Megabar-pressure infrared study of hydrogen deuteride

Solid hydrogen deuteride (HD) has been studied to a pressure of 159 GPa and to low temperatures using near infrared spectroscopy. Of the two high pressure phases observed in hydrogen and deuterium, known as the BSP (broken-symmetry phase) and the A phase, only the BSP had been observed in the lower pressure region of the phase line of HD and it was unusually different from the homonuclear diatomic species with a reentrant behavior. In this Letter the BSP phase line is identified to its maximum pressure of 159 GPa. Infrared absorption reveals a transition to the A phase, observed for the first time in HD with onset at 157+/-3 GPa. A new phase of electric dipolar order that should occur at low temperature is discussed.     

X-ray diffraction and infrared spectroscopy of monazite-structured CaSO4 at high pressures: Implications for shocked anhydrite

X-ray diffraction and infrared spectroscopy of CaSO₄ are conducted to pressures of 28 and 25 GPa, respectively. A reversible phase transition to the monoclinic monazite-structure occurs gradually between 2 and ∼5 GPa with a highly pressure-dependent volume change of ∼6-8%. A second-order fit of the X-ray data to the Birch-Murnaghan equation of state yields a bulk modulus (K) of 151.2 (±21.4) GPa for the high-pressure monoclinic phase. In the high-pressure infrared spectrum, the infrared-active asymmetric stretching and bending vibrations of the sulfate tetrahedra split at the phase transition, in accord with the results of factor group analysis. Additionally, the tetrahedral symmetric stretching vibration, which is weak in the anhydrite phase, becomes strongly resolved at the transition to the monazite structure. The infrared results indicate that the sulfate tetrahedra are more distorted in the monazite-structured phase than in anhydrite. Kinetic calculations indicate that the anhydrite to monazite transformation may generate the phase transition observed near 30 GPa under shock loading in CaSO₄. Our results indicate that the anhydrite- and monazite-structured phases may be the only phases that occur under shock loading of CaSO₄ to pressures in excess of 100 GPa.     

First-order isostructural Mott transition in highly compressed MnO

We present evidence for an isostructural, first-order Mott transition in MnO at 105+/-5 GPa, based on high-resolution x-ray emission spectroscopy and angle-resolved x-ray diffraction data. The pressure-induced structural and spectral changes provide a coherent picture of MnO phase transitions from paramagnetic B1 to antiferromagnetic distorted B1 at 30 GPa, to paramagnetic B8 at 90 GPa, and to diamagnetic B8 at 105+/-5 GPa. The last is the Mott transition, accompanied by a significant loss of magnetic moment, an approximately 6.6% volume collapse and the insulator-metal transition as demonstrated by recent resistance measurements.     

Pressure Study on New Superconducting Germanium Clathrates

We investigate the low temperature properties of the recently discovered clathrates Ba 6 Ge 25 and Na 2 Ba 4 Ge 25 by tuning both materials with hydrostatic pressure. At ambient pressure, Ba 6 Ge 25 undergoes a two-step structural phase transition between 230 K and 180 K from metallic behavior to a high-resistivity state. A superconducting transition occurs at T_{C}\approx 0.24\,\hbox{K} out of the resulting bad metal ( \rho_{0}\approx 1.5\,\hbox{m}\Omega\;\hbox{cm} ). With increasing pressure, the structural phase transition is shifted to lower temperature but T C increases drastically. T C reaches a maximum value of 3.85 K at the critical pressure p_{C}\approx 2.8\,\hbox{GPa} , where the structural distortion is completely suppressed and the system exhibits metallic behavior. On replacing 1/3 of the Ba atoms with Na (Na 2 Ba 4 Ge 25 ), no structural transformation is observed below room temperature, and the superconducting transition temperature is higher (T_{C}(p = 0) \approx 1.05\,\hbox{K}) than in the undoped case at ambient pressure but decreases slightly with increasing pressure.     

