Structural stability of tin clathrates under high pressure

High pressure Raman scattering experiments have been performed for Rb₈Sn₄₄□₂ in order to investigate the pressure induced phase transition. At pressures of 6.0 and 7.5 GPa, Raman spectrum was drastically changed, indicating the phase transitions. The irreversibility of the spectral change and the disappearance of Raman peak observed at 7.5 GPa strongly suggest the occurrence of irreversible amorphization.     

Structural stability of TiO and TiN under high pressure

The high pressure phase transition and elastic behavior of Transition Metal Compounds (TiO and TiN) which crystallize in NaCl-structure have been investigated using the three body potential model (TBPM) approach. These interactions arise due to the electron-shell deformation of the overlapping ions in crystals. The TBP model consists of a long range Coulomb, three body interactions, and the short-range overlap repulsive forces operative up to the second neighboring ions. The authors of this paper estimated the values of the phase transition pressures, associated volume collapses, and elastic constants, all of which were found to be closer to available experimental data than other calculations. Thus, the TBPM approach promises to predict the phase transition pressure and pressure variations of elastic constants of Transition Metal compounds.      

Structural and elastic properties of TiN under high pressure

We have investigated the structural and elastic properties of TiN at high pressures by the first-principles plane wave pseudopotential density functional theory method at applied pressures up to 45.4 GPa. The obtained normalized volume dependence of the resulting pressure is in excellent agreement with the experimental data investigated using synchrotron radial x-ray diffraction (RXRD) under nonhydrostatic compression up to 45.4 GPa in a diamond-anvil cell. Three independent elastic constants at zero pressure and high pressure are calculated. From the obtained elastic constants, the bulk modulus, Young's modulus, shear modulus, acoustic velocity and Debye temperature as a function of the applied pressure are also successfully obtained.     

Structural stability and vibrational characteristics of CaB_6 under high pressure

In situ Raman spectroscopy and x-ray diffraction measurements are used to explore the structural stability of CaB_6 at high pressures and room temperature. The results show no evidence of structural phase transitions up to at least 40 GPa.The obtained equation of state with smooth pressure dependencies yields a zero-pressure isothermal bulk modulus B0=170(5) GPa, which agrees well with the previous measurements. The frequency shifts for A_(1g), Eg, and T_(2g) vibrational modes of polycrystalline CaB_6 are obtained with pressure uploading. As the pressure increases, all the vibration modes have smooth monotonic pressure dependence. The Gr¨uneisen parameter of Eg modes is the largest, indicating its largest dependence on the volume of a crystal lattice.     

The electrical properties of HgTe and HgSe under very high pressure

The electrical properties of HgTe and HgSe have been investigated at pressures up to 200 kbar in an octahedral apparatus. Measurements of the electrical resistivity at room temperature showed that, beyond the well-known transition from the semimetallic to semiconductive state, both become metallic, at 84 kbar and 155 kbar, respectively. The energy gap at various fixed pressures was obtained from the resistance-temperature relationships. The energy gap of semiconducting HgTe decreases monotonically with pressure, the coefficient being ?l.53 × 10^?5$\text{eV}\text{bar}$. The energy gap of HgSe is rather insensitive to pressures up to 75 kbar, above which it decreases continuously ($\text{dE}\text{dP}$ = ?1.59 × 10^?5$\text{eV}\text{bar}$) before vanishing around 150 kbar. At high pressures the temperature coefficient of the resistance in the metallic state is 3.25 ~ 4.70 × $\text{10}{}^{\mathrm{?3}}\text{deg}$ for HgTe, and 5.7 ~ 5.9 × $\text{10}{}^{\mathrm{?3}}\text{deg}$ for HgSe.     

Structural, electronic and vibrational properties of InN under high pressure

The structural, electronic and vibrational properties of InN under pressures up to 20 GPa have been investigated using the pseudo-potential plane wave method (PP-PW). The generalized-gradient approximation (GGA) in the frame of density functional theory (DFT) approach has been adopted. It is found that the transition from wurtzite (B4) to rocksalt (B1) phase occurs at a pressure of approximately 12.7 GPa. In addition, a change from a direct to an indirect band gap is observed. The mechanism of these changes is discussed. The phonon frequencies and densities of states (DOS) are derived using the linear response approach and density functional perturbation theory (DFPT). The properties of phonons are described by the harmonic approximation method. Our results show that phonons play an important role in the mechanism of phase transition and in the instability of B4 (wurtzite) just before the pressure of transition. At zero pressure our data agree well with recently reported experimental results.     

