Reconstructive structural phase transitions in dense Mg

The question raised recently about whether the high-pressure phase transitions of Mg follow a hexagonal close-packed (hcp) → body centered cubic (bcc) or hcp → double hexagonal close-packed (dhcp) → bcc sequence at room temperature is examined by the use of first principles density functional methods. Enthalpy calculations show that the bcc structure replaces the hcp structure to become the most stable structure near 48 GPa, whereas the dhcp structure is never the most stable structure in the pressure range of interest. The characterized phase-transition mechanisms indicate that the hcp → dhcp transition is also associated with a higher enthalpy barrier. At room temperature, the structural sequence hcp → bcc is therefore more energetically favorable for Mg. The same conclusion is also reached from the simulations of the phase transitions using metadynamics methods. At room temperature, the metadynamics simulations predict the onset of a hcp → bcc transition at 40 GPa and the transition becomes more prominent upon further compression. At high temperatures, the metadynamics simulations reveal a structural fluctuation among the hcp, dhcp, and bcc structures at 15 GPa. With increasing pressure, the structural evolution at high temperatures becomes more unambiguous and eventually settles to a bcc structure once sufficient pressure is applied.     

HIGH pressure structural investigations of zirconium using LMTO method

Abstract

The structural energy differences have been calculated for zirconium as a function of pressure at zero temperature using the Andersen force theorem and the linear muffin tin orbital method. The structures included are the following: α (hcp), the room temperature room pressure phase, ω- a three atom simple hexagonal, bcc and fcc. Our calculations show that the bcc structure would become energetically most favourable above 11 GPa. This results is in agreement with well known correlation between the crystal structure and the d-electron population in transition metals at normal volume. The diamond anvil cell based high pressure x-ray diffraction experiments are in progress to verify this result.     

单轴应变驱动铁bcc—hcp相转变的微观模拟

用分子动力学方法模拟了沿〈001〉晶向应变加载和卸载情况下单晶铁中体心立方(bcc)与六方密排(hcp)结构的相互转变,分析了相变的可逆性和微结构演化特征.微观应力的变化显示样品具有超弹性性质,而温度变化表明在相变和逆相变过程中均出现放热现象.相变起始于爆发式均匀形核,晶核由块状颗粒迅速生长为沿{011}晶面的片状分层结构; 而卸载逆相变则从形核开始就呈现片状形态,且相界面晶面指数与加载相变完全一致,表现出形态记忆效应.在两hcp晶核生长的交界面易形成面心立方(fcc)堆垛层错. fcc通过在hcp晶粒内     

The effect of silicon impurities on the phase diagram of iron and possible implications for the Earth's core structure

The hexagonal-close-packed (hcp) structure is the accepted stable form of pure iron (Fe) under Earth's core conditions. Recently, however, a body-centred-cubic (bcc) phase of iron alloyed with lighter elements has been proposed. At relatively modest conditions, experiments have shown that small amounts of silicon (Si) can stabilise the bcc phase with respect to the hcp phase. This result has motivated our present study examining the effect of silicon on the bcc-hcp phase transition. We have performed ab initio calculations on both phases at zero Kelvin; our results are in good agreement with experiment. Extending our results to core pressures and taking into account previous studies of pure iron at core temperatures, we conclude that the bcc phase of iron alloyed with silicon is likely to be the stable crystalline phase in the inner core.     

单轴应变条件下Fe从α到ε结构相变机制的第一性原理计算

采用基于密度泛函理论的平面波赝势方法,研究了沿［001］方向单轴应变条件下Fe从体心立方结构(bcc,α相)到六角密排结构(hcp,ε相)相变的临界压力、相变路径、相变势垒以及相变过程中原子磁性的变化.结果发现:单轴应变条件下Fe从α到ε结构的相变路径与以前理论计算模拟给出的静水压力条件下的相变路径明显不同;原子磁矩沿着相变路径突然降低,同时伴随着能量和体积的突然变化,是典型的一阶磁性相转变,表明原子磁性的丧失导致了bcc结构不稳定而向hcp结构转变.对单轴应变下吉布斯自由能的计算表明,相变势垒随着单轴应 关键词： 相变 单轴应变 第一性原理 铁     