Effect of shear strain on the α-ε phase transition of iron: a new approach in the rotational diamond anvil cell

The effect of shear strain on the iron α-ε phase transformation has been studied using a rotational diamond anvil cell (RDAC). The initial transition is observed to take place at the reduced pressure of 10.8?GPa under pressure and shear operation. Complete phase transformation was observed at 15.4?GPa. The rotation of an anvil causes limited pressure elevation and makes the pressure distribution symmetric in the sample chamber before the phase transition. However, it causes a significant pressure increase at the centre of the sample and brings about a large pressure gradient during the phase transformation. The resistance to the phase interface motion is enhanced due to strain hardening during the pressure and shear operations on iron and this further increases the transition pressure. The work of macroscopic shear stress and the work of the pressure and shear stress at the defect tips account for the pressure reduction of the iron phase transition.     

Evidence of a fcc-hcp transition in aluminum at multimegabar pressure

The structure phase transition and the equation of state (EOS) of the third-period simple metal Al were investigated at pressure up to 333 GPa by powder x-ray diffraction experiments. The theoretically predicted fcc-hcp transition was observed at the reduced volume V/V0 of 0.509(1), corresponding to the pressure of 217+/-10 GPa. From the obtained pressure-volume data, the pressure derivative of the bulk modulus K0' for the EOS of fcc-Al was determined to be 4.83(3) by fitting to the Vinet formulation with a fixed value 72.7 GPa of K0 obtained from previous ultrasonic experiments.     

Experimental constraints on the phase diagram of elemental zirconium

The phase diagram of zirconium metal has been studied using synchrotron X-ray diffraction and time-of-flight neutron scattering at temperatures and pressures up to 1273 K and 17 GPa. The equilibrium phase boundary of the α-ω transition has a dT/dP slope of 473 K/GPa, and the extrapolated transition pressure at ambient temperature is located at 3.4 GPa. For the ω-β transition, the phase boundary has a negative dT/dP slope of 15.5 K/GPa between 6.4 and 15.3 GPa, which is substantially smaller than a previously reported value of −39±5 K/GPa in the pressure range of 32-35 GPa. This difference indicates a significant curvature of the phase boundary between 15.3 and 35 GPa. The α-ω-β triple point was estimated to be at 4.9 GPa and 953 K, which is comparable to previous results obtained from a differential thermal analysis. Except for the three known crystalline forms, the β phase of zirconium metal was found to possess an extraordinary glass forming ability at pressures between 6.4 and 8.6 GPa. This transformation leads to a limited stability field for the β phase in the pressure range of 6-16 GPa and to complications of high-temperature portion of phase diagram for zirconium metal.     

Observation of a pressure-induced first-order polyamorphic transition in a chalcogenide glass at ambient temperature

An apparently first-order polyamorphic transition has been observed with increasing pressure at ambient temperature in a molecular glass of composition Ge(2.5)As(51.25)S(46.25) Raman spectroscopic measurements on pressure-quenched samples and in situ x-ray diffraction measurements indicate that this transition corresponds to a collapse of the ambient-pressure molecular phase to a high-pressure network phase. The high-pressure phase first appears at a pressure of approximately 8-9 GPa and the transformation becomes complete at approximately 14-15 GPa. Calorimetric measurements indicate that the low- and high-pressure phases are thermodynamically distinct and that they coexist in the transition range.     

Novel gamma-phase of titanium metal at megabar pressures

Group IV transition metals titanium, zirconium, and hafnium are expected to transform from an ambient hexagonal close packed (hcp, alpha-phase) to a body centered cubic (bcc, beta-phase) at high pressures. This transition path is usually facilitated by the occurrence of an intermediate hexagonal phase (distorted bcc, omega-phase). The existence of a bcc phase in zirconium and hafnium at high pressures has been known for the past ten years; however, its occurrence in titanium has been theoretically predicted but never observed. We report a novel unexpected transformation in titanium metal from an omega phase to an orthorhombic phase (distorted hcp, gamma-phase) at a pressure of 116+/-4 GPa.     

