Comparative study of Mo_2Ga_2C with superconducting MAX phase Mo_2GaC: First-principles calculations

The structural, electronic, optical and thermodynamic properties of Mo_2Ga_2C are investigated using density functional theory(DFT) within the generalized gradient approximation(GGA). The optimized crystal structure is obtained and the lattice parameters are compared with available experimental data. The electronic density of states(DOS) is calculated and analyzed. The metallic behavior for the compound is confirmed and the value of DOS at Fermi level is 4.2 states per unit cell per e V. Technologically important optical parameters(e.g., dielectric function, refractive index, absorption coefficient, photo conductivity, reflectivity, and loss function) are calculated for the first time. The study of dielectric constant(ε1) indicates the Drude-like behavior. The absorption and conductivity spectra suggest that the compound is metallic.The reflectance spectrum shows that this compound has the potential to be used as a solar reflector. The thermodynamic properties such as the temperature and pressure dependent bulk modulus, Debye temperature, specific heats, and thermal expansion coefficient of Mo_2Ga_2C MAX phase are derived from the quasi-harmonic Debye model with phononic effect also for the first time. Analysis of T c expression using available parameter values(DOS, Debye temperature, atomic mass,etc.) suggests that the compound is less likely to be superconductor.     

Au-Sn金属间化合物的第一性原理研究

采用基于密度泛函理论的第一性原理平面波赝势法,计算研究了Au-Sn二元系金属间化合物的生成焓、结合能、电子结构、弹性性质和结构稳定性. 计算结果表明：Au₅Sn合金的生成焓最小,说明Au₅Sn较容易生成,但Au₅Sn在热力学和力学上是不稳定的;AuSn₂和AuSn₄的键合作用较强,弹性模量、剪切模量均大于AuSn和Au₅Sn;从电子结构的角度,AuSn₂和AuSn₄ 的成键主要来自于Au原子d 轨道与Sn原子p轨道的杂化;而AuSn以Sn–Sn键的相互作用为主,Au₅Sn相中Au 的占比较大,导致Au–Au共价键发挥作用,抑制了Sn导带p电子的成键. 关键词： 电子结构 弹性性质 第一性原理 Au-Sn金属间化合物     

The vacancy defects and oxygen atoms occupation effects on mechanical and electronic properties of Mo_5Si_3 silicides

Improving brittle behavior and mechanical properties is still a big challenge for high-temperature structural materials.By means of first-principles calculations,in this paper,we systematically investigate the effect of vacancy and oxygen occupation on the elastic properties and brittle-orductile behavior on Mo_5Si_3.Four vacancies (Si_(–Va1),Si_(–Va2),Mo_(–Va1),Mo_(–Va2)) and oxygen occupation models (O_(–Mo1),O_(–Mo2),O_(–Si1),O_(–Si2)) are selected for research.It is found that Mo_(–Va2)vacancy has the stronger structural stability in the ground state in comparison with other vacancies.Besides,the deformation resistance and hardness of the parent Mo_5Si_3are weakened due to the introduction of different vacancy defects and oxygen occupation.The ratio of B/G indicates that oxygen atoms occupation and vacancy defects result in brittle-to-ductile transition for Mo_5Si_3.These vacancies and the oxygen atoms occupation change the localized hybridization between Mo–Si and Mo–Mo atoms.The weaker O–Mo bond is a contributing factor for the excellent ductile behavior in the O_(-Si2)model for Mo_5Si_3.     

Calculation of Half-Metal,Debye and Curie Temperatures of Co_2 VAl Compound: First Principles Study

By FP-LAPW calculations, the structural, elastic, Debye and Curie temperatures, electronic and magnetic properties of Co2 VAl are investigated. The results indicate that Ferromagnetic(FM) phase is more stable than AntiFerromagnetic(AFM) and Non-magnetic(NM) ones. In addition, C11–C12 0, C44 0, and B 0 so Co2 VAl is an elastically stable material with high Debye temperature. Also, the B/G ratio exhibits a ductility behavior. The relatively high Curie temperature provides it as a favorable material for spintronic application. It's electronic and magnetic properties are studied by GGA+U approach leading to a 100% spin polarization at Fermi level.     

