Structure of Rb-III: novel modulated stacking structures in alkali metals

The crystal structure of Rb-III, stable between 13 and 17 GPa, has been determined from quasi-single-crystal x-ray diffraction data. It is orthorhombic, space group C222(1), with 52 atoms in the unit cell, and has an 8-10-8-8-10-8 stacking of 8- and 10-atom layers. The recently reported 84-atom structure of Cs-III can be understood as an 8-8-10-8-8-8-8-10-8-8 stacking of the same layers. These represent a new class of modulated elemental structures.     

Predicted novel high-pressure phases of lithium

Under high pressure, "simple" lithium (Li) exhibits complex structural behavior, and even experiences an unusual metal-to-semiconductor transition, leading to topics of interest in the structural polymorphs of dense Li. We here report two unexpected orthorhombic high-pressure structures Aba2-40 (40 atoms/cell, stable at 60-80 GPa) and Cmca-56 (56 atoms/cell, stable at 185-269 GPa), by using a newly developed particle swarm optimization technique on crystal structure prediction. The Aba2-40 having complex 4- and 8-atom layers stacked along the b axis is a semiconductor with a pronounced band gap >0.8 eV at 70 GPa originating from the core expulsion and localization of valence electrons in the voids of a crystal. We predict that a local trigonal planar structural motif adopted by Cmca-56 exists in a wide pressure range of 85-434 GPa, favorable for the weak metallicity.     

Raman modes of metastable phases of Si and Ge

Abstract

We have measured Raman spectra of metastable phases of Si and Ge prepared in a diamond anvil cell for pressures up to 12 GPa. For Si we observe eight Raman lines with mode Grüneisen parameters varying between -0.3 and 1.5. These lines can be assigned to the zone-center phonons of the cubic BC8-structure (Z = 8) by assuming a violation of Raman selection rules presumably due to disorder. In the case or Ge we observe two phases with different Raman spectra. The spectrum of the first phase is strikingly similar to that of BC8-Si. Below about 5 GPa this phase transforms into a second phase, which can be identified as Ge in the hexagonal diamond structure.     

压力对有机半导体均苯四甲酸晶体结构转变和电子性质的影响

研究高压条件下均苯四甲酸(C₁₀H₆O₈)材料的结构和性质对探索有机半导体材料的应用有积极意义.基于密度泛函理论的第一性原理赝势平面波方法,开展了0-300 GPa压强下C₁₀H₆O₈晶体的结构、电子和光学性质的研究.晶格常数在压强20 GPa和150 GPa下出现了明显跳变,且原子之间随着压强变化反复地出现成键/断键现象,表明压强可诱导晶体结构变化.电子结构的性质表明,0 GPa的C₁₀H₆O₈晶体是带隙为3.1 eV的直接带隙半导体,而压强增加到150 GPa时,带隙突变为0 eV,表明了晶体由半导体转变为导体.当压强为160 GPa时,晶体又变成了能隙约为1eV的间接带隙半导体,这可能是费米能级附近仅受O-2p轨道电子影响所导致.通过对C₁₀H₆O₈晶体介电函数的分析,再次验证了晶体在150 GPa时发生了结构相变.同时...     

Static compression of rare earth metal holmium to 282 GPa

ABSTRACT

The phase transitions and equation of state measurements were carried out on rare earth metal Holmium (Ho) to 282?GPa using toroidal diamond anvils thereby doubling the pressure range to which it has been studied previously. The first set of experiment employed standard beveled diamond anvils utilizing copper as an x-ray pressure standard to 217?GPa. The second set of experiment employed toroidal diamond anvils utilizing platinum as an x-ray pressure standard to 282?GPa. The recently proposed 16-atom orthorhombic structure (oF16) appeared to be stable between 103 and 282?GPa. The scaled axial ratio (c/a) shows a narrow range of variation of 1.58?±?0.05 for the five known crystalline phases of Ho to 282?GPa. The experimental equation of state of Ho is presented up to a threefold volume compression V/V_o?=?0.322.     

Response of high-purity titanium to high-pressure impulsive loading

Abstract

Measurements of free surface velocity profiles of high-purity titanium samples under shock-wave loading were performed to study the dynamic strength and phase transition parameters. The peak pressure of the initial compression waves was within the range of 4 to 40 GPa, and the load duration was vaned between 10^?8 and 10^?6 s. An anomalous structure of shock waves was observed at pressures of ～ 2.0 to 5.0 GPa due to the α-ω phase transition. The dynamic strength of pure titanium is lower than that of titanium alloys but exceeds the spall strength of commercial grade titanium.     