Structural stability and electronic properties of AgInS<Subscript>2</Subscript> under pressure

We employ state-of-the-art ab initio density functional theory techniques to investigatethe structural, dynamical, mechanical stability and electronic properties of the ternaryAgInS₂ compoundsunder pressure. Using cohesive energy and enthalpy, we found that from the six potentialphases explored, the chalcopyrite and the orthorhombic structures were very competitive aszero pressure phases. A pressure-induced phase transition occurs around 1.78 GPa from the low pressure chalcopyritephase to a rhombohedral RH-AgInS₂ phase. The pressure phase transition around 1.78 GPa isaccompanied by notable changes in the volume and bulk modulus. The calculations of thephonon dispersions and elastic constants at different pressures showed that thechalcopyrite and the orthorhombic structures remained stable at all the selected pressure(0, 1.78 and 2.5 GPa), where detailed calculations were performed, while the rhombohedralstructure is only stable from the transition pressure 1.78 GPa. Pressure effect on thebandgap is minimal due to the small range of pressure considered in this study. Themeta-GGA MBJ functional predicts bandgaps which are in good agreement with availableexperimental values.     

Structural stability and phase transitions in K8Si46 clathrate under high pressure

The structural stability of type-I K8Si46 clathrate has been investigated at high pressure by synchrotron x-ray diffraction. In contrast to that observed in the Na-doped structure-II analogue [A. San-Miguel, Phys. Rev. Lett. 83, 5290 (1999)]], no phase separation into the beta-Sn Si structure was identified at 11 GPa. Instead, K8Si46 is found to undergo a transition to an isostructural positional disordered phase at around 15 GPa. Ab initio phonon band structure calculations reveal a novel phenomenon of phonon instabilities of K atoms in the large cavities is responsible for this transition. Above 32 GPa, the new structure transforms into an amorphous phase.     

Structural transitions in NaNH_2 via recrystallization under high pressure

Multiple phase transitions are detected in sodium amide(NaNH_2), an important hydrogen storage material, upon compression in diamond anvil cells(DAC) by using Raman spectroscopy and x-ray diffraction(XRD) measurements.Additional Bragg reflections appear on lower and higher angle sides of the original ones at ～1.07 GPa and 1.84 GPa,accompanied by obvious changes in Raman spectroscopy, respectively.It reveals that NaNH_2 undergoes the high-pressure phase sequence(α–β–γ) up to 20 GPa at room temperature.Spectral analysis indicates an orthorhombic structure with PBAN space group for the γ phase.We also experimentally observe high pressure induced recrystallization in alkaline amide compounds for the first time.     

高温高压下钙钛矿晶体结构变化

最近高压单晶X射线衍射实验明确显示正交晶系（Pbnm或Pnma）（钙钛矿）ABO3的高压压缩行为完全由晶体框架结构（framework）中的BO6八面体和AO12多面体的相对压缩性所确定,即对一些钙钛矿晶体,BO6较AO12多面体更易压缩时,压力导致晶体结构向高对称性结构演变;对另外一些钙钛矿,BO6较AO12多面体更不易压缩时,压力导致晶体结构向低对称性结构演变.基于价键匹配关系假设,建立多面体压缩率之间关系：βB/βA=MA/MB,由价键参数和常压晶体结构数据计算参量Mi,可以估计BO6和AO12多面体的相对压缩率,从而正确地预言高压压缩行为.文章最后引入高温高压钙钛矿倾斜相变的一般性规律,即MA/MB＞1时,相变温度和高压关系为dTc/dP＜0,当MA/MB＜1时,dTc/dP＞0。     

First-principles calculations of structural stability and mechanical properties of tungsten carbide under high pressure

The structural stability and mechanical properties of WC in WC-, MoC- and NaCl-type structures under high pressure are investigated systematically by first-principles calculations. The calculated equilibrium lattice constants at zero pressure agree well with available experimental and theoretical results. The formation enthalpy indicates that the most stable WC is in WC-type, then MoC-type finally NaCl-type. By the elastic stability criteria, it is predicted that the three structures are all mechanically stable. The elastic constants C_ij, bulk modulus B, shear modulus G, Young?s modulus E and Poisson?s ratio ν of the three structures are studied in the pressure range from 0 to 100 GPa. Furthermore, by analyzing the B/G ratio, the brittle/ductile behavior under high pressure is assessed. Moreover, the elastic anisotropy of the three structures up to 100 GPa is also discussed in detail.     

