High-pressure organic synthesis

Abstract

Some important problems of organic synthesis and ways to solve them by the use of hgh pressure are the topic of this paper. Three representative groups of organic reactions, cycloadditions, simple additions, and nucleophilic and electrophilic substitutions, illustrate the possibilities and usefulness of the high-pressure technique in organic synthesis. Moreover, applications of high-pressure methodology to syntheses of natural products are described. Examples are given of the influence of pressure on organic reactions in the following essential aspects: acceleration of the reaction rate, modification of regio-and stereochemistry, and changes in the reaction equilibrium.     

High pressure phase transitions in organic solids I:α → β transition in resorcinol

An experimental program has been started to study polymorphic phase transitions under pressure in organic solids using the Be gasketing technique developed by us. This allows us to obtain x-ray diffraction patterns of low symmetry organic solids with high resolution, employing CuK _α radiation. The first organic solid studied is α-resorcinol. At 0.5 GPa, it transforms to its high temperature and denser modification, β-resorcinol. The transformation mechanism is discussed with the help of molecular packing calculations.     

Evidence for vacancy-driven phase transitions in BaMnF 4 at elevated temperatures

Anomalies near 370 K and/or 400 K in dielectric constant, diffuse x-ray scattering, C₁₁ elastic coefficient, electrical conductivity, and piezoelectric resonance have been reported for BaMnF ₄. Particularly curious is the dielectric constant along the ac-diagonal, which rises from 15 at 300 K to a sharp peak of 73 at 400 K. These anomalies are discussed in terms of 2D ionic conduction mechanisms (fluorine vacancy hopping), and the disappearance of short-range antiferroelectric order at temperatures above 400 K. At 650 K the crystals lose all piezoelectricity, which is interpreted as a 3D vacancy-driven C_2v – D_2h, transition.     

Crystalline structures as an approximant of quasicrystal and distortion of B12 icosahedron in boron-rich solids: Search for semiconducting quasicrystal

Analyzing the crystalline structure of α- and β-rhombohedral boron as an approximant structure of a quasicrystal, atomic structures of two unit cells (prolate and oblate rhombohedra) of icosahedral quasicrystal are constructed. According to molecular orbital calculation, a neutral B ₁₂ H ₁₂ icosahedral cluster is distorted to a cubic or rhombohedral type by the Jahn–Teller effect. The distortion of B ₁₂ in the β-rhombohedral boron and K₂B₁₂H₁₂ has the same sign as the lowest energy distortion in the calculation. Among the α-rhombohedral type structures, the distortion of B₁₂ is correlated with the rhombohedral axis angle, and the angle is the closest to the icosahedral angle for B₆O and the distortion is the smallest for B–C. A meta-stable phase has been found on the way towards crystallization of amorphous B–C films.     

High-pressure structures of InBi predicted by particle swarm optimization algorithm

We extensively explore the high-pressure structures of InBi by using a newly developed particle swarm optimization algorithm. An orthorhombic Imma structure is discovered to be stable from 43.7 GPa to 107.9 GPa, ruling out the previously speculated cubic structure. Further increasing the pressure, we find a tetragonal P4/nmm structure which is energetically more favourable from 107.9 GPa to 200 GPa. Especially, the tetragonal P4/nmm structure is known to occur at high pressure in the structures of ZnO and MgTe. We also predict this structure to be a high-pressure structure of ZnTe. Thus the tetragonal P4/nmm structure may be a universal high-pressure structure of the Ⅱ-Ⅵ and the Ⅲ-Ⅴ compounds.     

Limiting long-range-ordered solids to finite sizes in condensed-matter physics

We have examined some of the consequences of finite size effects in solids which exhibit cooperative behaviour. These are materials with long-range interactions based on ferromagnetism, ferroelectricity, and superconductivity. Limiting the range of interaction is achieved by creating nanocrystals, nanodomains, disorder, high-concentration solid solutions and submicron microstructure in sintered compacts. The attempt is to elucidate underlying principles essential at a microscopic level for each of the three phenomena. Not much work has been reported in this area earlier and most of the results are from our own studies. Some of the work is reported for the first time. The experimental techniques used are Mössbauer, Raman and infrared spectroscopies, high-temperature x-ray diffraction, electron energy loss spectroscopy, dielectric and piezoelectric response, ferromagnetic resonance and spinwave dispersion, 4-probe resistivity, DC & AC magnetic susceptibilities and differential scanning calorimetry.     

