Electronic Structure,Optical Properties,and Pressure Behavior of the CdB<Subscript>4</Subscript>O<Subscript>7</Subscript> and HgB<Subscript>4</Subscript>O<Subscript>7</Subscript> Compounds

Ab initio calculations of the structural, electronic, and optical properties of the CdB₄O₇ and HgB₄O₇ tetraborate compounds in three structural modifications with the Pbca, Cmcm, and Pmn2₁ symmetry have been performed in the framework of the density functional theory using the VASP package. The calculations of the electronic band structure showed that these compounds in all the investigated modifications are dielectrics with a band gap of 2–4 eV. The calculation of the structural properties of the tetraborates under pressure showed that the phase transition between the Pbca and Pmn2₁ structures in cadmium and mercury tetraborates occurs under pressures of 4.8 and 4.7 GPa, respectively.     

Electronic and magnetic properties of Fe<Subscript>2</Subscript>SiC

The electronic structure and magnetic properties of Fe₂SiC compound have been studiedusing the framework of an all-electron full-potential linearized augmented-plane wave(FP-LAPW) method within the local density (LSDA) and + U corrected(LSDA + U)approximations. An antiferromagnetic spin ordering of Fe atoms is shown to be the groundstate for this compound. From the electronic band structures and density of states (DOS),Fe₂SiC has ametallic character and from the analysis of the site and momentum projected densities, itis deduced that the bonding is achieved through hybridization of Fe-3d with C-2p states andFe-3d withSi-3pstates. It is also pointed out that the Fe-C bonding is more covalent than Fe-Si. In theFM phase, the spin polarized calculations indicate that the total magnetic moment ofFe₂SiC increasesfrom 0.41 to 4.33μ _B when the Hubbard U parameter for iron isconsidered.     

Energy band structure and X-ray spectra of phenakite Be<Subscript>2</Subscript>SiO<Subscript>4</Subscript>

The electronic structure of crystalline phenakite Be₂SiO₄ is investigated using x-ray emission spectroscopy (XES) (Be K _α XES, Si L _{2, 3} XES, O K _α XES) and x-ray absorption spectroscopy (XAS) (Be 1s XAS, Si 2p XAS, O 1s XAS). The energy band structure is calculated by the ab initio full-potential linearized augmented-plane-wave (FLAPW) method. The total and partial densities of states and the dispersion curves for the Be₂SiO₄ compound are presented. It is shown that the top of the valence band and the bottom of the conduction band of the Be₂SiO₄ compound are predominantly formed by the oxygen 2p states. According to the results obtained, the electron transition with the lowest energy supposedly can occur at the center of the Brillouin zone. The effective masses of electrons (0.5m _e ) and holes (3.0m _e ) for the Be₂SiO₄) compound are estimated.     

Pressure-induced superconductivity and structural transitions in Ba(Fe<Subscript>0.9</Subscript>Ru<Subscript>0.1</Subscript>)<Subscript>2</Subscript>As<Subscript>2</Subscript>

Electrical transport and structural characterizations of isoelectronically substituted Ba(Fe_0.9Ru_0.1)₂As₂ have been performed as a function of pressure up to ～ 30 GPa and temperature down to ～ 10 K using designer diamond anvil cell. Similar to undoped members of the AFe₂As₂ (A = Ca, Sr, Ba) family, Ba(Fe_0.9Ru_0.1)₂As₂ shows anomalous a-lattice parameter expansion with increasing pressure and a concurrent ThCr₂Si₂ type isostructural (I4/mmm) phase transition from tetragonal (T) phase to a collapsed tetragonal (cT) phase occurring between 12 and 17 GPa where the a is maximum. Above 17 GPa, the material remains in the cT phase up to 30 GPa at 200 K. The resistance measurements show evidence of pressure-induced zero resistance that may be indicative of high-temperature superconductivity for pressures above 3.9 GPa. The onset of the resistive transition temperature decreases gradually with increasing pressure before completely disappearing for pressures above ～ 10.6 GPa near the T-cT transition. We have determined the crystal structure of the high-T _c phase of Ru-doped BaFe₂As₂ to remain as tetragonal (I4/mmm) by analyzing the X-ray diffraction pattern obtained at 10 K and 9.7 ± 0.7 GPa, as opposed to inferring the structural transition from electrical resistance measurement, as in a previous report [S.K. Kim, M.S. Torikachvili, E. Colombier, A. Thaler, S.L. Bud’ko, P.C. Canfield, Phys. Rev. B 84, 134525 (2011)].     