第一性原理计算Fe从bcc到hcp结构的相变路径及其磁性边界

本文采用基于密度泛函理论的第一性原理方法,计算了压力作用下Fe从bcc到hcp结构相变的势能面、相变路径以及相变过程中的磁性相边界.结果表明:与Burgers路径不同,相变过程中bcc结构(110)bcc面的剪切和相对滑移相互耦合,并伴随有(110)bcc面间距的减小;这一相变机制可以解释Fe的静高压实验中在相变初期观察到的hcp结构异常.因此,并不需要像Wang和Ingalls提出的那样,在相变过程中引入一个亚稳定的fcc相来解释这些实验结果.对相变势能面的计算表明剪切对相变的发生有激活作用.此外,分析表明相变过程中涉及复杂的磁性转变,相变过渡态位置正好位于磁性相边界上,并对原子磁性对结构转变影响的物理机制进行了讨论.     

Magnetic ordering temperatures in rare earth metal dysprosium under ultrahigh pressures

Magnetic ordering temperatures in heavy rare earth metal dysprosium (Dy) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to a pressure of 69 GPa and a temperature of 10 K. Previous studies using magnetic susceptibility measurements at high pressures were able to track magnetic ordering temperature only till 7 GPa in the hexagonal close packed (hcp) phase of Dy. Our studies indicate that the magnetic ordering temperature shows an abrupt drop of 80 K at the hcp-Sm phase transition followed by a gradual decrease that continues till 17 GPa. This is followed by a rapid increase in the magnetic ordering temperatures in the double hcp phase and finally leveling off in the distorted face centered cubic phase of Dy. Our studies reaffirm that 4f-shell remains localized in Dy and there is no loss of magnetic moment or 4f-shell delocalization for pressures up to 69 GPa.     

Prediction of a bcc-hcp phase transition for Sn: A first-principles study

The high-pressure structural transformation of elemental Sn is studied using an ab initio density functional theory implementation of the metadynamics method that predicts with sufficient compression, Sn will transform from the bcc structure into an hcp structure. The low-free-energy pathway associated with this phase transition is characterized as the Burgers transition mechanism. The superconducting properties of Sn under pressure are also investigated. Both bcc and hcp structures of Sn exhibit very weak electron-phonon coupling and therefore would not sustain superconductivity at high pressure.     

一维应变加载下单晶铁结构转变的微观研究

采用嵌入原子势和分子动力学方法,模拟了单晶铁在一维应变条件下由体心立方（bcc）转变为六角密排（hcp）结构的微观过程. 当应变加载至相变临界值时,hcp相开始均匀形核并沿{011}晶面长大为薄片状体系.弹性常数C₃₁和C₃₂在相变前被逐渐硬化,C₃₃则在相变前出现软化行为;当体系完全相变后,上述各弹性常数显示开始随体积压缩而迅速硬化,温度效应对晶格具有软化作用,可削弱C₃₃的硬化和软化过程;样品在压缩过程可出现孪晶结构,孪晶结构使晶格发生剪切变形.混合相中,hcp相势能比bcc相高,最大剪应力方向与bcc相反向;系统的偏应力与hcp相质量分数近似呈线性关系. 关键词： 结构转变 分子动力学 一维应变     

Structural properties of complex (dusty) plasma upon crystallization and melting

A change in the local order of a bounded complex (dusty) plasma in the process of its crystallization and melting has been examined by molecular dynamics simulations. The dynamics of microparticles is considered in the framework of a Langevin thermostat, the pair interaction between charged particles is described by a screened Coulomb potential (Yukawa potential) with the hard wall potential as a confinement. It has been shown that the beginning of the crystallization of such a system is accompanied by the formation of clusters with the hexagonal close packed (hcp) structure; a noticeable number of these clusters are then transformed to the face centered cubic (fcc) phase. A plasma crystal formed after crystallization consists of the metastable hcp phase, fcc clusters, and a small number of clusters with a body centered cubic (bcc) crystal lattice. Beginning with a certain threshold value of the thermostat temperature, the number of fcc/bcc clusters decreases sharply with increasing temperature, which is an important signature of the beginning of the melting of the plasma crystal.     