The structural, elastic, and electronic properties of the pyrite-type phase for SnO2

We have studied some structural, thermodynamic, elastic, and electronic properties of pyrite-type SnO₂ polymorph by performing ab initio calculations within the LDA approximation. The basic physical properties, in particular lattice constant, bulk modulus, second-order elastic constants (C_ij), and the electronic structure, are calculated, and compared with the available experimental data. In order to gain some further information on the mechanical properties, we have also calculated the Young's modulus, Poison's ratio (ν), anisotropy factor (A), sound velocities, and Debye temperature for the same compound.     

Electronic structure and bonding properties for Laves-phase RV2 (R=Ti, Nb, Hf, and Ta) compounds

The electronic structure and bonding properties of Laves-phase compounds RV₂ (R=Ti, Nb, Hf, and Ta) with C15 structure have been investigated using the full-potential linearized augmented plane-wave method. The results show that the chemical bonding is metallic–ionic–covalent in nature in these compounds, and the covalent bonding between V and V atoms strengthens with the atomic number, increasing among the RV₂ (R=Ti, Nb, Hf, and Ta) compounds. The density of states (DOS), equilibrium volume, and elastic properties are discussed, which is important for understanding the physical properties of RV₂ (R=Ti, Nb, Hf, and Ta) and may inspire future experimental research.     

Stability,electronic structures,and mechanical properties of Fe–Mn–Al system from first-principles calculations

The stability, electronic structures, and mechanical properties of the Fe–Mn–Al system were determined by firstprinciples calculations. The formation enthalpy and cohesive energy of these Fe–Mn–Al alloys are negative and show that the alloys are thermodynamically stable. Fe_3Al, with the lowest formation enthalpy, is the most stable compound in the Fe–Mn–Al system. The partial density of states, total density of states, and electron density distribution maps of the Fe–Mn–Al alloys were analyzed. The bonding characteristics of these Fe–Mn–Al alloys are mainly combinations of covalent bonding and metallic bonds. The stress-strain method and Voigt–Reuss–Hill approximation were used to calculate the elastic constants and moduli, respectively. Fe_(2.5)Mn_(0.5)Al has the highest bulk modulus, 234.5 GPa. Fe_(1.5)Mn_(1.5)Al has the highest shear modulus and Young's modulus, with values of 98.8 GPa and 259.2 GPa, respectively. These Fe–Mn–Al alloys display disparate anisotropies due to the calculated different shape of the three-dimensional curved surface of the Young's modulus and anisotropic index. Moreover, the anisotropic sound velocities and Debye temperatures of these Fe–Mn–Al alloys were explored.     

Structural stability of ultra-high temperature refractory material MoSi_2 and Mo_5Si_3 under high pressure

In-situ angle dispersive x-ray diffraction(ADXRD) with synchrotron radiation source is performed on an ultra-high temperature refractory of MoSi_2 and Mo_5Si_3 by using a diamond anvil cell(DAC) at room temperature. While the pressureinduced volume reduction is almost constant, the value of the bulk modulus increases with the decrease of molybdenum content in the system. According to the Brich–Murnaghan equation, the bulk modulus 222.1(2.1) GPa with its pressure derivative 4 of MoSi_2, and the bulk modulus 308.4(7.6) GPa with its pressure derivative 0.7(0.1) of Mo_5Si_3 are obtained.The experimental data show that MoSi_2 has distinct anisotropic behavior, Mo_5Si_3 is less anisotropic than MoSi_2. The result shows that MoSi_2 and Mo_5Si_3 have the structural stabilities under high pressure. When the pressure reaches up to 41.1 GPa, they can still maintain their body-cantered tetragonal structures.     

