Structural phase transitions and the equation of state of SnTe at high pressures up to 2 mbar

Synchrotron X-ray diffraction studies of the structure of SnTe have been performed at room temperature and high pressures under the conditions of quasihydrostatic compression up to 193.5 GPa created in diamond anvil cells. Two structural phase transitions have been detected at P ≈ 3 and 23 GPa. The first phase transition is accompanied by a stepwise decrease in the volume of the unit cell by 4% because of the orthorhombic distortion of the initial SnTe-B1 cubic structure of the NaCl type. It has been found that two intermediate rhombic phases of SnTe with the space groups Cmcm and Pnma coexist in the pressure range of 3–23 GPa. The second phase transition at 23 GPa occurs from the intermediate rhombic modification to the SnTe-B2 cubic phase with the CsCl structure type. This phase transition is accompanied by an abrupt decrease in the volume of the unit cell by 8%. The pressure dependence of the volumes per formula unit at room temperature has been determined.     

Thermoelectric properties of high-pressure silicon phases

The thermo emf in Czochralski-grown silicon single crystals (Cz-Si) was experimentally studied in a range of pressures up to 20 GPa. The pressure dependences revealed phase transitions in the metallic phase of silicon, which passed from tetragonal to orthorhombic and then to hexagonal lattice. The high-pressure silicon phases, as well as the metallic high-pressure phases in A_NB_8?N semiconductors, possess conductivity of the hole type. As the pressure decreases, the emf behavior reveals transitions to the metastable phases Si-XII and Si-III. Preliminary thermobaric treatment of the samples at a pressure of up to 1.5 GPa and a temperature of T=50–650°C influences the thermoelectric properties of Cz-Si at high pressures.     

Structural Phase Transitions and the Equation of State in SnSe at High Pressures up to 2 Mbar

The crystal structure of tin selenide SnSe has been studied under quasihydrostatic compression at pressures up to 205 GPa created in diamond anvil cells at room temperature. Two structural phase transitions have been detected at and P ≈ 2.5 32 GPa. The former phase transition is continuous from the GeS-type structure (space group Pbnm) to the TlI-type structure (space group Cmcm). The phase transition to the CsCl-type cubic structure (space group Pm\(\bar 3\)m) occurs at 32 GPa and is accompanied by a stepwise decrease in the volume of the unit cell by 7%. The pressure dependence of the specific volume of the unit cell at room temperature has been constructed up to 205 GPa.     

Thermophysical studies of the phase transitions in (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>NbOF<Subscript>6</Subscript> crystals

The thermophysical properties of oxyfluoride (NH₄)₃NbOF₆ were studied in detail over wide ranges of temperatures and pressures. At atmospheric pressure, a sequence of four structural phase transitions was established with the following changes in entropy: ΔS ₁ = Rln 2.7, δS ₂ = Rln38.3, ΔS ₃ = 0.08R, and ΔS ₄ = 0.17R. An external hydrostatic pressure was found to narrow the region of existence of the initial cubic phase. A triple point was detected in the p-T diagram; at a pressure above 0.07 GPa, the transition between the tetragonal and monoclinic phases occurs through a distorted high-pressure phase.     

Thermoelectric properties of the trigonal and orthorhombic modifications of zinc telluride

Thermoelectric measurements are performed to study the phase transformations occurring in ZnTe under high pressure. It is shown that the thermoelectric power S of the cinnabar trigonal phase corresponds to a semiconductor with a hole-type conduction. In the Cmcm orthorhombic phase, the value of S≈+10 μV/K and the sign of the thermoelectric power testify to the metallic hole-type conduction, as in the high-pressure phases of other Group II chalcogenides (HgSe, HgTe, CdTe) with similar crystal lattices. In the transition region between the trigonal and orthorhombic phases, the pressure dependence of the thermoelectric power is found to exhibit an anomaly (a sharp dip), which leads to a change in the sign of S under decreasing pressure. This feature may presumably be related to the formation of the intermediate phase with the NaCl structure, which has an electron-type conduction in other zinc and cadmium chalcogenides.     

Thermopower of lead chalcogenides at high pressures

Thermopower measurements on PbX crystals (X=Te, Se, S) at high hydrostatic pressures of up to 35 GPa are reported. New data were obtained on the magnitude and on the pressure dependence of the thermopower of high-pressure semiconducting and metallic phases. The phase transitions occurring in PbX are treated in terms of a model in which the transition to an insulator electronic spectrum is caused by the Peierls lattice distortion.     