On phase diagrams and on cBN formation in the system BN-Ca3B2N4

Abstract

The phase diagrams of Ca₃B₂N₄ and of the system BN-Ca₃B₂N₄ has been studied by high pressure differential thermal analysis Ca₃B₂N₄ has 3 structural phases and melts at higher temperature. The system BN-Ca₃B₂N₄ formes an eutectic melt and cBN is synthesized by nucleation and crystal growth.     

Measurements of compressibility of solids and powder compacts by a strain gauge technique at hydrostatic pressure up to 9GPa

Abstract

An experimental technique is described which enables one to measure the pressure-volume (P-V) relationship of solids and powder compacts and the linear compressibility of anisotropic single crystals by means of the resistive strain gauges at hydrostatic pressure up to 9 GPa. The potential of this technique is demostrated for solids possessing pressure induced phase transitions (PbTe, SmSe) and anisotropic crystals (Sb). For the first time P-V relationship is measured for highly compressible powder compact at increase and decrease of pressure.     

Nonequilibrium states of driven disordered polymorphic solids

Condensed matter systems, when driven far from equilibrium, often exhibit a far more varied set of phases than their equilibrium counterparts. The existence of non-equilibrium analogs of ‘solids’ and ‘liquids’ has been demonstrated earlier in the context of models for driven disordered vortex lattices in superconductors. Here we study the effects of a structural (polymorphic) transition in a driven two-dimensional crystal placed in a quenched random background. Such a polymorphic crystal is shown to exhibit a complex sequence of unusual dynamical phases as the external drive is varied, including some which have no analog in the undriven pure system. We propose that such states should be accessible in experiments.     

High-pressure spectroscopic studies of free and self-trapped excitons in alkali halides at low temperatures

Abstract

A brief survey of our studies of free and self-trapped excitons (FE and STE) in alkali halide crystals under hydrostatic pressure up to 12.5 kbar at 4.2–140 K is presented. Main attention is paid to the following effects observed: (1) the strong coupling of three energy levels of FE in CsI revealing itself as an exciton analog of pressure-scanned Fermi resonance; (2) emergence of a new emission band of STE in CsI under pressure; (3) a large pressure shift of the thermal quenching curve for STE emission in NaCl.     

高温高压下钠长石的阻抗谱实验研究

 在压力为1.0、2.0 GPa和温度为673～973 K条件下,采用交流阻抗谱法在YJ-3000t紧装式六面顶高压设备上原位测量了钠长石的电导率。实验结果表明：在实验的温度和压力范围内,钠长石的电导率在10^-3.0～10^-5.5 S/m变化;钠长石复阻抗的模和相角对频率有很强的依赖性;随着温度T升高,钠长石的电阻率迅速减小,电导率σ增大,并且lg σ与T^-1之间符合Arrhenius关系;在实验压力范围内,随着压力升高,钠长石的电导率降低。采用离子导电机制,对高温高压下钠长石的导电行为进行了合理解释。     

Pressure induced phase transformations and band structure of different high pressure phases in tellurium

We report here high-pressure x-ray diffraction (XRD) studies on tellurium (Te) at room temperature up to 40 GPa in the diamond anvil cell (DAC). The XRD measurements clearly indicate a sequence of pressure-induced phase transitions with increasing pressure. The data obtained in the pressure range 1 bar to 40 GPa fit five different crystalline phases out of Te: hexagonal Te (I) → monoclinic Te(II) → orthorhombic Te (III) → Β-Po-type Te(IV) → body-centered-cubic Te(V) at 4, 6.2, 11 and 27 GPa, respectively. The volume changes across these transitions are 10%, 1.5%, 0.3% and 0.5%, respectively. Self consistent electronic band structure calculations both for ambient and high pressure phases have been carried out using the tight binding linear muffin tin orbital (TB-LMTO) method within the atomic-sphere approximation (ASA). Reported here apart from the energy band calculations are the density of states (DOS), Fermi energy (E _f) at various high-pressure phases. Our calculations show that the ambient pressure hexagonal phase has a band gap of 0.42 eV whereas high-pressure phases are found to be metallic. We also found that the pressure induced semiconducting to metallic transition occurs at about 4 GPa which corresponds to the hexagonal phase to monoclinic phase transition. Equation of state and bulk modulus of different high-pressure phases have also been discussed.     