室温下压致铁钴镍合金的bcc→hcp相变

 本文采用高压X光衍射方法在金刚石对顶压砧中在位地（in situ）研究了Fe₆₈Co₂₄Ni₈（wt%）合金在室温下的压致bcc→hcp结构相变和直到40.5 GPa的等温压缩行为。实验结果表明该合金在常压下为bcc结构，晶格常数a₀=(0.287 0±0.000 1) nm，体积V₀=(7.119±0.007) cm³/mol，密度ρ₀=(7.981±0.008) g/cm³；在20.9 GPa附近出现bcc→hcp结构相变，两相共存压力区约10 GPa，在此区域内有晶面间距d(002)_hcp=d(110)_bcc，且原子平面(002)_hcp//(110)_bcc，hcp相比bcc相体积减小(0.33±0.02) cm³/mol；高压相hcp结构的晶格参数比值c/a=1.608±0.004；相变后原子配位数的增加使得hcp相(002)平面内及(002)平面间的最近邻原子间距比bcc相最近邻原子间距分别增大约1.6%和0.5%；用Murnaghan状态方程对实验数据进行最小二乘法拟合，得到bcc相B₀=(130±13) GPa，B₀'=12.6±0.5；hcp相V₀=(6.62±0.04) cm³/mol，B₀=(243±21) GPa，B₀'=6.8±0.3；对于该合金的bcc→fcp相变时的结构转变机制做了详细的讨论。     

An ab initio molecular dynamics study of iron phases at high pressure and temperature

The crystal structure of iron, the major component of the Earth's inner core (IC), is unknown for the IC high pressure (P; 3.3-3.6 Mbar) and temperature (T; 5000-7000 K). There is mounting evidence that the hexagonal close-packed (hcp) phase of iron, stable at the high P of the IC and a low T, might be unstable under the IC conditions due to the impact of high T and impurities. Experiments at the IC P and T are difficult and do not provide a conclusive answer as regards the iron stability at the pressure of the IC and temperatures close to the iron melting curve. Recent theory provides contradictory results regarding the nature of the stable Fe phase. We investigated the possibility of body-centered cubic (bcc) phase stabilization at the P and T in the vicinity of the Fe melting curve by using ab initio molecular dynamics. Thermodynamic calculations, relying on the model of uncorrelated harmonic oscillators, provide nearly identical free energies within the error bars of our calculations. However, direct simulation of iron crystallization demonstrates that liquid iron freezes in the bcc structure at the P of the IC and T = 6000 K. All attempts to grow the hcp phase from the liquid failed. The mechanism of bcc stabilization is explained. This resolves most of the earlier confusion.     

非静水压条件下铁从α到ε结构相变的第一性原理计算

采用基于密度泛函理论的平面波赝势方法,研究了三轴加载的非静水压力和静水压力对铁从体心立方结构（bcc,α相）到六角密排结构（hcp,ε相）相变压力和磁性的影响,结果发现：在0—18 GPa压力范围内,相对静水压力条件,随着压力的升高,bcc结构的原子磁矩在非静水压力下降低得更快;在非静水压力下,相变更容易发生,相变压力随着非静水压力程度的增加而降低;并且对非静水压力对相变压力影响的物理机理进行了讨论. 关键词： 相变 非静水压力 第一性原理 铁     

Structural phase transitions in yttrium under ultrahigh pressures

X-ray diffraction studies were carried out on the rare earth metal yttrium up to 177?GPa in a diamond anvil cell at room temperature. Yttrium was compressed to 37% of its initial volume at the highest pressure. The rare earth crystal structure sequence hcp?→?Sm?type?→?dhcp?→?mixed(dhcp?+?fcc)?→?distorted fcc (dfcc) is observed in yttrium below 50?GPa. The dfcc (hR24) phase has been observed to persist in the pressure range of 50-95?GPa. A structural transition from dfcc to a low symmetry phase has been observed in yttrium at 99?±?4?GPa with a volume change of -?2.6%. This low symmetry phase has been identified as a monoclinic C2/m phase, which has also been observed in other rare earth elements under high pressures. The appearance of this low symmetry monoclinic phase in yttrium shows that its electronic structure under extreme conditions resembles that of heavy rare earth metals, with a significant increase in d-band character of the valence electrons and possibly some f-electron states near the Fermi level.     