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.     

Modeling of Phase Transitions of Graphites to Diamond-Like Phases

The method of the density functional theory is used to study structural transformations between graphites and diamond-like phases. The calculations have been carried out in two approximations: a local density approximation and a generalized gradient approximation. It is found that the phase transitions of hexagonal graphene layers to a cubic diamond and diamond-like phases must occur at uniaxial compressions of ~57–71 GPa, whereas some diamond-like phases can be obtained from tetragonal graphene layers at significantly lower pressures of 32–52 GPa. The X-ray diffraction patterns have been calculated for the phase transition of graphite I4₁/amd to tetragonal LA10 phase that takes place at the minimum pressure that can be used for experimental identification of these compounds.     

Superconducting transition temperature in hafnium under pressures up to 64 GPa

The superconducting transition temperature T _c of hafnium is measured as a function of pressure up to 64 GPa. The character of the pressure dependence of T _c observed at α–ω–β transitions in Hf is found to be similar to that observed for Zr. In the regions of α and β phases, T _c increases with pressure with the slopes dT _c /dP=0.05 and 0.16 K/GPa, respectively. At the α–ω transition, T _c (P) exhibits a tendency to a decrease, while at the ω–β transition, T _c increases stepwise from 5.8 to 8.0 K. The α–ω transition occurs at pressures between 31.2 and 35.9 GPa, and the ω–β transition, at a pressure of 62±2 GPa.     

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.     

Global geometric entanglement and quantum phase transition in three-leg spin-3/2 Heisenberg tubes

Based on the tensor network representations, we have developed an efficient scheme to calculate the global geometric entanglement as a multipartite entanglement measure for the three-leg spin tubes. From the geometric entanglement, the phase diagram of a spin-3 / 2 isosceles triangle spin tube has been investigated varying the base interaction α. Two Berezinsky-Kosterlitz-Thouless phase transitions are estimated to be α_c1 ? 0.68 and α_c2 ? 3.85, respectively. Then, even though the spin tube is in gapless spin liquid phases for α<α_c1 and α >α_c2, the geometrical structure difference between the groundstate wavefunctions for the two regions is found to reflect the global geometric entanglement that contains bipartite and multipartite contributions. Further, the phase transition points from the von Neumann entropies and fidelity are consistent with that from the geometric entanglement. As a result, the global geometric entanglement can be used to explore a geometrical nature of quantum phases as well as an indicator for quantum phase transitions in many-body lattice systems.     

High-pressure magnetic properties and <Emphasis Type="Italic">P-T</Emphasis> phase diagram of iron borate

The high-pressure magnetic states of iron borate ⁵⁷FeBO₃ single-crystal and powder samples have been investigated in diamond anvil cells by nuclear forward scattering (NFS) of synchrotron radiation at different temperatures. In the low-pressure (0 < P < 46 GPa) antiferromagnetic phase, an increase of the Neél temperature from 350 to 595 K induced by pressure was found. At pressures 46–49 GPa, a transition from the antiferromagnetic to a new magnetic state with a weak magnetic moment (magnetic collapse) was discovered. It is attributed to the electronic transition in Fe³⁺ ions from the high-spin 3d⁵ (S = 5/2, ⁶A_1g) to the low-spin (S = 1/2, ²T_2g) state (spin crossover) due to the insulator-semiconductor-type transition with extensive suppression of strong d-d electron correlations. At low temperatures, NFS spectra of the high-pressure phase indicate magnetic correlations in the low-spin system with a magnetic ordering temperature of about 50 K. A tentative magnetic P-T phase diagram of FeBO₃ is proposed. An important feature of this diagram is the presence of two triple points where magnetic and paramagnetic phases of the high-spin and low-spin states coexist.     

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.     

Anomalous behavior of a α-iron zero-temperature isotherm in the region of negative pressures

The detailed ab initio calculations of the electronic structure of α-iron crystals revealed the presence of a narrow interval of specific volumes in the P(V, T=0) isotherm where dP/dV>0. According to the calculations, this anomaly occurs at pressures from ?3 to ?5 GPa and is due to the intensive energy-spectrum rearrangement accompanied by the almost simultaneous appearance of eight electronic topological transitions.     