Pressure-induced structural transformations,orbital order and antiferromagnetism in La<Subscript>0.75</Subscript>Ca<Subscript>0.25</Subscript>MnO<Subscript>3</Subscript>

High pressure evolution of structural, vibrational and magnetic properties of La_0.75Ca_0.25MnO₃ was studied by means of X-ray diffraction and Raman spectroscopy up to 39 GPa, and neutron diffraction up to 7.5 GPa. The stability of different magnetic ground states, orbital configurations and structural modifications were investigated by LDA + U electronic structure calculations. A change of octahedral tilts corresponding to the transformation of orthorhombic crystal structure from the Pnma symmetry to the Immaone occurs above P ~ 6 GPa. At the same time, the evolution of the orthorhombic lattice distortion evidences an appearance of the e _g d _{x² ? z²} orbital polarization at high pressures. The magnetic order in La_0.75Ca_0.25MnO₃ undergoes a continuous transition from the ferromagnetic 3D metallic (FM) ground state to the A-type antiferromagnetic (AFM) state of assumedly 2D pseudo-metallic character under pressure, that starts at about 1 GPa and extends possibly to 20–30 GPa.     

Electronic structures of ternary iron arsenides <Emphasis Type="Italic">A</Emphasis>Fe<Subscript>2</Subscript>As<Subscript>2</Subscript> (<Emphasis Type="Italic">A</Emphasis> = Ba,Ca, or Sr)

We have studied the electronic and magnetic structures of the ternary iron arsenides AFe₂As₂ (A = Ba, Ca, or Sr) using the first-principles density functional theory. The ground states of these compounds are in a collinear antiferromagnetic order, resulting from the interplay between the nearest and the next-nearest neighbor superexchange antiferromagnetic interactions bridged by As 4p orbitals. The correction from the spin-orbit interaction to the electronic band structure is given. The pressure can reduce dramatically the magnetic moment and diminish the collinear antiferromagnetic order. Based on the calculations, we propose that the low energy dynamics of these materials can be described effectively by a t-J _H -J ₁-J ₂-type model [2008, arXiv: 0806.3526v2].     

Mott Transition in GdMnO<Subscript>3</Subscript>: an Ab Initio Study

Orthorhombic GdMnO₃ is studied using density functional theory considering the pseudo-potential plane-wave method within local-spin-density approximation, LSDA. The electronic band structure and density of states, for several hydrostatic pressures, are studied. The Mott transition was observed at 60 GPa. Calculated lattice parameters are close to the experimental measurements, and some indirect band gaps (S→Γ) were obtained within the LSDA level of calculation, between the occupied O-2p and unoccupied Gd-4f states. The variation of the gap reduces with increasing pressure, being well fitted to a quadratic function.     

