Stability of Ferromagnetism in Fe, Co, and Ni Metals under High Pressure with GGA and GGA+U

The stability of the ferromagnetic state in Fe, Co, and Ni metals under high pressure is investigated using generalized gradient approximation (GGA) and GGA+U within the density functional theory (DFT). It is found that the ferromagnetic state under pressure is very different for Fe, Co, and Ni metals, and is closely associated with the crystal structure. In the case of Fe, a ferromagnetic bcc ground state is obtained at ambient pressure and a nonmagnetic hcp ground state is found at pressure around 12 and 115 GPa for GGA and GGA+U, respectively. For Co, the phase transition from a ferromagnetic hcp to a nonmagnetic fcc is found around 107 GPa for GGA. In contrast to Fe and Co, a ferromagnetic fcc state in Ni is maintained even at 200 GPa. The calculated results suggest that the suppression of ferromagnetism in Fe, Co, and Ni is due to pressure-induced decrease of the density of state at the Fermi level.     

New beta(fcc)-cobalt to 210 GPa

We report a new phase transition in cobalt from the magnetic varepsilon(hcp) to a beta(fcc) phase, likely nonmagnetic, at 105 GPa. It occurs martensitically in an extended pressure region between 105 and 150 GPa without any apparent volume change. The fcc phase of Co is in systematic accordance with the 4d and 5d counterparts. The pressure-volume isotherm of beta-Co resembles those of alpha(fcc)-Ni and varepsilon(hcp)-Fe within 1%. The phase diagram of cobalt suggests that the fcc stability increases with increasing occupancy of d-band electrons from Fe to Co to Ni.     

Structure and magnetism in compressed iron–cobalt alloys

Combined Co K-edge XANES-XMCD and XRD measurements were used to shed light on the magnetic and structural phase diagram of the Fe_1?x Co _x alloy under HP in the Co-rich region (x≥0.5). At 0.5≤x≤0.75, the alloy shows a pressure-induced structural/magnetic phase transition from bcc-FM to hcp-non-FM phase just like pure iron but at higher pressures. The x=0.9 sample has an fcc structure in the pressure range investigated but presents an FM to non-FM transition at P=64 GPa, a significantly lower pressure compared with pure Co (predicted ≈120 GPa), showing that Fe impurities strongly affect the HP Co response.     

室温下Fe62Ni27Mn11（wt%）合金的压致fcc-hcp相变

 本文采用Mao-Bell型金刚石对顶砧（DAC）及高压在位（in situ）粉末X光衍射照相方法研究了Fe₆₂Ni₂₇Mn₁₁（wt%）合金在0~43.2 GPa压力范围内的压致结构相变和等温压缩行为，实验结果表明，该合金在低压时为fcc结构，在19.4 GPa压力附近出现压致fcc→hcp结构相变，直到43.2 GPa一直保持fcc、hcp二相共存；相变过程中，二相的molar体积相同；高压hcp相得晶格参数比值c/a基本上不随压力而变，可以表示为c/a=1.630±0.006；在卸压过程中，hcp相可保持到5.8 GPa，当卸压到常压时，该合金完全恢复到fcc结构；用Murnaghan等温固体状态方程对其压缩数据进行最小二乘法拟合，得到B₀=(166±12) GPa，B₀'=5.2±0.5；本文还给出了该合金的压致fcc→hcp结构相变模型，并对存在很宽的二相共存区间问题进行了初步探讨。     

Relativistic multiple scattering theory of K-edge X-ray magnetic circular dichroism

We discuss the angular dependent K-edge X-ray magnetic circular dichroism (XMCD) spectra based on the non-relativistic Green’s function expansion of the relativistic 4×4 Green’s function developed by Gesztesy et al. [Ann. Inst. Henri Poincaré 40 (1984) 159]. For the core functions we use the Dirac equation solutions whereas the relativistic effects for photoelectrons are automatically taken into account in the Gesztesy expansion. Analyses of the angular anisotropy provides us useful information on local symmetry violation around X-ray absorbing atoms even though we include relativistic effects. We explicitly show three different types of the symmetry which give rise to the suppression of the sin β-dependence in XMCD spectra. We also present explicit formulas of XMCD for randomly oriented and spatially fixed systems. Discussion on Debye–Waller factors is given in the present theoretical framework. Some illustrative calculations are also shown to understand the relativistic effects on the XMCD. The results are given for the Gd L₁-edge and Fe K-edge XMCD.     

Structure of alkali borate glasses at high pressure: B and Li K-edge inelastic X-ray scattering study

We report the first in situ boron K-edge inelastic x-ray scattering (IXS) spectra for alkali borate glasses (Li2B4O7) at high pressure up to 30 GPa where pressure-induced coordination transformation from three-coordinated to four-coordinated boron was directly probed. Coordination transformation (reversible upon decompression) begins around 5 GPa and the fraction of four-coordinated boron increases with pressure from about 50% (at 1 atm) to more than 95% (at 30 GPa) with multiple densification mechanisms, evidenced by three distinct pressure ranges for (d[4]B/dP)T. The lithium K-edge IXS spectrum for Li-borate glasses at 5 GPa shows IXS features similar to that at 1 atm, suggesting that the Li environment does not change much with pressure up to 5 GPa. These results provide improved understanding of the structure of low-z glass at high pressure.     