Analysis of the strain-rate sensitivity of flow stresses in nanocrystalline FCC and BCC metals

The dependence of the strain-rate sensitivity coefficient of flow stresses S = dlnσ/dln\(\dot \varepsilon \) on temperature, strain rate, and grain size in nanocrystalline (NC) metals is analyzed quantitatively in terms of the dislocation-kinetics approach taking into account the properties of grain boundaries as sources, sinks, and barriers for moving dislocations. The interaction of moving dislocations with a dislocation forest in nanograin boundaries is shown to be responsible for the fact that the values of this coefficient in NC fcc metals (Cu, Ni) are an order of magnitude greater than those in coarse-grained metals and for the strong dependence of the coefficient S on the above factors. This dependence is largely caused by the annihilation of lattice dislocations in grain boundaries controlled by the activation energy of grain boundary diffusion. The values of the coefficient S in NC bcc metals (α-Fe) are an order of magnitude lower than those in coarse-grained samples, because dislocations move in a Peierls relief in nanograins     

Die charakteristische Thermokraft der Grenzflächenatome

For a single-band conductor where two or more scattering mechanisms are present, each giving rise to a characteristic thermoelectric powerS _n and a electrical resistivity? _n the resultant thermoelectric powerS is given, as a first approximation, by\(S = \sum\limits_n {\varrho _n S_n /\varrho } \). Denoting withS ₀ the characteristic thermoelectric power due to the scattering of the conduction electrons by the boundary atoms, and withS _i and? _i the resultant thermoelectric power and electrical resistivity arising from all other scattering mechanisms, one may writeS=S ₀+? _i(S _i?S ₀)/?. The thermoelectric powerS and the electrical resistivity? of thin layers of potassium, evaporated in a vacuum ～5·10^?9 Torr on a glass substrate at 90° K temperature, were measured at different thicknesses. The variation ofS as a function of 1/? verifies the above mentioned relation. Thus, the thermoelectric power, characteristic for the scattering by potassium boundary atoms can be determined.     

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.     

Metal-insulator transition in whiskers of the NbS<Subscript>3</Subscript> quasi-one-dimensional conductor under pressure

The effect of pressure on the conduction of the NbS₃ quasi-one-dimensional conductor is studied. A pressure-induced insulator-metal transition is observed. The transition is accompanied by an increase in conductivity by six orders of magnitude at room temperature. Under pressures of 3–4 GPa, an additional phase transition appears in the temperature dependences of resistance. This transition manifests itself in an increase in the local conduction activation energy. The quantity dln(R)/d(1/T) reaches its maximum under pressures of 4–5 GPa, and the temperature position of the maximum of dln(R)/d(1/T) depends on the pressure as T* ≈ 7.5P + 202 K.     

Fluctuations of orientational order in a uniaxial nematic liquid crystal with biaxial molecules and its response to an external field

Homogeneous thermal fluctuations of the orientational order parameters S and G of biaxial molecules in a uniaxial nematic liquid crystal are investigated in the framework of the molecular-statistical theory. It is demonstrated that the molecular biaxiality significantly affects the order parameters S and G, their temperature dependences in the nematic phase, the amplitude and the temperature dependence of the order parameter fluctuations in the nematic and isotropic phases, and the character of the transition from the nematic phase to the isotropic liquid phase. It is established that the fluctuations of the parameters S and G in the nematic phase are related to the temperature dependences of S and G and the susceptibilities χ_S and χ_G of the nematic liquid crystal to external fields, which leads to a change in the parameters S and G at a fixed director orientation. Explanations are offered for the known experimental data on the orientational ordering of biaxial molecules under the action of external fields in the isotropic phase of nematic liquid crystals.     

Crossover between the thermodynamic and nonequilibrium scenarios of structural transformations of H<Subscript>2</Subscript>O I<Emphasis Type="Italic">h</Emphasis> ice during compression

A detailed investigation of different scenarios of structural transformations of H₂O Ih ice during compression to a pressure of 2 GPa in the temperature range from 77 to 200 K is performed. In the range of temperatures and pressures being treated, detailed data are obtained for the density and the shear modulus for different phases of ice including the hda, IX, and XII phases. The experimentally obtained correlations for the density and ultrasonic velocities, with due regard for the available data of structural investigations, are used to identify the transformation sequences Ih→hda (below 135 K), Ih→II→VI (above 165 K), and Ih→IX→VI (from 155 to 180 K). In the vicinity of the crystallization temperature of amorphous ice, i.e., at about 140 K, an anomalous transformation pattern is observed, which is interpreted as predominantly the Ih→XII phase transition. The temperature crossover is discussed between the mode of solid-phase amorphization (Ih→hda) and crystal-crystal transitions, as well as the metastable nature of IX ice and the mechanism of solid-phase amorphization.