Pressure-induced phase transition(s) in KMnF3 and the importance of the excess volume for phase transitions in perovskite structures

We report a pressure-dependent investigation of KMnF(3) by x-ray diffraction up to 30 GPa. The results are discussed in the framework of Landau theory and in relation to the isostructural phase transition in SrTiO(3). The phase transition temperature near 186 K in KMnF(3) shifts to room temperature at a critical pressure of P(c) = 3.4 GPa; the pressure dependence of the transition point follows ΔP(c)/ΔT(c) = 0.0315 GPa K(-1). The transition becomes second order under high pressure, close to the tricritical point. The phase transition is determined by the rotation of MnF(6) octahedra with their simultaneous expansion along the rotation axis. The rotation angle was found to increase to 10.5° at 24 GPa. An additional anomaly was observed at higher pressure around 25 GPa, suggesting a further phase transition.     

A new structure of mercury under pressure

A reentrant trigonal (α)-Hg phase and a new hcp (δ)-Hg phase have been observed in energy dispersive X-ray diffraction measurements on mercury at room temperature and pressures up to 39 GPa. Studies at higher temperatures give first indications for a maximum in the α-β phase line at about 8(1) GPa and 380(10) K and an α-β-δ triple point at about 27(5) GPa and 180(20) K.     

Evidence of polymorphic transformations of Sn under high pressure

The high-pressure polymorphs and structural transformation of Sn were experimentally investigated using angledispersive synchrotron x-ray diffraction up to 108.9 GPa. The results show that at least at 12.8 GPa β-Sn→bct structure transformation was completed and no two-phase coexistence was found. By using a long-wavelength x-ray, we resolved the diffraction peaks splitting and discovered the formation of a new distorted orthorhombic structure bco from the bct structure at 31.8 GPa. The variation of the lattice parameters and their ratios with pressure further validate the observation of the bco polymorph. The bcc structure appears at 40.9 GPa and coexists with the bco phase throughout a wide pressure range of40.9 GPa–73.1 GPa. Above 73.1 GPa, only the bcc polymorph is observed. The systematically experimental investigation confirms the phase transition sequence of Sn as β-Sn→bct→bco→ bco + bcc→bcc upon compression to 108.9 GPa at room temperature.     

氨的半水合物的高压拉曼光谱研究

在室温条件下, 利用金刚石对顶砧超高压技术, 对氨的半水合物(2NH3·H2O) 进行了原位高压拉曼光谱研究, 采用红宝石荧光压标测压, 实验的最高压力为41.0 GPa。装入金刚石对顶砧样品腔的初始样品为液态的氨的半水合物, 当压力达到3.5 GPa时, 显微镜下观察到整个样品腔内均匀的出现块状晶体, 同时, 测量到的拉曼谱上出现许多新的拉曼峰。因此, 我们判断在此压力下液态的2NH3·H2O发生了液固相变。当压力增加到19.0 GPa左右时, 2NH3·H2O的拉曼频移随压力变化的曲线有拐点, 并且具有软化特性的N-H伸缩振动模式消失。我们分析这是因为在高压下, 通过O-H…N成键的II型氨分子发生了旋转, 所以2NH3·H2O在此压力下发生了一次固固相变。     

Mn effect on wurtzite-to-cubic phase transformation in ZnO

Mn doping effect on a wurtzite-to-cubic phase transformation in ZnO has been investigated by in situ high pressure X-ray powder diffraction using synchrotron radiation. Unit cell expansion is clearly observed in Mn-doped ZnO samples. Mn ions sit at Zn site in the wurtzite structure. The onset transition pressure for the wurtzite-to-cubic phase transformation decreases from about 9.5 GPa for pure ZnO to 6 GPa for sintered 2at.% Mn-doped ZnO while the compressibility and volume collapse at transition pressures are not sensitive to the Mn doping in the wurtzite phase. The doping of Mn ions in ZnO increases the onset transition pressure for the cubic-to-wurtzite phase transformation. The results could be explained by a reduction of phase transformation barriers for both transition paths by the Mn doping. The observation of reduction of the wurtzite-to-cubic phase transformation pressure might point out a new direction to synthesize cubic wurtzite phase of ZnO by doping transition element(s).     

