthening of the bonds, respectively, is consistent with bond order conservation in adsorbates on metal surfaces. Although a charge transfer of 0.4 electrons towards the metal is observed, the adsorbate remains very much sulfate-like. The molecular orbital analysis indicates that there is also some charge back-donation towards unoccupied orbitals of sulfate. This results in an increased electron density around sulfur as revealed in the electron density difference maps. Analysis of the Laplacian of the charge density of free sulfate provides a suitable framework to understand the nature of the different charge transfer processes and allows us to establish some similarities with the CO- and SO₂-metal bondings.     

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.     

Dielectric properties and magnetoelectric effect of (x)NiFe2O4+(1−x)Ba0.8Sr0.2TiO3 composites

Magnetoelectric composites of NiFe₂O₄ and Ba_0.8Sr_0.2TiO₃ were prepared using conventional double-sintering ceramic method. The phase formation of magnetoelectric composites was confirmed by XRD technique. Variation of dielectric constant and loss tangent at room temperature with frequency in the range 100 Hz-1 MHz has been studied. Also the variation of dielectric constant and loss tangent with temperature and composition at fixed frequencies of 1 kHz, 10 kHz, 100 kHz and 1 MHz is reported. The static value of the magnetoelectric conversion factor was measured as a function of intensity of the magnetic field. The ME voltage coefficient of about 430 μV/cm Oe was observed for 15% NiFe₂O₄+85% Ba_0.8Sr_0.2TiO₃ composite. All the samples show linear variation of magnetoelectric conversion in the presence of static magnetic field.     

Structural and electrical impedance study of Pb(Sr1/3Nb2/3)O3

Lead-based ceramic Pb(Sr_1/3Nb_2/3)O₃ (PSN) is prepared by the columbite precursor method and structurally characterized using XRD. The X-ray diffraction shows a perovskite structure with cubic pyrochlore phase. Detailed studies of ε′ and ε″ of the compounds show that the compounds exhibit dielectric anomaly. Impedance spectroscopy is used to characterize the electrical behaviour. Results indicate that the relaxation mechanism of the material is temperature dependent and has dominant bulk contribution in different temperature ranges. Modulus spectroscopic data were used to gain an insight into the electrical properties of the samples and with a view to observe the relaxations in them. Frequency dependence dielectric permittivity shows typical Debye-type dielectric dispersion. Temperature-dependent DC resistivity shows that resistance decreases with the increase in temperature and follows Arrhenius behaviour in different temperature regions.     

Structural stability and electronic properties of Co2N, Rh2N and Ir2N

The structural stability and electronic properties of Co₂N, Rh₂N and Ir₂N were studied by using the first principles based on the density functional theory. Two structures were considered for each nitride, orthorhombic Pnnm phase and cubic Pa3¯ phase. The results show that they are all mechanically stable. Co₂N in both phases are thermodynamically stable due to the negative formation energy, while the remaining two compounds are thermodynamically unstable. The calculated properties show that they are all metallic and non-magnetic. Ir₂N at Pnnm phase is a potentially hard material. The bonding behavior is analyzed.     

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.     

Electronic structure,optical dielectric constant and born effective charge of EuAlO3

EuAlO₃ (EAO) is synthesized by the sol–gel process. The Rietveld refinement of the X-ray diffraction data shows that the material has orthorhombic structure with Pbnm space group. The density functional theory calculations are initiated with the experimental lattice parameters. The full potential linearized augmented plane wave method and projector augmented wave method are used to investigate the ground state properties of EAO. An indirect band gap of 1.8 eV is observed with the valence band maximum at the Γ point and the conduction band minimum at the R point. The X-ray photoemission spectroscopy (XPS) spectra of EAO are obtained in the energy window of 0–1000 eV. Using the electronic density of states, the valence band (VB) spectrum of EAO is generated and compared with the observed VB-XPS spectrum. The optical dielectric constant and the refractive index of the material are calculated for the photon energy radiation. The optical properties show a considerable anisotropy in the material. The Born effective charge of various elements and the dielectric tensor of EAO have been calculated.     

