Density functional theory study on LaNi4.5Al0.5 hydride phase： electronic properties and sites occupation＊

In this paper the crystal structure, electronic structure and hydrogen site occupation of LaNi4.5Al0.5Hy hydride phase （y = 5.0, 6.0） have been investigated by using full-potential linearized augmented plane wave method. The hydrogen atoms were found to prefer the 6m, 12o and 12n sites, while no 4h sites were occupied. A narrowed Ni-d band is found due to the lattice expansion, the total density of states at EF increases with y, which indicates that the compounds become less stable. The interaction between Al and Ni, H plays a dominant role in the stability of LaNi4.5Al0.5 hydride phase. The smaller the shift of EF towards the higher energy region, the more stable the compounds will be. The obtained results are compared with experimental data and discussed in the light of previous works.     

Neutron powder diffraction study on the structures of LaNi5−xAlxDy compounds

The structures of LaNi_5−xAl_xD_y (x=0.75,0.25,y=1.01, 1.10, 1.91 and 3.1) were systematically investigated by neutron and X-ray diffraction. D atoms are found to enter the 6m site of the α-phase but not the reported 12n site, while the 6m and 12n sites of the β-phase. In the case of LaNi_4.75Al_0.25D_y with lower Al content and symmetry, D atoms do not enter the α-phase but occupy the 4h site besides the 6m and 12n sites of the β-phase. The relationship between structures and properties is also discussed.     

First-principles study of the crystal structures and electronic properties of LaNi5TxHey tritide

The micro-arrangement of helium atoms and electronic properties of tritides LaNi₅T_xHe_y (x=5, 5.5, 6, 6.5; y=0.5, 1.0) have been systematically investigated by means of the full-potential linearized augmented plane wave (FLAPW) method with the generalized gradient approximation (GGA). Those optimized results indicate that helium atoms prefer to occupy the tetrahedral interstitial sites (6c₁) in LaNi₅ tritides. From the analysis of the electronic structure, a strong and narrow peak appears in the low energy region (about −4.0 eV), which is due to the contribution of the He-s band. With increasing in the helium content, the empty band in the low energy region gradually moves to the right. Compared with H atoms, the interactions between He atom and La, Ni atoms are quite weaker, which can easily cause the pulverization of the host alloy.     

金属氢化物LaNi4.5Mn0.5Hx的热中子非弹性散射谱

本文报道了用铍过滤探测器谱仪对LaNi_4.5Mn_0.5H_x在三种不同氢含量时测量的中子非弹性散射谱。结果表明,Mn原子部分置换LaNi₅中的Ni原子后,使M—H键增强,当x=6时,高能段的第二、三振动峰分别向高频方向位移了6meV和10meV。该结果与LaNi_4.5Mn_0.5H_x的平台压力(P-C-T等温线)下降的宏观热力学性能相一致。 关键词：     

Hydrogen-induced reconstruction of the W(100) surface,studied by surface core level spectroscopy

We report W(4?) surface core level shifts which yield new information on the energetics of the W(100) (1 × 1) → C(2 × 2)H phase transition. At small hydrogen coverages we find two co-existing surface core levels from atoms on normal lattice sites and from atoms in reconstructed domains. These surface levels are shifted to smaller binding energy (toward E_F) by 0.35 eV and 0.13 eV relative to the bulk level, respectively. The most stable configuration is obtained at a fractional coverage θ_H ? 0.2, at which all surface atoms are shown to be paired with neighboring atoms in the surface plane.     

