Neutron diffraction study of the pressure-driven structural transition in the HgTe<Subscript>0.85</Subscript>S<Subscript>0.15</Subscript> ternary compound

The structure of the HgTe_0.85S_0.15 ternary mercury compound was studied by neutron diffraction at high pressures of up to 40 kbar. A phase transition from the cubic (sphalerite-type) to the hexagonal (cinnabar-type) structure was established to occur with increasing pressure and to be accompanied by an abrupt change in the unit-cell volume and interatomic distances. The unit cell parameters, the positions of the Hg and Te/S atoms in the hexagonal cinnabar phase, and their pressure dependences were found.     

Hydrostatic pressure-induced phase transitions in RbMnCl<Subscript>3</Subscript>: Raman spectra and lattice dynamics

Raman scattering spectra of RbMnCl₃ are measured at room temperature under high hydrostatic pressure. The results are interpreted based on first principles lattice dynamics calculations. The experimental data obtained correlate with the calculations in the low frequency domain but disagree slightly in the region of high-frequency vibrations. The transition from the hexagonal to the cubic perovskite phase observed earlier (near 0.7 GPa) was confirmed, and new transitions to lower symmetry distorted phases were discovered (at 1.1 and 5 GPa).     

Magnetic resonance of the RbMnBr<Subscript>3</Subscript> antiferromagnet under pressure

The antiferromagnetic resonance spectrum was experimentally studied for a noncollinear RbMnBr₃ antiferromagnet under a mechanical pressure applied to the sample in various directions. It is shown that the incommensurate magnetic phase existing in the initial system in the presence of regular crystallographic distortions is sensitive to the pressure applied along one of the sample axes. The critical transition field to the commensurate phase decreased under pressure. It was also found that the pressure influences the uniaxial anisotropy appearing in the crystal basal plane in the presence of orthorhombic distortions. These effects were analyzed with allowance for the domain structure of the sample.     

Formation and composition of the clathrate phase in the H<Subscript>2</Subscript>O-H<Subscript>2</Subscript> system at pressures to 1.8 kbar

The transition of the hexagonal ice phase I_h to the clathrate phase sII has been found in the H₂O-H₂ system at a pressure of about 1 kbar under conditions of an excess of gaseous hydrogen. The pressures of the I_h → sII and sII → I_h transitions have been determined over a temperature range from ?36 to ?18°C, and the pressure dependence of the synthesis temperature of the clathrate phase from a liquid at pressures from 1.0 to 1.8 kbar has been constructed. The solubility of hydrogen in the I_h and sII phases and in liquid water has been measured. The concentration of hydrogen in the clathrate phase sII is about 1.2 wt % (10 mol %) near the boundary of the sII → I_h transition, and it increases to 2 wt % (16 mol %) at a pressure of 1.8 kbar.     

Neutron diffraction investigation of the structural transition in HgSe1−x Sx ternary mercury chalcogenide systems at high pressures

The structure of HgSe_1?x S_x ternary mercury chalcogenides at high pressures up to 35 kbar is investigated by neutron diffraction. It is found under pressure, that the HgSe_1?x S_x compounds undergo, a phase transition from the cubic sphalerite-type to the hexagonal cinnabar-type structure, which is accompanied by a jump-wise change in the unit cell volume and interatomic distances. The unit cell parameters and the positional parameters of Hg and Se (S) atoms in the high-pressure hexagonal phase are determined. A two-phase state is revealed in the phase transition region.     

Structure and dynamics of the pure and mixed fluorites <Emphasis Type="Italic">Me</Emphasis>F<Subscript>2</Subscript> (<Emphasis Type="Italic">Me</Emphasis> = Ca,Sr, Ba,and Pb)

The structure and dynamics of the crystal lattice of MeF₂ fluorites (Me = Ca, Sr, Ba, and Pb) under external hydrostatic compression (0–3.5 GPa) are calculated within the shell model in the pair potential approximation. The first-order structural phase transition from the cubic to the orthorhombic phase in these crystals under pressure is investigated. The effect of chemical pressure on the BaF₂ crystal is analyzed by the simulation of mixed crystals, namely, Ba_1?xCa_xF₂ and Ba_1?xSr_xF₂. It is demonstrated that the supercell method, as applied to the simulation of mixed crystals, results in a lower lattice energy per formula unit as compared to the lattice energy obtained by the virtual-crystal method.     

