Optical phonon modes and structure of ZnGa2Se4 and ZnGa2S4

We present the infrared and Raman study of the optical phonon modes of the defective compounds ZnGa₂Se₄ and ZnGa₂S₄. Most of the compounds have been found to crystallize in the thiogallate structure (defect chalcopyrite) with space group where all cations and vacancies are ordered. For some Zinc compounds a partially disordered cationic sublattice with various degrees of cation and vacancy statistical distribution, which lead to the higher symmetry (defect stannite), has been reported. For ZnGa₂Se₄ we have found three modes of A symmetry, showing Raman activity only. In addition, we have observed each five modes of B and E symmetry, showing infrared as well as Raman activity. The number of modes and their symmetry assignment, based on polarized measurements, clearly indicate space group for the investigated crystals of ZnGa₂Se₄.Regarding ZnGa₂S₄ we have found three modes exclusively showing Raman activity (2A⊕1B₁), and only eight modes showing infrared as well as Raman activity (3B₂⊕5E). The assignment of the modes has been derived by analyzing the spectral positions of the vibrational modes in comparison to a number of compounds. From the number and symmetry assignment of the optical phonon modes we confirm that ZnGa₂S₄ most likely crystallizes in space group .     

Cation ordering and crystal structures in AGa2X4 compounds (CoGa2S4, CdGa2S4, CdGa2Se4, HgGa2Se4, HgGa2Te4)

Single crystals of some AGa₂X₄ compounds (CoGa₂S₄, CdGa₂S₄, CdGa₂Se₄, HgGa₂Se₄, HgGa₂Te₄) were prepared by chemical vapour deposition and flux method.The X-ray structural investigations indicated blende or defect chalcopyrite structures.A simple relationship is suggested between the c/a ratio and the cationic sublattice ordering.     

First-principles calculations of electronic, optical and elastic properties of ZnAl2S4 and ZnGa2O4

The optimized crystal structures, band structures, partial and total densities of states (DOS), dielectric functions, refractive indexes and elastic constants for ZnAl₂S₄ and ZnGa₂O₄ were calculated using the CASTEP module of Materials Studio package. Pressure effects were modeled by performing these calculations for different values of external hydrostatic pressure up to 50 GPa. Obtained dependencies of the unit cell volume on pressure were fitted by the Murnaghan equation of state, and the relative changes of different chemical bond lengths were approximated by quadratic functions of pressure. Variations of applied pressure were shown to produce considerable re-distribution of the electron densities around ions in both crystals, which is evidenced in different trends for the effective Mulliken charges of the constituting ions and changes of contour plots of the charge densities. The longitudinal and transverse sound velocities and Debye temperatures for both compounds were also estimated using the calculated elastic constants.     

Effective ionic charges in CdGa2Se4 and CdGa2S4

Available experimental data (Raman and Infrared) on the optic phonon spectra in defect chalcopyrite crystals CdGa₂Se₄ and CdGa₂S₄ are used to determine the dynamical ionic effective charges. The results are compared with those found in other ternary compounds as spinels and chalcopyrites. An emperical correlation between the normalized Szigeti charges and the optical dielectric constant is discussed.     

非线性光学晶体HgGa2S4 和 Hg0.5Cd0.5Ga2S4的能带结构、化学键及光学性质研究

用密度泛函理论和非谐振子模型计算了晶体HgGa₂S₄和Hg_0.5Cd_0.5Ga₂S₄的能带结构、态密度、化学成键及线性、非线性光学性质。结果表明：HgGa₂S₄的价带顶部主要是Ga-S成键态的贡献，导带底部主要是Ga-S反键态的贡献; Hg_0.5Cd_0.5Ga₂S₄的价带顶部主要由S-3p轨道组成，导带底部主要是Ga-S反键态的贡献。布居分析表明Ga-S键主要是共价成分，而Hg-S和Cd-S键主要是离子成分。HgGa₂S₄的折射率计算值与实验值在低能量区很好吻合。另外，HgGa₂S₄的能隙计算值比Hg_0.5Cd_0.5Ga₂S₄小，而二阶非线性极化率比Hg_0.5Cd_0.5Ga₂S₄大。     

Na_2Ge_2Se_5电子结构和光学性质的第一性原理研究

Na_2Ge_2Se_5是一种优异的红外非线性晶体材料.采用基于第一性原理的密度泛函理论赝势平面波方法对Na_2Ge_2Se_5进行结构优化,并以此为基础计算研究了Na_2Ge_2Se_5的电子结构和光学性质.结果表明:Na2Ge2Se5是宽禁带间接带隙半导体,价带至导带的电子跃迁主要来自于Ge和Se的48,4p态;Na对光学性质的贡献较小,Ge和Se之间的相互耦合作用决定了Na_2Ge_2Se_5的光学性质;该晶体在紫外区有强烈的反射和吸收,静态折射率为2.133,双折射率值适中,为0.145.理论计算结果表明,Na_2Ge_2Se_5是一种性能优良的红外非线性光学晶体材料.     