High-pressure structural properties of tetramethylsilane

High-pressure structural properties of tetramethylsilane are investigated by synchrotron powder x-ray diffraction at pressures up to 31.1 GPa and room temperature. A phase with the space group of Pnma is found to appear at 4.2 GPa. Upon compression, the compound transforms to two following phases: the phase with space groups of P2_1/c at 9.9 GPa and the phase with P2/m at 18.2 GPa successively via a transitional phase. The unique structural character of P2_1/c supports the phase stability of tetramethylsilane without possible decomposition upon heavy compression. The appearance of the P2/m phase suggests the possible realization of metallization for this material at higher pressure.     

高温高压下闪锌矿相GaN结构和热力学特性的分子动力学研究

利用分子动力学方法和Buckingham经验势模型对重要半导体材料GaN立方闪锌矿相的晶格常数、相变压力(从闪锌矿到岩盐结构)、热膨胀、等温体模量、定压热容等结构和热力学特性在300—3000K的温度范围和0—65GPa的压力范围内进行了研究.研究表明，闪锌矿相GaN常态下的结构和热力学参数的模拟结果与实验数据及其他理论结果相符.同时在所选作用势模型可靠性检验的基础上，对等温体模量、定压热容诸非谐性参量在高温高压下的热力学行为进行了预测.所得结果在材料科学等领域的研究中具有一定的应用背景和参考价值. 关键词： GaN Buckingham势 分子动力学模拟 高温高压     

Enhanced hardness of CVD diamond after high pressure and high-temperature treatments

The diamond thick layers prepared using chemical vapor deposition (CVD) methods have been treated at high pressures and high temperatures (HP-HT). It was found that the Vickers hardness of the HP-HT treated bulks was nearly two times as high as that of the starting CVD diamond samples. The hardness of the samples treated at 8?GPa and 1800°C is ～80?GPa at a loading force of 49?N, close to that of the single-crystal diamond (～100?GPa). In addition, the oxidation resistance of CVD diamond samples was also enhanced greatly after HP-HT treatments, and the diamondization of sp² bonded carbon in the CVD diamond samples could occur at 7–8?GPa and 1600–1800°C. The HP-HT conditions of diamondization in our works are much lower than the case of the graphite-to-diamond direct transformation without the presence of catalyst (>15?GPa and 2000°C).     

A fiber-array probe technique for measuring the viscosity of a substance under shock compression

A fiber-array probe is designed to measure the damping behavior of a small perturbed shock wave in an opaque substance, by which the effective viscosity of substance under the condition of high temperature and high pressure can be constrained according to the flyer-impact technique. It shows that the measurement precision of the shock arrival time by using this technique is within 2 ns. To easily compare with the results given by electrical pin technique, the newly developed method is used to investigate the effective viscosity of aluminum （Al）. The shear viscosity coefficient of A1 is determined to be 1700 Pa.s at 71 GPa with a strain rate of 3.6× 10^6 s-1, which is in good agreement with the results of other methods. The advantage of the new technique over the electrical pin one is that it is applicable for studying the non-conductive substances.     

High-pressure phase transitions of TiN: an ab initio constant pressure study

An ab initio constant pressure molecular dynamics technique is carried out to explore the behaviour of rock salt-structured titanium nitride (TiN) under pressure. Two successive phase transformations are successfully observed in the dynamical simulations. The first one is an isostructural phase transition accompanied by an anomalous volume compression without any symmetry breaking. The second one is a reconstructive phase transformation into a CsCl-type structure. For the first time, the previously proposed two-phase transformations for TiN are confirmed through the simulations.     

High-pressure,high-temperature thermophysical measurements on tungsten

Abstract

Wire shaped tungsten samples (0.25 mm diameter, 40 mm length, 99.97%) are resistively pulse heated as part of a coaxially built up capacitor discharge circuit. With heating rates of more than 10⁹ K/s, temperatures up to 12000 K are reached. The tungsten wire is contained with the surrounding medium water in a high pressure vessel with sapphire windows and a maximum pressure capability of 0.5 GPa. Time correlated measurements of the current through the wire and the voltage drop across it as well as surface radiation and wire expansion can be performed simultaneously and allow the determination of thermophysical properties for the liquid tungsten (see key words). All measuring systems have rise times less than 10 ns.