Synthesis and structural study of LaNi1−xMnxO3+δ perovskites

The synthesis of LaNi_1−xMn_xO_3+δ samples with different oxygen contents has been performed. Structural characterization was carried out by X-ray and neutron powder diffraction. The crystallographic structure of stoichiometric samples, δ=0, evolves from an orthorhombic (LaMnO₃) to a rhombohedral (LaNiO₃) unit cell. Oxygen excess, δ>0, seems to stabilize the rhombohedral unit cell. For instance, the unit cells at room temperature are orthorhombic and rhombohedral for LaNi_0.1Mn_0.9O_3.0 and LaNi_0.1Mn_0.9O_3.13, respectively. The X-ray patterns show the coexistence of both phases for LaNi_0.5Mn_0.5O_3+δ at room temperature. This coexistence is not ascribed to chemical inhomogeneities, but to a structural phase transition. Neutron patterns collected from 1.5 to 300 K show a continuous evolution except for LaNi_0.5Mn_0.5O_3.08 and LaNi_0.1Mn_0.9O_3.13, which show a phase transition at around 290 and 220 K, respectively. The neutron patterns suggest the presence of an ordered arrangement of Ni and Mn atoms in the crystallographic unit cell. Such arrangement indicates that LaNi_0.5Mn_0.5O₃ could be considered as a double perovskite (nominal formula, La₂NiMnO₆).     

Microstructure characterization and magnetic behavior of NiAlxFe2−xO4 and Ni1−yMnyAl0.2Fe1.8O4 ferrites

NiAl_xFe_2−xO₄ and Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites were prepared by the conventional ceramic method and were characterized by X-ray diffraction, scanning electron microscopy, and magnetic measurements. The single spinel phase was confirmed for all prepared samples. A proper explanation of data is possible if the Al³⁺ ions are assumed to replace Fe³⁺ ions in the A and B sites simultaneously for NiAl_xFe_2−xO₄ ferrites, and if the Mn²⁺ ions are assumed to replace Ni²⁺ ions in the B sites for Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites. Microstructural factors play an important role in the magnetic behavior of Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites with large Mn²⁺ content.     

氦对LaNi5晶体结构的影响及其扩散特性研究

从密度泛函理论为基础的第一性原理出发,运用全势能线性缀加平面波(FLAPW)方法,对氚衰变后氦在合金中的占位以及LaNi₅He晶体结构进行了理论计算,并系统给出了氦在间隙间的迁移曲线.结果表明,氦原子在十二面体(1b)格位最稳定,并且氦从6m格位向1b格位迁移不存在势垒,而从2d格位向1b格位迁移则需越过1.55eV高的势垒.另外,氦从12n格位穿过12o格位最后到达6m格位也无明显势垒存在,并且处于4h格位之间的氦原子可以自由迁移,而相应12n格位之间的直接迁移则需跨越13.6eV高的势垒.最后还计算给出了氚衰变后合金的态密度、电子密度以及势能分布图,并与相应的LaNi₅H结构作了详细比较. 关键词： 全势能线性缀加平面波(FLAPW) 5He')" href="#">LaNi₅He 态密度 扩散     

The configuration of the hydrogen atoms in HfV2Hx compounds at low temperatures: A NMR study

The ⁵¹V nuclear electric quadrupole interaction and the shape of the proton resonance line in the low temperature phase of the HfV₂H_x (0≤x≤4) compounds has been studied by NMR. The data yield information about the hydrogen arrangement in the low temperature phase. They confirm the results of recent neutron diffraction studies that for x=4 and ordered super lattice of the hydrogen atoms exists, with the hydrogen atoms occupying only tetrahedral interstitial sites formed by two Hf and two V atoms. Our results show that in the lower concentration compound the hydrogen atoms most probably also occupy the same type of interstices, but without crystallographic order.     

H2 storage efficiency and sorption kinetics in composite materials

We have prepared two different kinds of composite materials for hydrogen storage and studied their H₂ storage capacity and desorption kinetics. The first composite material consists of magnesium-containing transition metal nanoclusters distributed in the Mg matrix (Mg:TM): this composite material shows better H₂ desorption performances than pure Mg. This improvement is attributed to the role of the MgH₂-TM nanocluster interface as preferential site for hexagonal Mg (h-Mg) nucleation and to the rapid formation of interconnected h-Mg domains where H diffusion during desorption occurs. The second composite material consists of LaNi₅ particles (size<30 μm) distributed in a polymeric matrix. The H₂ storage capacity is negligible at low metal content (50 wt%) when the metal particles are completely embedded in the polymeric matrix. The H₂ storage capacity is comparable to that of the pure LaNi₅ powders at high metal content (80 wt%) when a percolative distribution is assumed by the LaNi₅ particles: this evidence points out the role of metal-metal interfaces and of interconnected metallic networks for H transport.     