Hf-N体系的晶体结构预测和性质的第一性原理研究

为了寻找具有优异力学性能的新型超高温陶瓷材料, 结合进化算法和第一性原理, 系统研究了Hf-N二元体系所有稳定存在的化合物及其晶体结构. 除了实验已知的岩盐结构的HfN之外, 本文还找到了Hf₆N(R-3), Hf₃N(P6₃22), Hf₃N₂(R-3m), Hf₅N₆(C2/m)和Hf₃N₄(C2/m)五种新结构, 基于准简谐近似原理计算了这些稳定结构的声子谱以验证其动力学稳定性, 常温甚至更高温度下的吉布斯自由能以验证其高温热力学稳定性. 结果表明, 这些结构是动力学稳定的, 且在1500 K以下都是热力学稳定的. 同时, 本文还列出了在搜索过程中出现的空间对称性较高、能量较低的亚稳态结构, 包括Hf₂N(P4₂/mnm), Hf₄N₃(C2/m), Hf₆N₅(C2/m), Hf₄N₅(I4/m), Hf₃N₄(I-43d)和Hf₃N₄(Pnma). 之后计算了上述所有结构的力学性质(弹性常数、体模量、 剪切模量、 杨氏模量、硬度), 随着N 所占比例的增加, 硬度呈现的整体趋势是先增大后下降, 在Hf₅N₆处取得最大值, 为21 GPa. 其中Hf₃N₂和Hf₄N₅也展现出了较高的硬度, 都为19 GPa. 最后, 计算了这些结构的电子态密度和晶体轨道汉密尔顿分布, 从电子结构的角度分析了力学性能的成因. 研究结果显示, 较强的Hf-N共价键和较低的结构空位率是Hf₅N₆具有优异力学性能的主要原因.     

Theoretical study on the structural,mechanical, electronic properties and QTAIM of CrB_4 as a hard material

Using the first-principles calculations based on spin density functional theory(DFT), we investigate the structure,elastic properties, and electronic structure of Pnnm-CrB4. It is found that Pnnm-CrB_4 is thermodynamically and mechanically stable. The calculated elastic properties such as the bulk modulus, shear modulus, Young's modulus, and Poisson's ratio indicate that CrB_4 is an incompressible material. Vicker's hardness of Pnnm-CrB_4 is estimated to be 26.3 GPa, which is in good agreement with the experimental values. The analysis of the investigated electronic properties shows that PnnmCrB_4 has the metallic character and there exist strong B–B and Cr–B bonds in the compound, which are further confirmed by Bader's quantum theory of atoms in molecules(QTAIM). Thermodynamic properties are also investigated.     

高压下ErNi2B2C弹性性质、电子结构和热力学性质的第一性原理研究

采用密度泛函理论中的赝势平面波方法研究了高压下超导材料 ErNi₂B₂C 的弹性性质、电子结构和热力学性质.分析表明, 弹性常数、体弹模量、剪切模量、杨氏模量和弹性各向异性因子的外压力效应明显. 电子态密度(DOS)的计算结果显示, 在费米能级(E_F)处的 DOS 峰随外界压强的增大显著降低, 由于 ErNi₂B₂C 相对较高的超导温度(T_c)起因于E_F处的 DOS 峰, 因此推测压强增大可能会降低 ErNi₂B₂C 的 T_c.类似的现象在超导材料 MgB₂和 SrAlSi 中已被发现.此外, 基于准谐德拜模型, 对 ErNi₂B₂C 在高温高压下的热力学性质的研究表明, 在一定范围内, 温度和压强将对其热膨胀系数和热容产生明显的影响. 关键词： 高压 弹性性质 电子结构 热力学性质     

NbSi2奇异高压相及其热力学性质的第一性原理研究

采用基于粒子群优化算法的结构预测程序CALYPSO, 并结合第一性原理的VASP程序, 在175 GPa发现NbSi₂的奇异立方高压相. 在此结构中, Nb原子形成金刚石结构, 而Si原子则形成正四面体镶嵌在金刚石结构中. 声子谱计算结果表明该结构是动力学稳定的. 电子结构分析表明, 六角相和立方相NbSi₂均为金属, 对金属性贡献较大的是Nb原子, 而且Nb和Si原子之间存在明显的p-d杂化现象, 电荷更多地聚集在Si四面体中. 利用“应力应变”方法, 计算了NbSi₂的弹性常数, 分析了其体积模量、剪切模量、杨氏模量和德拜温度等热动力学性质随压力的变化并进行了详细的讨论. 根据剪切模量和体积模量的比值分析了NbSi₂两种相结构的脆性和延展性, 发现压力会导致六角相NbSi₂的延展性增加, 但对立方相结构的延展性影响较小; 采用经验算法计算了NbSi₂两种相结构硬度变化情况, 结合这一比值进行了详细的分析. 弹性各向异性计算结果表明, 随着压力增加, 六角结构的各向异性增强, 而立方结构的各向异性减小.     