High-pressure effect on the ferroelectric-paraelectric transition in PbTiO<Subscript>3</Subscript>

The crystal structure of lead titanate PbTiO₃ was investigated by energy dispersive X-ray diffraction at high pressures up to 4 GPa in a temperature range of 300–950 K. At the ambient conditions, the PbTiO₃ structure is tetragonal with the space group P4mm (ferroelectric phase). A structural phase transition into the cubic phase with a space group Pm[`3]mPm\bar 3m is observed at T = 747 K. It was found that the phase transition temperature decreases upon applying the high pressure with the coefficient dT _C /dP = -65 K/GPa. Dependences of parameters and volume of the unit cell on the pressure and temperature was found, and the bulk modulus and thermal expansion coefficients for the tetragonal and cubic phases of lead titanate have been calculated.     

Luminescence properties of “relatively” trap-free crystals of anhydrous salts containing divalent manganese

Crystals of RbMnCl₃, Rb₂MnCl₄, CsMnCl₃, RbMnBr₃, CsMnBr₃ and CsMnI₃ which are grown from melts in contact with elemental manganese luminescence strongly throughout the 10K to 300K range. At room temperature the emission intensities from these crystals are larger by orders of magnitude than those observed from crystals of the same salts prepared without metallic manganese. Emission lifetime and intensity measurements made as a function of temperature are consistent with the view that the contact of the molten salt with metallic manganese during crystal growth yields materials which are relatively free of quenching traps. The effect appears to be quite general.     

Magneto-optical investigations of the domain structure and magnetization of the ferrite-garnet Tb<Subscript>0.2</Subscript>Y<Subscript>2.8</Subscript>Fe<Subscript>5</Subscript>O<Subscript>12</Subscript> in the temperature range of the spontaneous spin-reorientation phase transition

The transformation of a domain structure and technical magnetization of the Tb_0.2Y_2.8Fe₅O₁₂ single crystal in the temperature range of the spontaneous orientational phase transition have been investigated by the magneto-optical method. It has been shown that the phase transition is extended in a certain temperature range in which domains of the low-temperature and high-temperature magnetic phases coexist. It has been found that the evolution of the domain configuration in the temperature range of spin reorientation substantially depends on the presence of mechanical stresses in the crystal. Anomalies in the temperature dependences of the coercivity and magneto-optical susceptibility of the crystal due to the transformation of its domain structure during the phase transition have been revealed. The experimental results have been interpreted within the existing theory of orientational phase transitions in cubic crystals.     

Magnetotransport characteristics of strained La<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> epitaxial manganite films

The electrical and magnetic characteristics of La_0.7Sr_0.3MnO₃ (LSMO) epitaxial manganite films are investigated by different methods under conditions when the crystal structure is strongly strained as a result of mismatch between the lattice parameters of the LSMO crystal and the substrate. Substrates with lattice parameters larger and smaller than the nominal lattice parameter of the LSMO crystal are used in experiments. It is shown that the behavior of the temperature dependence of the electrical resistance for the films in the low-temperature range does not depend on the strain of the film and agrees well with the results obtained from the calculations with allowance made for the interaction of electrons with magnetic excitations in the framework of the double-exchange model for systems with strongly correlated electronic states. Investigations of the magneto- optical Kerr effect have revealed that an insignificant (0.3%) orthorhombic distortion of the cubic lattice in the plane of the NdGaO₃(110) substrate leads to uniaxial anisotropy of the magnetization of the film, with the easy-magnetization axis lying in the substrate plane. However, LSMO films on substrates (((LaAlO₃)_0.3+(Sr₂AlTaO₆)_0.7)(001)) ensuring minimum strain of the films exhibit a biaxial anisotropy typical of cubic crystals. The study of the ferromagnetic resonance lines at a frequency of 9.76 GHz confirms the results of magnetooptical investigations and indicates that the ferromagnetic phase in the LSMO films is weakly inhomogeneous.     

Magnetostriction of Hexagonal HoMnO<Subscript>3</Subscript> and YMnO<Subscript>3</Subscript> Single Crystals

We report on the magnetostriction of hexagonal HoMnO₃ and YMnO₃ single crystals in a wide range of applied magnetic fields (up to H = 14 T) at all possible combinations of the mutual orientations of magnetic field H and magnetostriction ΔL/L. The measured ΔL/L(H, T) data agree well with the magnetic phase diagram of the HoMnO₃ single crystal reported previously by other authors. It is shown that the nonmonotonic behavior of magnetostriction of the HoMnO₃ crystal is caused by the Ho³⁺ ion; the magnetic moment of the Mn³⁺ ion parallel to the hexagonal crystal axis. The anomalies established from the magnetostriction measurements of HoMnO₃ are consistent with the phase diagram of these compounds. For the isostructural YMnO₃ single crystal with a nonmagnetic rare-earth ion, the ΔL/L(H, T) dependences are described well by a conventional quadratic law in a wide temperature range (4–100 K). In addition, the magnetostriction effect is qualitatively estimated with regard to the effect of the crystal electric field on the holmium ion.     