Gas-sensing properties of perovskite La0.875Ba0.125FeO3 nanocrystalline powders

La_0.875Ba_0.125FeO₃ nanocrystalline powders have been prepared by a sol-gel method. The structure, conductance and gas-sensing properties were investigated. La_0.875Ba_0.125FeO₃ crystallizes as a perovskite phase with the orthorhombic structure. The La_0.875Ba_0.125FeO₃ based sensor shows good sensitivity and selectivity to alcohol gas. The highest sensitivity to 500 ppm alcohol gas reached was 58 at 170 °C. The adsorption of O₂ on the La_0.875Ba_0.125FeO₃ (0 1 0) surface was studied with the first-principles calculation based on the density functional theory. The results show that the surface states are near the Fermi energy level and that the Fe ion plays an important role in the process of oxygen adsorption, which affects the gas-sensing properties.     

Synthesis and characterization of Co7(OH)12(C2H4S2O6)(H2O)2—a single crystal structural study of a ferrimagnetic layered cobalt hydroxide

A novel layered hydrotalcite-like material, Co₇(H₂O)₂(OH)₁₂(C₂H₄S₂O₆), has been prepared hydrothermally and the structure determined using single crystal X-ray diffraction (a=6.2752(19) Å, b=8.361(3) Å, c=9.642(3) Å, α=96.613(5)°, β=98.230(5)°, γ=100.673(5)°, R1=0.0551). The structure consists of brucite-like sheets where 1/6 of the octahedral sites are replaced by two tetrahedrally coordinated Co(II) above and below the plane of the layer. Ethanedisulfonate anions occupy the space between layers and provide charge balance for the positively charged layers. The compound is ferrimagnetic, with a Curie temperature of 33 K, Curie-Weiss θ of −31 K, and a coercive field of 881 Oe at 5 K.     

Density functional theory study of AunMn(n=1-8) clusters

Equilibrium geometries, relative stabilities, and magnetic properties of small Au_nMn (n=1-8) clusters have been investigated using density functional theory at the PW91P86 level. It is found that Mn atoms in the ground state Au_nMn isomers tend to occupy the most highly coordinated position and the lowest energy structure of Au_nMn clusters with even n is similar to that of pure Au_n+1 clusters, except for n=2. The substitution of Au atom in Au_n+1 cluster by a Mn atom improves the stability of the host clusters. Maximum peaks are observed for Au_nMn clusters at n=2, 4 on the size dependence of second-order energy differences and fragmentation energies, implying that the two clusters possess relatively higher stability. The HOMO-LUMO energy gaps of the ground state Au_nMn clusters show a pronounced odd-even oscillation with the number of Au atoms, and the energy gap of Au₂Mn cluster is the biggest among all the clusters. The magnetism calculations indicate that the total magnetic moment of Au_nMn cluster, which has a very large magnetic moment in comparison to the pure Au_n+1 cluster, is mainly localized on Mn atom.     

Reformulation of density functional theory for N-representable densities and the resolution of the v-representability problem

Density functional theory for the case of general, N-representable densities is reformulated in terms of density functional derivatives of expectation values of operators evaluated with wave functions leading to a density, making no reference to the concept of potential. The developments provide proof of existence of a mathematical procedure that determines whether a density is v-representable and in the case of an affirmative answer determines the potential (within an additive constant) as a derivative with respect to the density of a constrained search functional. It also establishes the existence of an energy functional of the density that, for v-representable densities, assumes its minimum value at the density describing the ground state of an interacting many-particle system. The theorems of Hohenberg and Kohn emerge as special cases of the formalism. Numerical results for one-dimensional non-interacting systems illustrate the formalism. Some direct formal and practical implications of the present reformulation of DFT are also discussed.     

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.