First-Principles Calculations of Structural,Elastic and ElectronicProperties of Tetragonal HfO2under Pressure

Structural, elastic and electronic properties of tetragonal HfO₂ at applied hydrostatic pressure up to 50 GPa have been investigated using the plane-wave ultrasoft pseudopotential technique based on the first-principles density-functional theory (DFT). The calculated ground-state properties are in good agreement with previous theoretical and experimental data. Six independent elastic constants of tetragonal HfO₂ have been calculated at zero pressure and high pressure. From the obtained elastic constants, the bulk, shear and Young's modulus, Poisson's coefficients, acoustic velocity and Debye temperature have been calculated at the applied pressure. Band structure shows that tetragonal HfO₂ is an indirect band gap. The variation of the gap versus pressure is well fitted to a quadratic function.     

Elastic,dynamical, and electronic properties of LiHg and Li3Hg: First-principles study

The elastic, dynamical, and electronic properties of cubic LiHg and Li₃Hg were investigated based on first-principles methods. The elastic constants and phonon spectral calculations confirmed the mechanical and dynamical stability of the materials at ambient conditions. The obtained elastic moduli of LiHg are slightly larger than those of Li₃Hg. Both LiHg and Li₃Hg are ductile materials with strong shear anisotropy as metals with mixed ionic, covalent, and metallic interactions. The calculated Debye temperatures are 223.5 K and 230.6 K for LiHg and Li₃Hg, respectively. The calculated phonon frequency of the T_2g mode in Li₃Hg is 326.8 cm⁻¹. The p states from the Hg and Li atoms dominate the electronic structure near the Fermi level. These findings may inspire further experimental and theoretical study on the potential technical and engineering applications of similar alkali metal-based intermetallic compounds.     

First-principles analysis of the structural,electronic, and elastic properties of cubic organic-inorganic perovskite HC(NH_2)_2PbI_3

The structural, electronic, and elastic properties of cubic HC(NH_2)_2PbI_3 perovskite are investigated by density functional theory using the Tkatchenko–Scheffler pairwise dispersion scheme. Our relaxed lattice parameters are in agreement with experimental data. The hydrogen bonding between NH_2 and I ions is found to have a crucial role in FAPbI_3 stability. The first calculated band structure shows that HC(NH_2)_2PbI_3 has a direct bandgap(1.02 eV) at R-point, lower than the bandgap(1.53 eV) of CH_3NH_3PbI_3. The calculated density of states reveals that the strong hybridization of s(Pb)–p(I) orbital in valence band maximum plays an important role in the structural stability. The photo-generated effective electron mass and hole mass at R-point along the R–Γ and R–M directions are estimated to be smaller: m_e~*= 0.06 m0 and m_h~*= 0.08 m0 respectively, which are consistent with the values experimentally observed from long range photocarrier transport. The elastic properties are also investigated for the first time, which shows that HC(NH_2)_2PbI_3 is mechanically stable and ductile and has weaker strength of the average chemical bond. This work sheds light on the understanding of applications of HC(NH_2)_2PbI_3 as the perovskite in a planar-heterojunction solar cell light absorber fabricated on flexible polymer substrates.     

First-principles study on electronic structure and elastic properties of Ti2SC

We have performed first-principles study on electronic structure and elastic properties of Ti₂SC. The absence of band gap at the Fermi level and the finite value of the density of states at the Fermi energy reveal the metallic behavior of this compound. The five independent elastic constants were derived and the bulk modulus, Young's modulus, shear modulus, and Poisson's ratio were determined. The high bulk modulus and hardness was found to be originated from the strong Ti 3d-S 2p hybridization. Such strong MA bonding is unusual in the MAX phases studied so far. Ti₂SC is elastically stable and exhibits highly elastic isotropy.     