Fine structure and magnetism of the cubic oxide compound Ni<Subscript>0.3</Subscript>Zn<Subscript>0.7</Subscript>O

The fine structure and spin system of the cubic oxide Ni_0.3Zn_0.7O compound prepared from the initial hexagonal phase by quenching a sample with a high temperature and applying an external hydrostatic pressure to it have been studied using magnetic measurements, synchrotron and X-ray diffraction. It has been revealed that the diffraction patterns of this compound contain a system of weak diffuse maxima with the wave vectors q = (1/6 1/6 1/6)2π/a and (1/3 1/3 1/3)2π/a, along with strong Bragg peaks of the cubic phase. It has been shown that the origin of the diffuse peaks is due to longitudinal and transverse displacements of ions with respect to symmetric crystallographic directions of the {111} type. The reasons for the ion displacement and specific features of the structure of the spin system of the strongly correlated oxide Ni_0.3Zn_0.7O compound have been briefly discussed.     

Structural and magnetic phase transitions in Pr<Subscript>0.7</Subscript>Ca<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> at high pressures

The crystal structure and Raman spectra of Pr_0.7Ca_0.3MnO₃ manganite at high pressures of up to 30 GPa and the magnetic structure at pressures of up to 1 GPa have been studied. A structural phase transition from the orthorhombic phase of the Pnma symmetry to the high-pressure orthorhombic phase of the Imma symmetry has been observed at P ∼ 15 GPa and room temperature. Anomalies of the pressure dependences of the bending and stretching vibrational modes have been observed in the region of the phase transition. A magnetic phase transition from the initial ferromagnetic ground state (T _C = 120 K) to the A-type antiferromagnetic state (T _N = 140 K) takes place at a relatively low pressure of P = 1 GPa in the low-temperature region. The structural mechanisms of the change of the character of the magnetic ordering have been discussed.     

Pressure‐induced anomalous phase transformation in nano‐crystalline dysprosium sesquioxide

The phase transformation in nano‐crystalline dysprosium sesquioxide (Dy₂O₃) under high pressures is investigated using in situ Raman spectroscopy. The material at ambient was found to be cubic in structure using X‐ray diffraction (XRD) and Raman spectroscopy, while atomic force microscope (AFM) showed the nano‐crystalline nature of the material which was further confirmed using XRD. Under ambient conditions the Raman spectrum showed a predominant cubic phase peak at 374 cm⁻¹, identified as F_g mode. With increase in the applied pressure this band steadily shifts to higher wavenumbers. However, around a pressure of about 14.6 GPa, another broad band is seen to be developing around 530 cm⁻¹ which splits into two distinct peaks as the pressure is further increased. In addition, the cubic phase peak also starts losing intensity significantly, and above a pressure of 17.81 GPa this peak almost completely disappears and is replaced by two strong peaks at about 517 and 553 cm⁻¹. These peaks have been identified as occurring due to the development of hexagonal phase at the expense of cubic phase. Further increase in pressure up to about 25.5 GPa does not lead to any new peaks apart from slight shifting of the hexagonal phase peaks to higher wavenumbers. With release of the applied pressure, these peaks shift to lower wavenumbers and lose their doublet nature. However, the starting cubic phase is not recovered at total release but rather ends up in monoclinic structure. The factors contributing to this anomalous phase evolution would be discussed in detail. Copyright © 2010 John Wiley & Sons, Ltd.     

Transition of iron ions from high-spin to low-spin state and pressure-induced insulator-metal transition in hematite Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>

For the analysis of the electron structure of hematite under pressure, methods of the generalized transition state and local electron density approximation combined with the dynamical mean-field theory have been used. The transition of iron ions from the high-spin to low-spin state and the insulator-metal transition observed in Fe₂O₃ at high pressures have been considered. It is shown that in the low-symmetry crystal structure of Fe₂O₃ experimentally revealed at high pressures a low-spin metallic state is also preferable. The theoretical results obtained agree well with experimental data.     