Pressure-induced antiferromagnetism in La<Subscript>0.75</Subscript>Ca<Subscript>0.25</Subscript>MnO<Subscript>3</Subscript> manganite

The crystal and magnetic structures of La_0.75Ca_0.25MnO₃ manganite are studied under high pressures up to 4.5 GPa in the temperature range 12–300 K by the neutron diffraction method. At normal pressure and temperature T _C = 240 K, a ferromagnetic state is formed in La_0.75Ca_0.25MnO₃. At high pressures P ≥ 1.5 GPa and at temperatures T < T _N ≈ 150 K, a new A-type antiferromagnetic state appears. A further increase in pressure leads to an increase in the volume fraction of the antiferromagnetic phase, which coexists with the initial ferromagnetic phase. The effect of high pressure causes a considerable increase in T _C with the slope dT _C /dP ≈ 12 K/GPa. Calculations performed in the framework of the double exchange model with allowance for the electron-phonon interaction make it possible to explain this pressure dependence of T _C on the basis of experimental data.     

The electronic structure and optical and magnetooptical properties of the CaCo<Subscript>2</Subscript> compound synthesized at a high pressure: Experiment and theory

The optical properties (the real ε₁ and imaginary ε₂ permittivity parts, optical conductivity σ, and reflectivity R) of the new ferromagnetic compound CaCo₂ in the Laves cubic phase (C15) synthesized at a pressure of 8.0 GPa were studied over the spectral range ?ω = 0.2–9 eV. The field and spectral (?ω = 0.5–4.2 eV) dependences of the equatorial Kerr effect were determined. The electronic structure and optical characteristics of CaCo₂ were calculated using the electron density functional theory by the linearized augmented-plane-wave method. The main band structure parameters of the compound were determined. The experimental and theoretical σ(ω) and R(ω) dependences were in satisfactory agreement with each other. The formation of the main absorption bands was found to be caused by the (p,d → d,p)-type electronic transitions related to the cobalt and calcium atoms. The exchange splitting of the 3d band of CaCo₂ was estimated, 2Δ_exc ～ (1–1.3) eV.     

Transport and optical properties of iron borate FeBO<Subscript>3</Subscript> under high pressures

The optical absorption spectra of iron borate FeBO₃ were measured in diamond anvil cells at high pressures up to P=82 GPa. The electronic transition with an abrupt jump in the absorption edge from ～3 to 0.8 eV was observed at P≈46 GPa. The resistance and its temperature dependence were directly measured for FeBO₃ at high pressures up to 140 GPa. It was established that the electronic transition at P≈46 GPa was accompanied by the insulator-semiconductor transition. In the high-pressure phase, the thermoactivation gap decreases smoothly at 46<P<140 GPa approximately from 0.55 to 0.2 eV following the linear law. The extrapolated value of the pressure at which the sample becomes fully metallic is equal to about 210 GPa.     

Band structure and the magnetic and elastic properties of SrFeO<Subscript>3</Subscript> and LaFeO<Subscript>3</Subscript> perovskites

The band structure and the magnetic and elastic characteristics of SrFeO₃ and LaFeO₃ perovskites with ferromagnetic and antiferromagnetic collinear spin configurations (of the A, C, and G types) are investigated using the ab initio pseudopotential method (the VASP program package) with the inclusion of the single-site Coulomb correlations (the LSDA + U formalism). It is shown that, in the pressure range 0–50 GPa, the most stable states are the ferromagnetic metal state for the SrFeO₃ compound and the antiferromagnetic insulator state of the G type for the LaFeO₃ compound.     

Magnetic ordering in Fe<Subscript>1.087</Subscript>Te under pressure

The crystal and magnetic structures of Fe_1.087Te have been studied by neutron powder diffraction in the temperature range from 1.7 to 80 K at pressures of  ≈0.4 and ≈1.2 GPa. No symmetry change of the tetragonal paramagnetic ambient pressure phase (space group P4/nmm) was observed for temperatures above 60 K and pressures up to  ≈1.2 GPa. A novel pressure-induced phase of Fe_1.087Te having orthorhombic symmetry (space group Pmmn) and incommensurate antiferromagneticbicollinear order was observed in the temperature range from 50 to 60 K at  ≈1.2 GPa. The known monoclinic ambient pressure phase of Fe_1.087Te (space group P2 ₁/n) with commensurate antiferromagnetic order was found to be stable up to at least  ≈1.2 GPa at low temperature.     