NMR studies of hydrogen diffusion in β-LaNi5−yAly hydrides

Proton relaxation times have been measured in β-phase LaNi_5?yAl_yH_x, where 0<y<1.2, to determine the role of Al on hydrogen diffusion. Al substitution significantly increases the observed activation energy with a corresponding 100-fold decrease in the room temperature (300K) diffusion constant between y=0 and y=1.2. Comparisons are also made with previous studies of β-LaNi₅H_x and possible diffusion mechanisms are suggested.     

Properties suggesting H3+-type clusters in some metallic hydrides

The p-c-T relationships for the hydrogen-rich phase of some metallic hydrides are calculated supposing the formation of H₃⁺ -type clusters in the metal lattice in equilibrium with the hydrogen gas. The experimental data for the hydride phase of LaNi₅, Pd, Nb (H?Nb? 0.75) and U are consistent with this model. Other properties reported in literature which seem to support this model are discussed.     

A first-principles study of vibrational modes in Cu2O and Ag2O crystals

A first-principles investigation of cuprite crystals (Cu₂O and Ag₂O) has been performed. For Cu₂O, the calculated frequencies at the Γ point of the Brillouin zone are in very good agreement with the experimental frequencies. For Ag₂O, the presence of E_u and F_2u vibrational modes with negative frequencies indicates a low temperature phase transition, in agreement with recent high resolution X-ray and neutron diffraction measurements. The energy scanning along these two modes shows a double-well potential, within which only the Ag atoms vibrate. As a result, the origin of the phase transition can be attributed to displacive disorder of the Ag atoms.     

Doping effect of hydrogen on Al3 cluster

The doping effect of hydrogen atoms on geometric and electronic properties of small aluminum cluster, Al₃, where deviation from the jellium model may occur, is investigated from a first-principle method. It is found that the most favorable sites for H atoms to be bound to Al atoms depend on amount of H atoms. For each cluster, Al–H bond lengths have the smallest values when the H atoms are on the top sites and have the largest values when the H atoms are on face sites, while those corresponding to bridge-site H atoms are of medium value. The doping of H increases the binding energy of the Al₃ cluster. Al₃H₃ and Al₃H₅ are found to have much lower electron affinities, higher ionization potentials and significantly larger HOMO–LUMO gaps than their neighbors, which are typical characteristics of magic clusters. The high stabilities of the Al₃H₃ and Al₃H₅ suggest that they may have a good potential applications in cluster-assembled materials.     

Magnetic properties and magneto electric effect in ferroelectric rich Ni0.5Zn0.5Fe2O4+BPZT ME composites

Magneto electric composites with composition (x) Ni_0.5Zn_0.5Fe₂O₄+(1-x) Ba_0.8Pb_0.2Zr_0.8Ti_0.2O₃ (BPZT—barium lead zirconate titanate) in which x varies as 0.0, 0.15, 0.30, 0.45 and 1.0 mol% were prepared by standard double sintering ceramic method. The presence of constituent phases such as ferrite and ferroelectric was confirmed by X-ray diffraction. The structural analyses were carried out by using X-ray diffraction pattern. Scanning electron micrographs (SEM) were taken to understand the microstructure of the samples. The calculated values of the porosity of the samples lie between 4.5% and 16.2%. The hysteresis measurements were made to determine saturation magnetization (M_s), magnetic moment (μ_B) and coercivity (H_c). From the AC susceptibility measurements the contribution of both the single domain (SD) particles of the ferrite phase and mixed domain (SD+MD) particles of the composites in ME output were explained. The static magneto electric voltage coefficients (dE/dH)_H were measured as a function of intensity of magnetic field and the maximum ME coefficient were observed for the composites with 30% of ferrite+70% of ferroelectric phase.     