Electronic structure,lattice dynamics,and magnetoelectric properties of double perovskite La<Subscript>2</Subscript>CuTiO<Subscript>6</Subscript>

The results of ab initio calculations of the electronic structure, vibrational properties, and the magnetoelectric effect in the La₂CuTiO₆ crystal with double perovskite structure are presented. The lattice dynamics calculation shows the presence of unstable modes in the phonon spectrum of the high-symmetry cubic phase with space group \(Fm\overline 3 m\). Condensation of two most unstable modes belonging to the center and the boundary point X of the Brillouin zone leads to the formation of a nonpolar stable phase with space group P2₁/n. The calculation taking into account spin polarization shows that the magnetic ground state is E*-type antiferromagnetic with doubled magnetic cell and with the two spin-up and two spin-down configuration of magnetic moments of copper ions along the [010] crystallographic direction. Such ordering of magnetic moments leads to polar space group and polarization formation. The polarization magnitude is estimated as 71 μC/m².     

Hydrogen solubility in amorphous Mg<Subscript>0.6</Subscript>SiO<Subscript>2.6</Subscript> at high pressure

The solubility of hydrogen in amorphous Mg_0.6SiO_2.6 at a temperature of 250°C and pressures up to 75 kbar is studied using a quenching technique. The molar ratio H₂/formula unit is found to nonlinearly increase with pressure from x = 0.12 at P = 10 kbar to x = 0.303 at P = 75 kbar. An investigation of the quenched samples by Raman spectroscopy demonstrated that hydrogen dissolves in amorphous Mg_0.6SiO_2.6 in the form of H₂ molecules. X-ray diffraction and Raman studies showed that the hydrogenation of the samples is likely to be accompanied by a phase transition in the amorphous lattice of Mg_0.6SiO_2.6 at P ≈ 52.5 kbar to a denser amorphous modification.     

Phase transitions in the oxyfluoride (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>NbOF<Subscript>6</Subscript>

(NH₄)₃NbOF₆ single crystals were grown, polarization-optical studies were performed, and birefringence was measured over the temperature range 90–500 K. A sequence of first-order structural phase transitions was found at temperatures T _1↓ = 259.7 K and T _2↓ = 257.7 K with temperature hysteresis δT ₁ = 0.9 K and δT ₂ = 1.9 K. The transitions are accompanied by twinning and the following change in the crystal symmetry: cubic ? tetragonal ? monoclinic. Optical second harmonic generation is found to occur at room temperature, which indicates that the cubic phase is not centrosymmetric. It is assumed that the phase transitions are ferroelastic and ferroelectric in nature.     

Structural studies of phase transitions in crystalline and liquid halides (ZnCl<Subscript>2</Subscript>, AlCl<Subscript>3</Subscript>) under pressure

The results of investigating the phase diagrams of ZnCl₂ and AlCl₃ halides, as well as the structure of the shortrange order of the corresponding melts under pressures up to 6.5 GPa, by the method of energy-dispersive x-ray diffraction are reported. When a ZnCl₂ crystal is compressed, a phase transition occurs from the γ phase (HgI₂ structure type) to the δ phase (distorted CdI₂ structure, WTe₂ type). The structural studies of the liquid state of ZnCl₂ and AlCl₃ indicate that the intermediate-range order decreases rapidly in the tetrahedral network of both melts as the pressure increases to 1.8 and 2.3 GPa for ZnCl₂ and AlCl₃, respectively. With further compression, the transitions in both melts occur with a change in the structure of the short-range order and with an increase in the coordination number. In this case, the transition in AlCl₃ occurs at ≈4 GPa and is a sharp first order transition, whereas the transition in ZnCl₂ occurs more smoothly in a pressure range of 2–4 GPa with a maximum intensity near 3 GPa. Thus, the AlCl₃ and ZnCl₂ compounds exemplify the existence of two phenomena—gradual decay of intermediate-range structural correlations and a sharper liquid-liquid coordination transition.     

Structural study of ND4I at high pressures and low temperatures

Abstract

Structure, positional, and thermal parameters of ND₄I were studied at high pressures up to 90 kbar and low temperatures down to 10 K using time-of-flight neutron diffraction. The phase transition from a disordered CsCI-type cubic phase ND₄I(II) into a recently discovered high pressure phase ND₄I(V) was observed at P = 80(5) kbar. Surprisingly, the structure of the high pressure phase V was found to bear a strong resemblance to that of the ambient pressure, low-temperature phase III - tetragonal structure with an antiparallel ordering of ammonium ions, space group P4/nmm. The critical value of the deuterium positional parameter corresponding to the II-V transition is close to the one for the phase transition between the disordered and ordered CsCl-type cubic phases II and IV in other ammonium halides.