高压下MgN8晶体结构理论模拟与物性研究

基于密度泛函理论第一性原理的方法,使用CALYPSO结构搜索技术结合VASP软件,在0~100 GPa压强范围内对MgN8的晶体结构进行预测,并对预测的结构进行系统研究。结果表明:在常压下,空间群为P4/mbm的α-MgN8晶体结构的焓值最低;当压强达到24.3 GPa和68.3 GPa时发生相变,分别相变成空间群为P4/mnc的β-MgN8相和空间群为Cmcm的γ-MgN8相,两次相变均为对应体积坍塌的一级相变。电子性质计算结果表明,α-MgN8相的导带与价带之间具有3.09 eV的带隙,表明该结构具有非金属性;β相和γ相具有明显的金属特征。Bader电荷转移计算表明,随着压力的增加,Mg原子向N原子转移的电荷逐渐增多。     

Sr2Bi4Ti5O18的压致结构相变

 使用4∶1的甲醇-乙醇混合液作传压介质，利用金刚石对顶砧装置（DAC），研究了层状铁电体Sr₂Bi₄Ti₅O₁₈的在位高压拉曼光谱和压致结构相变（0～27 GPa）。发现在8.31 GPa，Sr₂Bi₄Ti₅O₁₈经历了一次结构相交。在23.13 GPa以上，Sr₂Bi₄Ti₅O₁₈似乎出现了压致非晶相交的先兆。并使用内模方法对Sr₂Bi₄Ti₅O₁₈的内模进行了指认。     

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.     

Thermopower of calcium at high pressures

Calcium at megabar pressures undergoes numerous structural transitions and has a complex phase diagram. At the same time, according to the recent theoretical investigations, an anomalous behavior of many physical properties, including a transition to the state of a narrow-gap semiconductor, can be expected even in the region of stability of the normal-pressure phase of calcium with the fcc structure at moderate pressures P ～ 5–15 GPa. Data on the thermopower of calcium in the pressure range up to 9 GPa have been reported. The thermopower in this pressure range is positive, has a smooth maximum at 5–6 GPa, and decreases quite rapidly at higher pressures. The absolute values of the thermopower (5–12 μV/K) indicate that calcium in this pressure range is a metal. The difference between the thermopowers in the direct and inverse passages in the range of 5–7.5 GPa is fairly noticeable (～10%). The possible reasons for such an anomalous behavior, as well as new calculations of the band structure of calcium, have been discussed.     

Evidence of a pressure-induced metallization process in monoclinic VO2

Raman and combined infrared transmission and reflectivity measurements were carried out at room temperature (RT) on monoclinic VO2 over the 0-19 GPa and 0-14 GPa pressure ranges. Both lattice dynamics and optical gap show a remarkable stability up to P* approximately 10 GPa whereas subtle modifications of V ion arrangements within the monoclinic lattice, together with the onset of a metallization process via band gap filling, are observed for P >P*. Differently from P=0, where the VO2 metallic phase is found only in conjunction with the rutile structure above 340 K, a new RT metallic phase within a monoclinic structure appears accessible in the high pressure regime.     

Pressure-induced hydrogen-dominant metallic state in aluminum hydride

Two structural transitions in covalent aluminum hydride AlH3 were characterized at high pressure. A metallic phase stable above 100 GPa is found to have a remarkably simple cubic structure with shortest first-neighbor H-H distances ever measured except in H2 molecule. Although the high-pressure phase is predicted to be superconductive, this was not observed experimentally down to 4 K over the pressure range 120-164 GPa. The results indicate that the superconducting behavior may be more complex than anticipated.     

Martensitic transition in single-crystalline α-GeO2 at compression

We present a structural study of single crystalline quartz-like α-GeO₂ compressed to pressures up to 12 GPa and subsequently quenched to ambient conditions. The transition to a new crystalline phase with a distorted rutile structure, occurring in the pressure interval 8 to 12 GPa, was established. The structure of the new phase was identified from X-ray and electron diffraction data as P2₁/c monoclinic. Electron transmission and scanning microscopy provide direct evidence of the martensitic (or displacive) nature of the transition, indicating, in particular, the lamellar morphology and crystallographic orientation relation between the initial α-quartz and final new monoclinic phases. Upon heating, the new monoclinic phase transforms to the rutile-type structure with a similar (and similarly oriented) oxygen structure motif. Finally, we discuss the difference in high-pressure behavior of single-crystalline and polycrystalline samples transforming to the new crystalline and amorphous phases, respectively.     