Electronic and magnetic structures of ternary iron telluride KFe2Te2

We examine the electronic and magnetic structures of iron telluride KFe₂Te₂ using first-principle calculations. We demonstrate that the ground state of this compound is in bicollinear antiferromagnetic order with Fe local moments (~ 2.6 μ_B) that are ferromagnetically aligned along a diagonal direction and antiferromagnetically aligned along the other diagonal in the Fe-Fe square lattice, similar to the alignment discovered in the parent compound of superconductor α-FeTe. This bicollinear antiferromagnetic order results from the interplay among the nearest, next-nearest, and next-nextnearest neighbor exchange interactions, which are mediated by Te 5p orbitals. This finding may aid our understanding of the interplay between magnetism and superconductivity in the family of iron-based materials.     

Heat capacity and thermal expansion of CdCr2Se4 and CdCr2S4

The thermodynamic properties of the spinel ferromagnetic compounds CdCr₂Se₄ and CdCr₂S₄ have been investigated by making heat capacity and thermal expansion measurements on single crystals. For both compounds, the ferromagnetic transition is marked by λ-type thermal anomalies, and the results provide a pressure dependence of the transition temperatures that is in agreement with direct measurements. Below the transition, CdCr₂S₄ shows an anomalous heat-capacity contribution and negative thermal expansion, which are in contrast to the conventional behavior found in CdCr₂Se₄.     

Pressure-induced phase transition in defect Chalcopyrites HgAl2Se4 and CdAl2S4

Results of angle dispersive X-ray diffraction (ADXRD) measurements on the defect chalcopyrites (DCP), HgAl₂Se₄ and CdAl₂S₄ up to 22.2 and 34 GPa, respectively, are reported. The ambient tetragonal phase is retained in HgAl₂Se₄ and CdAl₂S₄ up to 13 and 9 GPa respectively. The values of the bulk modulus estimated from the Equation of State is 66(1.5) and 44.6(1) GPa for HgAl₂Se₄ and CdAl₂S₄ in the chalcopyrite phase. At higher pressure a disordered rock-salt structure and on pressure release a disordered zinc blende structure with broad X-ray diffraction lines are observed as is the case for several defect chalcopyrites.     

Photoelectron spectra of As4S3, P4S3, P4Se3 and As4O6

The He(I) UV photoelectron spectra of As₄S₃, P₄S₃, P₄Se₃ and As₄O₆ are reported in this paper. The spectra of As₄S₃ and the isostructural molecules P₄S₃ and P₄Se₃ comprise seven broad but clearly defined peaks, whilst the spectrum of As₄O₆ consists of six peaks and two shoulders. By comparing the spectra with one another and with the photoelectron spectra of other arsenic and phosphorus compounds, the character and symmetry species of the highest-energy occupied molecular orbitals of the molecules have been assigned.     

High pressure X-ray diffraction study of CdAl2Se4 and Raman study of AAl2Se4 (A=Hg, Zn) and CdAl2X4 (X=Se, S)

We report the results of an X-ray diffraction study of CdAl₂Se₄ and of Raman studies of HgAl₂Se₄ and ZnAl₂Se₄ at room temperature, and of CdAl₂S₄ and CdAl₂Se₄ at 80 K at high pressure. The ambient pressure phase of CdAl₂Se₄ is stable up to a pressure of 9.1 GPa above which a phase transition to a disordered rock salt phase is observed. A fit of the volume pressure data to a Birch-Murnaghan type equation of state yields a bulk modulus of 52.1 GPa. The relative volume change at the phase transition at ∼9 GPa is about 10%. The analysis of the Raman data of HgAl₂Se₄ and ZnAl₂Se₄ reveals a general trend observed for different defect chalcopyrite materials. The line widths of the Raman peaks change at intermediate pressures between 4 and 6 GPa as an indication of the pressure induced two stage order-disorder transition observed in these materials. In addition, we include results of a low temperature Raman study of CdAl₂S₄ and CdAl₂Se₄, which shows a very weak temperature dependence of the Raman-active phonon modes.     

A comparison of the raman spectra of ZnGa2Se4 and other gallium defect chalcopyrites

We report and comment for the first time the Raman spectrum of ZnGa₂Se₄. Looking for family trends we compare the present results with those obtained in other gallium defect chalcopyrites. The proportionality law between the frequencies of corresponding phonons in different compounds is verified for all the modes with the exception of the lowest energy polar modes. Evidence of the peculiarity of these modes is obtained, confirming what reported for Zn_xCd_1-xGa₂S₄ pseudoternary compounds.     

Jahn-Teller band transition in La3S4 and La3Se4

La₃S₄ and La₃Se₄ undergo a cubic to tetragonal phase transformation at a temperature of 103 and 70 K respectively, the c/a ratio is 0.984 for La₃S₄ and 0.987 for La₃Se₄. In these compounds the conduction electron Fermi energy happens to be close to a band structure anomaly which drives the phase transition. We find some indication, that the anomaly might be of ?-type.     