Phase transition with suppression of magnetism in BiFeO<Subscript>3</Subscript> at high pressure

The magnetic behavior of a Bi⁵⁷FeO₃ powdered sample was studied at high pressures by the method of nuclear forward scattering (NFS) of synchrotron radiation. The NFS spectra from ⁵⁷Fe nuclei were recorded at room temperature under high pressures up to 61.4 GPa, which were created in a diamond anvil cell. In the pressure interval 0 < P < 47 GPa, the magnetic hyperfine field H^Fe at the ⁵⁷Fe nuclei increased reaching a value of ～52.5 T at 30 GPa, and then it slightly decreased to ～49.6 T at P = 47 GPa. As the pressure was increased further, the field H^Fe abruptly dropped to zero testifying a transition from the antiferromagnetic to a nonmagnetic state (magnetic collapse). In the pressure interval 47 < P < 61.4 GPa, the value of H^Fe remained zero. The field H^Fe recovered to the low-pressure values during decompression.     

Synthesis and properties of high-pressure phase [Er<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>3</Subscript>](V<Subscript>4</Subscript>)O<Subscript>12</Subscript>

A new perovskite-like compound Er_0.73Cu₃V₄O₁₂ (space group Im \(\bar 3\), Z = 2, a = 7.266 Å) has been synthesized barothermally (P = 8.0 GPa, t = 1000°C). Its electrical and magnetic properties have been studied. It is found that the temperature dependence of the electrical conductivity (in the range 78–300 K) has of semiconductor type. The behavior of the impedance and admittance has been analyzed at 290 K and frequencies of 200 Hz to 200 kHz under atmospheric pressure and at high (15–42 GPa) pressures.     

Electronic structure and energies of interatomic bonds in the TiSi<Subscript>2</Subscript> compound with a <Emphasis Type="Italic">C</Emphasis>49 crystal structure

Full-electron calculations of the electronic structure of the TiSi₂ compound in the structural modification C49 are performed using the augmented-plane-wave method. The total energy, the electronic band structure, and the density of states are calculated for an extended translational unit cell Ti₄Si₈, which is formed during the growth of a silicon nanowire on a p-Si substrate. Calculations are also carried out for two orthorhombic unit cells of the nonstoichiometric compositions Ti₃Si₉ and Ti₅Si₇. The energies of the interatomic bonds are determined to be E _Si-Si = 1.8 eV, E _Ti-Ti = 2.29 eV, and E _Ti-Si = 4.47 eV. The dependence of the total energy of the unit cell E _tot(V) on the unit cell volume V is obtained by optimizing the unit cell volume. The bulk modulus B ₀ = 132 GPa is determined from the Murnaghan equation of state for solids and the dependence E _tot (V). This value of the bulk modulus is used to estimate the activation energy for interstitial diffusion of silicon atoms Q _i(Si) ≈ 0.8 eV.     

Refractometry of mechanically compressed (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>SO<Subscript>4</Subscript> crystals

The effect of uniaxial mechanical pressure σ _m ≤ 150 bar on the spectral (300–800 nm) dependence of the birefringerence Δn _i and refractive indices n _i of (NH₄)₂SO₄ crystals has been investigated. It is shown that the dispersion of n _i (λ) and Δn _i (λ) is normal and sharply increases with approach to the absorption edge. It is established that uniaxial pressure does not change the character of the dispersions dn _i /dλ and dΔn _i /dλ and only affects their magnitudes. It is shown that the increase in the refractive indices under uniaxial stress is mainly due to the increase in the refraction caused by the increase in the band gap and long-wavelength shift of the UV absorption band maximum.     