X-ray diffraction study of liquid Cs up to 9.8 GPa

We describe an x-ray diffraction study of liquid Cs at high pressure and temperature conducted in order to characterize the structural changes associated with the complex melting curve and phase transitions observed in the solid phases. At 3.9 GPa we observe a discontinuity in the density of the liquid accompanied by a decrease in the coordination number from about 12 to 8, which marks a change to a nonsimple liquid. The specific volume of liquid Cs, combined with structural analysis of the diffraction data, strongly suggest the existence of dsp(3) electronic hybridization above 3.9 GPa, similar to that reported on compression in the crystalline phase.     

Computational Prediction of a Novel Superhard SP~3 Trigonal Carbon Allotrope with Bandgap Larger than Diamond

Searching for new carbon allotropes with superior properties has been a longstanding interest in material sciences and condensed matter physics.Here we identify a novel superhard carbon phase with an 18-atom trigonal unit cell in a full-sp~3 bonding network,termed tri-C_(18) carbon,by first-principles calculations.Its structural stability has been verified by total energy,phonon spectra,elastic constants,and molecular dynamics simulations.Furthermore,tri-C_(18) carbon has a high bulk modulus of 400 GPa and Vickers hardness of 79.0 GPa,comparable to those of diamond.Meanwhile,the simulated x-ray diffraction pattern of tri-C_(18) carbon matches well with the previously unexplained diffraction peaks found in chimney soot,indicating the possible presence of tri-C_(18)carbon.Remarkably,electronic band structure calculations reveal that tri-C_(18) carbon has a wide indirect bandgap of 6.32 eV,larger than that of cubic diamond,indicating its great potential in electronic or optoelectronic devices working in the deep ultraviolet region.     

Ultrahigh pressure equation of state of CaS to 1.5 Mbar

Abstract

Energy Dispersive X-ray Diffraction (EDXD) was performed at room temperature to gather structural data on CaS between approximately 1.7 GPa to nearly 150GPa. In these experiments, CaS retained the B1 structure up to approximately 40 GPa above which it began to transform to the B2 structure. The B2 structure remained stable to the highest pressure reached, 149 GPa, where the relative volume V/V₀ was 0.490. Previous studies on CaS extended only up to 52 GPa, which is barely 10 GPa after the B1 phase changes to the B2 structure. Thus it was not possible to accurately extrapolate the equation of state (EOS) for the B2 phase region to significantly higher pressures. In the present study EOS data for CaS was collected to 150 GPa and no other structural change was observed. EOS parameters for the B1 and B2 phase regions agree well with values reported in the literature.     

_LiIO_3的等温压缩和高温高压下的相变

用金刚石压砧高压x 射线衍射技术研究了_LiIO_3 在室温高压下的压缩行为, 压力达23.0GPa. 观察到晶格压缩的各向异性, 其c/a 轴比以-6.187 * l0**3 /GPa的速率减小. 得到其常压下的体弹模量B。= 3 9.2 G Pa, 体弹模量对压力的一阶导数B。=3.7 8 7. _LiIO_3在高温高压下转变成四方结构, 与淬火卸压所得的“_LiIO_3, 结构一致. 关键词：     

Pure iron compressed and heated to extreme conditions

The results of a first-principles study supported by the temperature-quenched laser-heated diamond anvil-cell experiments on the high-pressure high-temperature structural behavior of pure iron are reported. We show that in contrast to the widely accepted picture, the face-centered cubic (fcc) phase becomes as stable as the hexagonal-close-packed (hcp) phase at pressures around 300-360 GPa and temperatures around 5000-6000 K. Our temperature-quenched experiments indicate that the fcc phase of iron can exist in the pressure-temperature region above 160 GPa and 3700 K, respectively. This, in particular, means that the actual structure of the Earth's core may be a complex phase with a large number of stacking faults.     

Crystal structures of dense lithium: a metal-semiconductor-metal transition

Ab initio random structure searching and single-crystal x-ray diffraction have been used to determine the full structures of three phases of lithium, recently discovered at low temperature above 60 GPa. A structure with C2mb symmetry, calculated to be a poor metal, is proposed for the oC88 phase (60-65 GPa). The oC40 phase (65-95 GPa) is found to have a lowest-enthalpy structure with C2cb symmetry, in excellent agreement with the x-ray data. It is calculated to be a semiconductor with a band gap of ～1 eV at 90 GPa. oC24, stable above 95 GPa, has the space group Cmca, and refined atomic coordinates are in excellent agreement with previous calculations.