BCC结构TiCrTaV合金的电子结构及力学性能的第一性原理计算

利用基于密度泛函理论的第一性原理方法计算TiCrTaV多组元合金中两种BCC结构的结构稳定性、力学性能、德拜温度、电子结构和布居分析. 生成焓和内聚能结果表明BCC1的结构稳定性更好,更容易形成. 弹性常数和模量表明BCC1的强度和韧性更强,BCC2的抗剪切能力和刚度更好,两种结构均具有弹性各向异性. 德拜温度和Grüneisen参数结果表明BCC2的键合强度和热稳定性更好. 电子结构和布居分析表明两种结构均包含共价键和金属键. Ta原子形成的共价键强度更大,金属键仅存在于Ti、Cr和V原子之间. 元素成键后Ti和V原子失去电子,Cr和Ta原子得到电子.     

Theoretical Calculations for Structural, Elastic and Thermodynamic Properties of MgB2 under High Pressure

We have investigated the structural and elastic properties of MgB₂ under high pressures using the full-potential linearized muffin-tin orbital (FP-LMTO) scheme within the generalized gradient approximation correction (GGA) in the frame of density functional theory. The calculated pressure dependence of the normalized volume is in excellent agreement with the experimental results. At the same time the elastic constants and acoustic anisotropy as a function of applied pressure are presented. Through the quasi-harmonic Debye model, we also investigate the thermodynamic properties of MgB₂.     

β-PtO2: Phononic,thermodynamic, and elastic properties derived from first-principles calculations

β-PtO₂ is a useful transition metal dioxide, but its fundamental thermodynamic and elastic properties remain unexplored. Using first-principles calculations, we systematically studied the structure, phonon, thermodynamic and elastic properties of β-PtO₂. The lattice dynamics and structural stability of β-PtO₂ under pressure were studied using the phonon spectra and vibrational density of states. The vibrational frequencies of the optical modes of β-PtO₂ increase with elevating pressure; this result is comparable with the available experimental data. Then, the heat capacities and their pressure responses were determined based on the phonon calculations. The pressure dependence of the Debye temperature was studied, and the results were compared in two distinct aspects. The elastic moduli of β-PtO₂ were estimated through the Voigt–Reuss–Hill approximation. The bulk modulus of β-PtO₂ increases linearly with pressure, but the shear modulus is nearly independent of pressure. Our study revealed that the elastic stiffness coefficients C₄₄, C₅₅ and C₆₆ play a primary role in the slow variation of the shear modulus.     

Physical properties of tetragonal transition-metal borides Nb2MB2 (M = Mo,W, Re or Os) with a new superstructure

The mechanical and thermodynamic properties, chemical bonding characteristics and electronic structure of Nb₂MB₂ (M = Mo, W, Re or Os) with a new tetragonal U₃Si₂-type superstructure (space group P4/mnc, no. 128) were studied by means of density functional theory calculations. All Nb₂MB₂ structures studied were demonstrated to be thermodynamically and mechanically stable. The bulk, shear and Young's moduli, Poisson's ratio, Debye temperature and anisotropy factors were derived for ideal polycrystalline Nb₂MB₂ aggregates. Among these compounds, Nb₂WB₂ was found to have the highest shear modulus and hardness. The electronic densities of state and electronic localization function analysis revealed the metallicity and strong covalent B–B, Nb–B and M−B bonding in Nb₂MB₂. Moreover, these results reveal that the covalence between Nb 4d, M nd (n = 4 for Mo and 5 for W, Re and Os) and B 2p states is the cause of the relatively higher elastic modulus and hardness of the Nb-based compounds. Finally, thermodynamic properties, including the bulk modulus, heat capacity and thermal expansion coefficient of Nb₂WB₂ were obtained systematically under high temperature and pressure.