Lattice dynamics of solid xenon under pressure

We use density-functional perturbation theory to obtain the phonon spectrum of fcc xenon under pressure. Thermodynamic properties obtained within the quasiharmonic approximation are in fair to good agreement with experiment at zero pressure. The transition pressure from the fcc to hcp phase is predicted to occur at 5 GPa. The fcc structure is found to be dynamically stable up to a pressure of 100 GPa, beyond which the phonon modes at the X and L symmetry points soften. We attribute the observed sluggish kinetics of the fcc-hcp transition to the small energy difference between the phases as well as to the high dynamical stability of the fcc phase.     

高压下Fe从bcc到hcp结构相变机理的第一性原理计算

采用基于密度泛函理论的第一性原理方法, 分别研究了压力作用下Fe从体心立方 (bcc,α 相) 结构到六角密排(hcp, ε相) 结构相变的两种不同的相变机理: 相变过程中出现亚稳定的面心立方(fcc) 结构(bcc-fcc-hcp) , 以及相变过程中没有出现亚稳定的fcc结构(bcc-hcp) . 计算结果表明: 静水压力条件下, 相变过程中并不会产生亚稳定的fcc结构, 这与最近的原位XRD实验测量结果相一致. 随着压力的增加, fcc-hcp的相变势垒逐渐增加, 压力趋向于阻止Fe从fcc结构到hcp结构的相变. 计算得到了相变过程中原子磁性和结构的详细信息, 分析表明相变过程中涉及复杂的磁性转变, 并且讨论了原子磁性对结构转变影响的物理机理. 此外, 对分子动力学模拟中产生亚稳定的fcc结构的原因也进行了讨论. 关键词： 相变机理 静水压力 第一性原理 铁     

New scientific opportunities for high pressure research by energy-dispersive XMCD

ABSTRACT

XMCD under pressure is used to study the magnetic properties of the transition metal (TM) systems for over 15 years. We present the technique and how it has been developed. The energy dispersive XAS spectrometer is particularly suited for these studies. The effect of pressure on TM magnetism is discussed. Recent studies performed at different edges illustrate the information that can be obtained through XMCD. Finally, some results obtained on TMs are presented, either at the L_II,III edges of 5d metals or at the K edge of 3d metals, which correspond to the energy ranges that can be probed when using diamond anvil cells for high pressure. Different cases are treated: pure 3d metals, alloys, magnetic insulator and inorganic compounds.     

Disentanglement of magnetic contributions in multi‐component systems by using X‐ray magnetic circular dichroism at a single absorption edge

X‐ray magnetic circular dichroism (XMCD) has become in recent years an outstanding tool for studying magnetism. Its element specificity, inherent to core‐level spectroscopy, combined with the application of magneto‐optical sum rules allows quantitative magnetic measurements at the atomic level. These capabilities are now incorporated as a standard tool for studying the localized magnetism in many systems. However, the application of XMCD to the study of the conduction‐band magnetism is not so straightforward. Here, it is shown that the atomic selectivity is not lost when XMCD probes the delocalized states. On the contrary, it provides a direct way of disentangling the magnetic contributions to the conduction band coming from the different elements in the material. This is demonstrated by monitoring the temperature dependence of the XMCD spectra recorded at the rare‐earth L₂‐edge in the case of RT₂ (R = rare‐earth, T = 3d transition metal) materials. These results open the possibility of performing element‐specific magnetometry by using a single X‐ray absorption edge.     

Phase transition of samarium under high pressure

Abstract

The DAC X-ray power photograph method was employed for studing the phase transition of samarium up to 26.3 GPa. The experimental results show that the dhcp and fcc high pressure phase of Sm appeared at about 4.0 and 12.5 GPa and room temperature respectively. The dhcp phase was kept until 19.6 GPa. A model for Sm-type -? dhcp -? fcc phase transition is provided in this paper.     

A structural study of promethium metal under pressure

Abstract

The structural behaviour of Pm metal has been investigated up to 60 GPa of pressure using a Diamond Anvil Cell (DAC) and the energy dispersive X-ray diffraction technique. The room temperature/pressure structural form of Pm is dhcp and it transforms to a fcc phase by 10 GPa. This cubic phase of the metal converts by 18 GPa to a third phase, which has frequently been referred to as representing a distorted fcc structure. This latter form of Pm was retained up to 60 GPa, the maximum pressure studied, but subtle changes in the X-ray spectra between 50 and 60 GPa hinted that an additional structural change could be forthcoming at higher pressures. From the experimental data a bulk modulus (B₀) of 38 GPa and a B₀′ constant of 1.5 were calculated using the Birch equation. This modulus for Pm is in accord with the moduli reported for the neighboring lanthanide metals.     