Structural and optical properties of InSe under pressure

Abstract

We have investigated the high pressure behavior of InSe by x-ray powder diffraction and optical measurements. The rhombohedral γ-polytype of InSe (space group R3m) exhibits a strongly anisotropic compressibility characteristic of the layer-type structure. Mode Gruneisen parameters of intralayer modes have been determined by Raman scattering. At 10.3(5) GPa InSe undergoes a phase transition to the rocksalt structure, which remains stable up to at least 30 GPa. Optical reflectivity measurements show the cubic high pressure phase to have metallic character.     

"Devil's staircase"-type phase transition in NaV2O5 under high pressure

The "devil's staircase"-type phase transition in the quarter-filled spin-ladder compound NaV2O5 has been discovered at low temperature and high pressure by synchrotron radiation x-ray diffraction. A large number of transitions are found to successively take place among higher-order commensurate phases with 2a x 2b x zc type superstructures. The observed temperature and pressure dependence of modulation wave number q(c), defined by 1/z, is well reproduced by the axial next nearest neighbor Ising model. The q(c) is suggested to reflect atomic displacements presumably coupled with charge ordering in this system.     

Electronic and thermodynamic properties of ReB2 under high pressure and temperature

First-principles calculations of the crystal structures of rhenium diboride (ReB₂) have been carried out with the plane-wave pseudopotential density functional theory method. The calculated values are in very good agreement with experimental data as well as with some of the existing model calculations. The quasi-harmonic Debye model, using a set of total energy versus molar volume obtained with the first-principles calculations, is applied to the study of the thermal and vibrational effects. The structural parameters, thermal expansions, heat capacities, Grüneisen parameters and Debye temperatures dependence on the temperature and pressure are obtained in the whole pressure range from 0 to 70 GPa and temperature range from 0 to 2000 K as well as compared with available data.     

Structural investigation of high-tc superconductors under high pressure

Abstract

The results of X-ray investigations of Tl₂Ba₂Ca₂Cu₃O₁₀ show a preferential c-axis decrease under high pressure, leading to a bulk modulus of B = 1370 kbar at 300 K. The results are compared to previous investigations of La₂CuO₄, La_1.8Sr_0.2CuO₄ and Pr₂CuO₄, that show a similar linear compressibility in a- and b- axis direction. The linear compressibility in c-axis direction is dominated by the degeneration of the Cu-O octohedra and by the compressibility of intercalated layers.     

Structural and thermodynamic properties of WB at high pressure and high temperature

The structure parameters and electronic structures of tungsten boride (WB) have been investigated by using the density functional theory (DFT). Our calculating results display the bulk modulus of WB are 352±2 GPa (K′₀=4.29) and 322±3 GPa (K′₀=4.21) by LDA and GGA methods, respectively. We have analyzed the probable reason of the discrepancy from the bulk modulus between theoretical and experimental results. The compression behavior of the unit cell axes is anisotropic, with the c-axis being more compressible than the a-axis. By analyzing the bond lengths information, it also demonstrated that WB has a lower compressibility at high pressure. From the partial densities of states (PDOS) of WB, we found that the Fermi lever is mostly contributed by the d states of W atom and p states of B atom and that the contributions from the s, p states of W atom and s states of B atom are small. Moreover, using the Gibbs 2 program, the thermodynamic properties of WB are obtained in a wide temperature range at high pressure for the first time in this work.     

Thermodynamic properties of OsB under high temperature and high pressure

The energy-volume curves of OsB have been obtained using the first-principles plane-wave ultrasoft-pseudopotential density functional theory (DFT) within the generalized gradient approximation (GGA) and local density approximation (LDA). Using the quasi-harmonic Debye model we first analyze the specific heat, the coefficients of thermal expansion as well as the thermodynamic Grüneisen parameter of OsB in a wide temperature range at high pressure. At temperature 300 K, the coefficients of thermal expansion α_V by LDA and GGA calculations are 1.67×10⁻⁵ 1/K and 2.01×10⁻⁵ 1/K, respectively. The specific heat of OsB at constant pressure (volume) is also calculated. Meanwhile, we find that the Debye temperature of OsB increases monotonically with increasing pressure. The present study leads to a better understanding of how the OsB materials respond to pressure and temperature.