超高压下碘的结构相变

 采用DAC高压X光技术，在320 GPa压力下，对碘进行了结构相变的研究。用耐腐蚀材料Mo作封垫，在室温和无保护气氛下装样。采用Mo内标和红宝石荧光测量进行压力校准。结果表明，在21 GPa时，开始发生结构相变，由面心正交相（Ⅰ相），转变为体心正交相（Ⅱ相），体积缩小2%左右。在21~25 GPa之间为两相共存区；在25 GPa以上完全转变为新的高压单相（Ⅱ相）。此相变为可逆相变。     

纳米ZnO在高压下的性质与结构研究

 在金刚石压砧上测量了20 nm的ZnO和体相粉末ZnO的电阻-压力关系。研究结果表明，20 nm的ZnO在7.9 GPa 压力时出现了相变，而体相粉末ZnO在5 GPa 时有相变发生。虽然粒径小的相变压力大于粒径大的，但与以前关于体相粉末ZnO所报道的文献结果有所不同。文中对此作了解释，并对纳米ZnO在压力下的畴破裂进行了研究。     

Pressure-induced magnetization in FeO: evidence from elasticity and Mössbauer spectroscopy

The complete elastic tensor of Fe0.94O (wüstite) has been determined to 10 GPa using acoustic interferometry at GHz frequencies inside a diamond-anvil cell. The soft mode (C44) elastic constant of FeO is reduced by 20% over the experimental pressure range. An unusual discontinuity in the pressure derivatives of C11 and C12 at 4.7+/-0.2 GPa corresponds to the pressure at which the onset of a magnetic ordering transition is observed by high-pressure M?ssbauer spectroscopy and neutron powder diffraction. Our new results combined with literature structural high P-T data suggest that there is a magnetic, although still cubic, phase of FeO between approximately 5 and approximately 17 GPa.     

Phonon spectrum of a naphthalene crystal at a high pressure: Influence of shortened distances on the lattice and intramolecular vibrations

The Raman spectra of a naphthalene crystal have been measured at room temperature in the pressure range up to 20 GPa. The pressure shift and Grüneisen parameters for intermolecular and intramolecular phonons have been determined. The maximum rate of the pressure shift for intermolecular phonons is 44 cm^?1/GPa, and the rate of the pressure shift for intramolecular phonons lies in the range from 1 to 11 cm^?1/GPa for different modes. The pressure dependence of the phonon frequencies for direct and inverse pressure variations has a hysteresis in the pressure range from 2.5 to 16.5 GPa. It has been shown that the linear dependence of the intermolecular phonon frequency on the crystal density has a peculiarity, which indicates a possible phase transition at a pressure of 3.5 GPa. The pressure dependence of intramolecular phonons related to the stretching vibrations of hydrogen atoms exhibits features that are characteristic of intermolecular phonons, which is associated with the influence of shortened distances between the hydrogen atoms of the neighboring molecules on the intermolecular interaction potential.     

Elastic phase transitions in metals at high pressures

The elastic phase transitions of cubic metals at high pressures are investigated within the framework of Landau theory. It is shown that at pressures comparable with the magnitude of the bulk modulus the phase transition is connected with the loss of stability relative to uniform deformation of the crystalline lattice. Discontinuity of the order parameter at the transition point and its equilibrium value are expressed through the second-?to fourth-order elastic constants. The second-,third-?and fourth-order elastic constants and phonon dispersion curves of vanadium under hydrostatic pressure are obtained by first-principles calculations. Structural transformation in vanadium under pressure is studied using the obtained results. It is shown that the experimentally observed at P?≈?69?GPa phase transition in vanadium is the first-order phase transition close to a second-order phase transition.     

High-pressure phases of plutonium monoselenide studied by X-ray diffraction

Abstract

Plutonium monoselenide was studied under high pressure up to 47 GPa, at room temperature, using a diamond anvil cell in an energy dispersive X-ray diffraction facility. At ambient pressure, PuSe has the NaC1-type (B1) structure. The compound has been found to undergo a second-order crystallographic phase transition at around 20 GPa. This phase can be described as a distorted B1 structure, with a rhombohedral symmetry. PuSe transforms to a new phase at around 35 GPa, which can be indexed in the cubic CsCl-type (B2). The volume collapse at this phase transition is 11%. When releasing pressure, we observed a strong hysteresis to the inverse transformation down to 5 GPa. From the pressure-volume relationship, the bulk modulus has been determined to B ₀ = 98 GPa and its pressure derivative as B ₀ = 2.6. These results are compared to those obtained with other actinide monmictides and monochalcogenides.