Dependence of the interband transitions on the in mole fraction and the applied electric field in InxGa1−xAs/In0.52Al0.48As multiple quantum wells

Transmission electron microscopy (TEM) and photocurrent (PC) measurements were carried out to investigate the microstructural properties and excitonic transitions in In_xGa_1−xAs/In_0.52Al_0.48As multiple quantum wells (MQWs) for x = 0.54, 0.57 and 0.60. TEM images showed that high-quality 11-period In_xGa_1−xAs/In_0.52Al_0.48As MQWs had high-quality heterointerfaces. The results for the PC spectra at 300 K showed that the peaks corresponding to the excitonic transitions from the ground state electronic sub-band to the ground state heavy-hole band (E₁-HH₁) and the ground state electronic sub-band to the ground state light-hole band (E₁-LH₁) became closer to each other with decreasing In mole fraction and that E₁-HH₁ and E₁-LH₁ excitonic peaks shifted to longer wavelength with increasing applied electric field. The calculated values of the E₁-HH₁ interband transition energies were in qualitative agreement with those obtained form the PC measurements with and without applied electric field. These results can be helpful in understanding potential applications of In_xGa_1−xAs/In_yAl_1−yAs MQWs dependent on In mole fraction and applied electric field in long-wavelength optoelectronic devices.     

Principal energy band gaps of the quaternary alloy AlxGa1−xSbyAs1−y

The correlated function expansion (CFE) interpolation procedure was presented to efficiently estimate principal energy band gaps and lattice constants of the quaternary alloy Al_xGa_1−xSb_yAs_1−y over the entire composition variable space. The lattice matching conditions between x and y for the alloy Al_xGa_1−xSb_yAs_1−y substrated to InAs and GaSb were obtained by optimizing the alloy lattice constant to that of the substrates. The corresponding principal band gaps (E(Γ), E(L), and E(X)) were also calculated along the lattice matching condition on each substrate (InAs and GaSb).     

Investigation on densification of Al2O3/B4C ceramic by ab initio calculation and experiment

Compared to experiment, the adsorption energies, bonding properties, and electronic structure of two different Al₂O₃/B₄C bridge sites with seven different Al₂O₃ surfaces are investigated by ab initio periodic density functional theory. The Al₂O₃/B₄C ceramic sintered in Ar is synthesized and measured by XRD and TEM. The calculated results reveal that the densification of O_bridge site of Al₂O₃/B₄C surface is better than that of Al_bridge. The Al₂O₃ (1 1 3)/B₄C with O_bridge is the most favorable and stable. The electronic structure shows that the electron hybridization exists between Al, O atoms and C, B atoms. The results indicate that the calculated results are in good agreement with the experiment.     

Structural, elastic and electronic properties and formation energies for hexagonal (W0.5Al0.5)C in comparison with binary carbides WC and Al4C3 from first-principles calculations

First principle calculations have been performed with the purpose to understand the peculiarities of the structural, elastic parameters and electronic properties and interatomic bonding for novel hexagonal carbide (W_0.5Al_0.5)C in comparison with binary phases WC and Al₄C₃. The geometries of all phases were optimized and their structural, elastic parameters and theoretical density were established. Besides, we have evaluated the formation energies (E_form) of W_0.5Al_0.5C for different possible preparation routes (namely for the reactions with the participation of simple substances (metallic W, Al and graphite, binary W or Al carbides and metallic Al and W, or binary W and Al carbides). The results show that the synthesis of the ternary carbide from simple substances is more favorable in comparison with the reactions with participation of W and Al carbides. Moreover, band structures, total and partial densities of states were obtained and analyzed systematically for (W_0.5Al_0.5)C, WC and Al₄C₃ phases in comparison with available theoretical and experimental data. The bonding picture in W_0.5Al_0.5C was described as a mixture of metallic, ionic and covalent contributions with the high anisotropy for the covalent W-C and Al-C bonds, where p-p like Al-C bonds become weaker than p-d like W-C bonds.     

Magnetic and structural instabilities in the hexagonal Laves hydride ErMn2H4.6 under high-pressure

The structural and magnetic properties of ErMn₂H_4.6 have been studied by X-ray and neutron diffraction up to the pressures of 15 and 6 GPa, respectively. In the pressure range 0<P<3 GPa we observe a first-order phase transition to new high-pressure (HP) phase. The HP phase has the same hexagonal unit cell as the ambient-pressure phase but smaller lattice parameters (ΔV/V=−5%). The structural transition results in suppression of the long-range antiferromagnetic order. Our results suggest that pressure changes positions of the hydrogen atoms in the metal host. We speculate that the new arrangement of hydrogen atoms induces spin frustration and, therefore, suppresses long-range magnetic order in the HP phase.