Structural,elastic and thermodynamic properties under pressure and temperature effects of MgIn2S4 and CdIn2S4

A density functional-based method is used to investigate the structural, elastic and thermodynamic properties of the cubic spinel semiconductors MgIn₂S₄ and CdIn₂S₄ at different pressures and temperatures. Computed ground structural parameters are in good agreement with the available experimental data. Single-crystal elastic parameters are calculated for pressure up to 10 GPa and temperature up to 1200 K. The obtained elastic constants values satisfy the requirement of mechanical stability, indicating that MgIn₂S₄ and CdIn₂S₄ compounds could be stable in the investigated pressure range. Isotropic elastic parameters for ideal polycrystalline MgIn₂S₄ and CdIn₂S₄ aggregates are computed in the framework of the Voigt–Reuss–Hill approximation. Pressure and thermal effects on some macroscopic properties such as lattice constant, volume expansion coefficient and heat capacities are predicted using the quasi-harmonic Debye model in which the lattice vibrations are taken into account.     

High pressure optical study of KTbP2Se6

We have observed a pressure induced phase transition in KTbP₂Se₆ at about 9.2 GPa which was accompanied by a discontinuous jump of the absorption edge of about 0.5 eV into the red. We have proposed that the high pressure phase is due to charge transfer from the selenium to the phosphorous accompanied by the formation of a Se-Se bond. In order to exclude a model which involves a 4f-5d charge transfer in Tb, leading to the intervalence charge transfer from Tb³⁺P⁴⁺-Tb⁴⁺P³⁺,we have measured the pressure dependence of the luminescence of the crystal field split levels of the Tb-ion. A comparison of the pressure dependence of the luminescence spectra of KTb(MoO₄)₂ and KTbP₂Se₆ shows that such a charge transfer does not occur in KTbP₂Se₆.     

压力下Nd60Al10Fe20Co10块体金属玻璃的弹性行为

室温下在等静压最高达～0.5GPa的条件下，利用超声回波技术测量了超声波横波和纵波在Nd₆₀Al₁₀Fe₂₀Co₁₀块体金属玻璃中的传播时间来确定横波和纵波速度.测量时所采用的超声波频率为10MHz.利用所测量的数据，建立了超声波波速、样品的密度、弹性模量以及Debye温度等与所施加的压力之间的相互关系.并且推导出Murnaghan状态方程.另外，基于非晶态与晶态物理性能的相似性，对此块体非晶的压缩曲线、弹性常数和Debye温度等进行了理论计算，结果表明Nd₆₀Al₁₀Fe₂₀Co₁₀块体金属玻璃的弹性性能与其组成的元素有着密切的关系. 关键词： 块体金属玻璃 弹性性能 等静压     

The bulk band structure and inner potential of layered In4Se3

The layered In₄Se₃ system does have a bulk band structure (i.e. discernable and significant band dispersion) perpendicular to the cleavage plane. Band widths (the extent of dispersion) of 300 meV or more are observed, for In-p and Se-p weighted bands within the valence region, and is indicative of a bulk band structure. Two-dimensionality of state is clearly not conserved, and there must exist interactions between layers sufficient to support a bulk band structure.     

Electrical properties of FeCr2S4 and CoCr2S4

Resistivity and magnetoresistance are measured as functions of temperature (77–450 K) on several FeCr₂S₄ and CoCr₂S₄ single crystals (as-grown, annealed in vacuum, annealed in S-atmosphere, and doped) and found to be very sensitive to these treatments. These results are discussed on the basis of the model consisting of donor level due to S-deficiencies in addition to Fe²⁺ and Cr²⁺ levels.     

First-principles study on the electronic structure and optical properties of T12Cd2（SO4）3 and Rb2Cd2（SO4）3

With the help of ab initio full-potential linearized augmented plane wave （FPLAPW） method, calculating the electronic structure and linear optical properties is carried out for XCd2（SO4）3 （X =Tl, Rb）. The results show that Tl2Cd2（SO4）3 （TlCdS） has a larger band gap than Rb2Cd2（SO4）3 （RbCdS） and the energy bands for RbCdS are more dispersive than those of TlCdS. From their partial densities of states （PDOS）, we have observed that the hybridization between S ionic 2p and O atomic 2p orbitals forms SO4 ionic groups. The remarkable difference between RbCdS and TlCdS is, however, the degree of hybridization between cation （Tl and Rb） and its surrounding oxygen atoms. In the view of quantum chemistry, the strong p-d hybridization indicates the existence of their cation ionic bonds （Cd-O, Rb-O, and Tl-O）. The calculations of TlCdS and RbCdS show their optical properties to be less anisotropic. Their anisotropies in the optical properties mainly occur in a low photon energy region of 5-16 eV.