Multiple scattering approach to Co K-edge XMCD and XANES spectra in Gd–Co alloys

We have measured and analyzed Co K-edge X-ray absorption near edge structure (XANES) and X-ray magnetic circular dichroism (XMCD) near edge spectra in crystalline and amorphous GdCo₂ alloys. We have used a semi-relativistic full multiple scattering approach to the analyses of the XMCD spectra. A general formula is obtained which is applicable to randomly oriented systems in space. Useful information is obtained on both the electronic and geometric structure around a Co atom. The difference in XANES and XMCD spectra between crystalline and amorphous GdCo₂ is well explained by models referring to the anomalous X-ray scattering result, where three Gd atoms in the second shell are removed away. The calculated XANES are not so sensitive to the electronic structure, whereas the calculated XMCD spectra are rather sensitive to the spin polarization on Co atoms. The result shows that the spin polarization on Co atoms in GdCo₂ alloys is smaller than that in Co metals.     

Crystal Structure Transformations of Rare-Gas Solids Under Pressure

Pressure-induced structural changes in solid krypton (Kr) and xenon (Xe) have been studied using angle dispersive X-ray diffraction in a diamond-anvil cell (DAC) up to 50 GPa. The analysis of the results shows that in solid Kr (Xe) the phase transition from fcc to hcp starts below 3.2 GPa (1.5 GPa). Albeit the hcp/fcc ratio increases under pressure, both phases coexist up to the highest pressure reached in this study. Room temperature (RT) equations of state (EOS) are determined.     

Anharmonicity and quantum effects in thermal expansion of an Invar alloy

We have investigated the anharmonicity and quantum effects in the Invar alloy Fe(64.6)Ni(35.4) that shows anomalously small thermal expansion. We have performed Fe and Ni K-edge extended x-ray-absorption fine-structure spectroscopic measurements and the computational simulations based on the path-integral effective-classical-potential theory. The first nearest-neighbor (NN) shells around Fe show almost no thermal expansion, while those around Ni exhibit meaningful but smaller expansion than that of fcc Ni. At low temperature, the quantum effect is found to play an essentially important role, which is confirmed by comparing the quantum-mechanical simulations to the classical ones. The anharmonicity (asymmetric distribution) clearly exists for all the first NN shells as in normal thermal expansion systems, implying the breakdown of the direct correspondence between thermal expansion and anharmonicity.     

十种稀土金属电阻的压力效应

 使用Bundy和Dunn发展起来的带有烧结金刚石砧的Drickamer型高压装置，用固定点测压法标定实验压力，在室温及0~43 GPa的压力范围内测量了稀土金属中Pr、Nd、Sm、Gd、Tb、Dy、Ho、Tm、Lu和Yb的电阻随压力的变化。在各稀土元素的电阻随压力变化的曲线上，观测到了若干“凸起”和斜率突变点，根据Jayaraman提出的三价稀土在压力作用下的相变顺序，得到了这些突（凸）变点分别对应着hcp→Sm-type→dhcp→fcc相变顺序中的某一类型的相变压力。此外还观测到了Pr、Gd、Tb的fcc相随着压力再增高而发生的相变，根据已报导的关于Pr的工作，推测Gd和Tb的这一相变应为fcc→dfcc相变，它们分别发生在22.0和24.5 GPa。在本工作所得结果基础上对Johansson的三价稀土总相图进行了修正。     

Martensitic fcc-to-hcp transformation observed in xenon at high pressure

Angle-resolved x-ray diffraction patterns of Xe to 127 GPa indicate that the fcc-to-hcp transition occurs martensitically between 3 and 70 GPa in diamond-anvil cells without an intermediate phase. These data also reveal that the transition occurs by the introduction of stacking disorder in the fcc lattice at low pressure, which grows into hcp domains with increasing pressure. The small energy difference between the hcp and the fcc structures may allow the two phases to coexist over a wide pressure range. Evidence of similar stacking disorder and incipient growth of an hcp phase are also observed in solid Kr.     

Pressure-induced phase transition in an orthorhombic C60 crystal

X-ray diffraction studies of an orthorhombic C₆₀ single crystal grown from CS₂ solution have revealed a phase transition to a monoclinic phase between 1.1 and 2.2GPa. Compressibility of three principal axes is measured up to 3GPa and found to be nearly isotropic. Its bulk modulus is obtained as 10.5±1.9GPa, and this crystal is more compressible than an fcc one. We discuss the structural characteristic differences under pressure between the orthorhombic crystal and the fcc crystal.     

Fe-Al系统磁性及其压力效应

采用紧束缚线性muffin-tin轨道方法,研究了Fe-Al系统的磁性与Al组分的关系及其压力效应. bcc Fe-Al合金的铁磁磁矩随Al组分增大而单调减小,且会出现Al组分引起的铁磁—顺磁相变. bcc Fe-Al合金的铁磁磁矩随体积压缩单调减小,但与γ-Fe及某些fcc铁基合金不同的是bcc Fe-Al合金不会出现压力诱导的铁磁—顺磁相变.计算结果与实验符合. 关键词：