Anomalous temperature dependence of photoluminescence in GeO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> films and GeO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/SiO<Subscript>2</Subscript> nano-heterostructures

The optical properties of GeO _x film and GeO _x /SiO₂ multilayer heterostructures (with thickness of GeO _x layers down to 1 nm) were studied with the use of Raman scattering and infrared spectroscopy, ellipsometry and photoluminescence spectroscopy including temperature dependence of photoluminescence. The observed photoluminescence is related to defect (dangling bonds) in GeO _x and interface defects for the case of GeO _x /SiO₂ multilayer heterostructures. From analysis of temperature dependence of photoluminescence intensity, it was found that rate of nonradiative transitions in GeO _x film has Berthelot type, but anomalous deviations from Berthelot type temperature dependence were observed in temperature dependences of photoluminescence intensities for GeO _x /SiO₂ multilayer heterostructures.     

A first-principle study on the phase transition,electronic structure,and mechanical properties of three-phase ZrTi<Subscript>2</Subscript> alloy under high pressure*

We employed density-functional theory (DFT) within the generalized gradient approximation(GGA) to investigate the ZrTi₂ alloy, and obtained its structural phase transition,mechanical behavior, Gibbs free energy as a function of pressure, P-V equation of state,electronic and Mulliken population analysis results. The lattice parameters andP-V EOS for α, β and ω phases revealed by ourcalculations are consistent with other experimental and computational values. The elasticconstants obtained suggest that ω-ZrTi₂ and α-ZrTi₂ are mechanically stable, and that β-ZrTi₂ is mechanically unstableat 0 GPa, but becomes more stable with increasing pressure. Our calculated resultsindicate a phase transition sequence of α → ω → β forZrTi₂. Both thebulk modulus B and shear modulus G increase linearly withincreasing pressure for three phases. The G/B values illustrated goodductility of ZrTi₂alloy for three phases, with ω<α<β at0 GPa. The Mulliken population analysis showed that the increment of d electron occupancystabilized the β phase. A low value for B '₀ is the feature of EOS for ZrTi₂ and this softness in the EOS isrepresentative of pressure induced s-d electron transfer.     

Transport and magnetic properties of a Zn<Subscript>0.1</Subscript>Cd<Subscript>0.9</Subscript>GeAs<Subscript>2</Subscript> + 10 wt % MnAs composite with magnetic clusters at high pressure

The temperature (T = 77–420 K) dependences of the electrical resistivity and the magnetization, the magnetic-field (H ≤ 5 kOe) and pressure (P ≤ 7 GPa) dependences of the resistivity, the Hall coefficient, and the magnetization have been measured in the Zn_0.1Cd_0.9GeAs₂ + 10 wt % MnAs composite with the Curie temperature T _C = 310 K. The magnetoresistive effect has been observed at high hydrostatic pressure to 7 GPa. At nearly room temperature, the pressure dependence of the magnetization demonstrated a transition from the ferromagnetic to paramagnetic state at P ~ 3.2 GPa that was accompanied by the semiconductor–metal phase transition.     

Equation of state and structural transition at high hydrostatic pressures in the BiFeO<Subscript>3</Subscript> crystal

Change in the crystal structure of the BiFeO₃ multiferroic at high pressures up to 70 GPa in a diamond anvil cell has been studied by the method of synchrotron x-ray diffraction at room temperature. The experiment has been carried out under hydrostatic conditions with helium as a pressure-transferring medium. An anomaly has been observed in the behavior of the structural parameters at pressures P _c ≈ 40?50 GPa. This anomaly correlates with the effect of the magnetic collapse of iron moments revealed in this pressure range. It has been found that the bulk compression modulus is equal to B ₀ = (75.5 ± 15.5) GPa in the interval 0 < P < P _c and is almost quadrupled to a value of B = (292 ± 9) GPa in the interval P > P _c. When the pressure decreases, the behavior of the structural parameters is completely reversible in correlation with the reversibility of the magnetic transition. The “diffuseness” of the structural transition in pressure is explained by thermal fluctuations between the high-and low-spin states of Fe³⁺ ions in the transition region.