Cold brittleness and fracture of metals with various crystal lattices: Dislocation mechanisms

The dislocation mechanisms of formation of the ductile–brittle transition temperature and the low-temperature brittle fracture of metals (single crystals, polycrystals) with various crystal lattices (bcc, fcc, hcp) are considered. The conditions of appearance of cold shortness and intracrystalline crack propagation (brittle fracture) are determined. These conditions can be met in bcc and some hcp metals and cannot be met in fcc and many hcp metals. The nondestructive internal friction (at 100 kHz) method is used to determine the temperature ranges of cold shortness (ductile–brittle transition temperatures) in bcc metals (ferritic–martensitic EK-181 steel, V–4Ti–4Cr alloy), which depend on their structure–phase state and strength (yield strength).     

Pressure-induced phase transition of BaH2 : Post Ni2In phase

Up to now a Ni₂In structure is a final step in the structural sequence of ionic AX₂ compounds under high pressure. Powder X-ray diffraction experiments on BaH₂ were performed at room temperature and high pressures up to 69 GPa. Successive phase transformations were observed to occur in two stages. The first was from the cotunnite to the Ni₂In structure at 2.5 GPa. The second transition commenced at pressures around 50 GPa and was completed at 65 GPa. At the transition the arrangement of a cation sublattice changes from an hcp to a simple hexagonal lattice. This is the first observation of the post Ni₂In phase.     

Lattice dynamics and phase diagram of aluminum at high temperatures

The dispersion of phonons in the fcc, hcp, and bcc phases of aluminum is calculated at ultrahigh pressures by the method of small displacements in a supercell. The stability of the phonon subsystem is studied. The thermodynamic characteristics are calculated in the quasi-harmonic approximation, and a phase diagram of aluminum is plotted. As compared to the Debye model, the use of a phonon spectrum calculated in the quasi-harmonic approximation significantly broadens the hcp phase field and strongly shifts the phase boundary between the fcc and bcc phases. The normal isentrope is calculated at megabar pressures. It is shown to intersect the fcc-hcp and hcp-bcc phase boundaries. The sound velocity along the normal isentrope is calculated. It is shown to have a nonmonotonic character.     

Monte Carlo and cell model calculations for the solid—fluid phase behaviour of the triangle-well model

Monte Carlo simulations and cell model calculations are reported for the vapour-liquid and solid-liquid phase behaviour of the triangle-well model system. The behaviour is examined as a function of the range of the triangle-well attraction, from 1.05 to 2.5 times the diameter of the hard core of the potential. Cell model calculations indicate that the stable solid is almost always face-centred cubic (fcc), except for a small set of conditions where hexagonal close-packed (hcp) is favoured. This outcome differs markedly from a much earlier study performed for the square-well model potential, where a much richer phase diagram was observed, with significant regions of stability for hep and body-centred cubic (bcc) phases. Monte Carlo simulations indicate that the cell model calculations represent well the true phase behaviour for this model system. The differing behaviour between the triangle-well and square-well models indicates an important role for the flatness of the potential well in governing the stability of hcp and bcc phases relative to the fcc phase.     

高温高压下钼的结构稳定性研究

以钼为代表的一系列过渡金属,在高温高压的相变及结构稳定性研究是实验和理论研究的热点.钼在常温常压下是bcc结构,但是在高温高压下可能的相结构一直未能确定.本文首先预测了几种高压下的结构,并计算了其自由能及力学性质.针对可能的hcp结构,我们通过新近发展的自洽晶格动力学方法,充分考虑声子间相互作用,成功获得了hcp结构高温高压声子色散曲线,结果表明hcp相在热力学及动力学上都是能够稳定存在的结构,是一种可能的高压相.