Contribution ofd-like states to magnesium,aluminium and phosphorusL-emission bands of MgO,Al2O3 and AlPO4

We have measured the MgL-, AlL- and PL-emission bands of MgO, -Al₂O₃ and AlPO₄, respectively. For MgO and Al₂O₃ the electronic structure and the X-ray emission bands have been calculated. In spite of different crystal structure and chemical composition of these compounds the cationL-emission bands are very similar. We have found that for the interpretation of theL-emission bands of these compounds the cation 3d-like electrons are crucial.     

Prediction of novel ultra-incompressibility compounds TM2B (TM=Mo,W, Re and Os) by first-principles calculations

Abstract

Several novel ultra-incompressibility compounds TM₂B (TM = Mo, W, Re and Os) have been predicted by means of the first-principles calculations. Those novel compounds were assumed to have a ReB₂-type structure [P6₃/mmc space group (No.194, Z = 2), atomic sites: TM 4f (2/3, 1/3, z), B 2c (1/3, 2/3, 1/4)]. We calculated the mechanical properties of the TM₂B, and the results reveal that they exhibit brittle behaviour and mechanically stable. The hardness values are 23.8 GPa, 23.3 GPa, 26.6 GPa and 26.3 GPa for Mo₂B, W₂B, Re₂B and Os₂B, respectively, which suggests that they are hard materials. Additionally, we found that the anisotropy of Re₂B is weaker than the others. Finally, the Mo₂B has the highest Debye temperature (905.8 K), while Os₂B has the lowest Debye temperature (615.5 K). We hoped that our results can help to offer a theoretical data for future experimental work and application of TM₂B.     

Electronic structure and X-ray spectra of transition metal sulfides NiS,CuS, and ZnS

A numerical electronic band structure calculations for sulfides NiS, CuS, and ZnS are carried out. Using the results a detailed analysis of a valence states is performed; obtained partial densities of states are compared with X-ray SL _2,3 and $ SK_{\beta _{1,3} } $ SK_{\beta _{1,3} } -emission spectra. We showed that spectrum lineshape depends on hybridization strength between various Me(3d)-orbitals and 3p-states of sulfur. The hybridization strength and the symmetry of hybrid Me(3d)-orbitals are defined by crystal lattice structure. Finally a well splitted in energy bonding and antibonding states Me(3d)-S(3p) appear while weakly hybridized Me(3d)-states mainly contribute to spectra intensity in the energy between them. A good agreement between the theoretical and the experimental spectra of valence band for considered sulfides is obtained.     

Electronic structure of the diamondlike systems BN1−x Mex (Me = Ti, Cr, Mn, Fe, Ni, Cu)

The local coherent potential method is used within the framework of multiple scattering theory to calculate the electron energy structure of the diamondlike systems BN_1−x Me_x (Me is a 3d transition metal) with the ZnS structure. We used the cluster version of the muffin tin approximation to calculate the crystal potential. The framework of a single approximation is used to compare the electronic energy structure of ternary and binary boron-nitride systems. The width of the hybridized band of the ternary systems BN-Me (Me = Cr, Mn, Fe, Cu) is greater than in the binary system by more than 8 eV and is due to the resultant B-Me interaction. Fiz. Tverd. Tela (St. Petersburg) 39, 1338–1341 (August 1997)     

Au和3d过渡金属元素混合团簇结构、电子结构和磁性的研究

采用基于密度泛函理论的第一性原理方法系统研究了Au与3d过渡元素构成的混合小团簇的结构、稳定性、电子结构及磁性,得到了Au与3d过渡元素构成的混合小团簇的稳定结构.计算结果表明,Au与3d元素可形成大量的低能异构体,特别是有些异构体在结构上极相近,这不同于共价或离子键类型的团簇.与纯过渡金属团簇类似,这类团簇也表现出复杂的磁性.过渡金属元素的磁矩相比体材料而言既有增强的、也有减弱的,与轨道的交换劈裂密切相关.对于基态构型,AuCr₂,Au₂Cr_{2关键词： 密度泛函理论 第一性原理方法 团簇 电子结构}     

Physical properties of the doped manganites Ln0.5M0.5Mno3 (Ln = Pr,La; M = Sr,Ca, Ba)

We present the structural, magnetic and electrical properties of some manganese oxides such as Ln_0.5M_0.5MnO₃ (Ln = La, Pr and M = Ca, Sr, Ba) in which the average ionic radius <r_A> of the A site cation is varied while keeping the Mn³⁺/Mn⁴⁺ ratio fixed to 1. All the studied samples have a perovskite structure with rhombohedral or orthorhombic distortion. This distortion was related to the A cation size. The lattice volume increases lineraly with ( r _A) in all the range 1.179–1.3264 Å. The magnetic investigation shows that the magnetic transition temperature T _t, and magnetisation saturation M _s have similar behaviour by increasing and decreasing with (r _A). The electrical measurements show conduction by small polarons attributed to a large canting angle 9 in all the range 4–300 K in the two ferromagnetic compounds La_0.5Sr_0.5MnO₃ and La_0.5Sr_0.5MnO₃.     

Crystal structure of (La,Ca)MnO3 ultrathin films deposited on SrTiO3 substrates

Epitaxial La_1?x Ca _x MnO₃ (x???0.33) ultrathin films with thickness between 3 and 6?nm have been grown on (001) SrTiO₃ substrates by sputter deposition. The films do not exhibit an insulator-metal transition as a function of temperature, which is normal in thicker films. High-resolution transmission electron microscopy and electron diffraction were used to investigate the crystal structure. It was found that the films grow coherently on the substrates and are perfectly crystalline. Their crystal structure was determined to be a body-centred orthorhombic structure with space group Imma, instead of the orthorhombic Pnma bulk structure. This structure change is probably responsible for the insulating property of the films.     

Preparation and structural investigation of normalconducting and high-T c superconducting (Tl,Pb)Sr2(Ca,Tl)Cu2O7−y

We report on the synthesis and a structural investigation of two isomorphous variants of (Tl, Pb)Sr₂(Ca, Tl)Cu₂O_7–y with different conductive properties. Our analysis of their tetragonal crystal structure (space groupP4/m m m) from X-ray powder data revealed characteristic features such as Tl off-centering, multiple cations and partly vacant oxygen sites. We found that substitution of about 35% Pb²⁺ for Tl³⁺ in the TlO monolayers of the structure, accompanied by replacement of about 23% Tl³⁺ for Ca²⁺ in the perovskite-like layers, changed normalconducting into superconducting behavior, with a transition to zero resistivity at 76 K; normalconducting behavior was found for 25% Pb on Tl sites. Subtle differences in the comparably high levels of doping of the Cu–O pyramidal sheets with holes are assumed to be responsible for the different conductive properties observed. We suggest that an excessive hole concentration turns the compound from superconducting into metallic behavior.     

第一性原理计算MAlH4(M=Na,K)的结构和弹性性质

基于密度泛函理论研究并比较了两种储氢材料NaAlH₄和KAlH₄的晶格参数,弹性性质和电子结构.计算结果表明NaAlH₄和KAlH₄都是绝缘体,Al—H之间是共价键,M(M=Na,K)与AlH₄之间是离子键.NaAlH₄和KAlH₄的弹性常数都比较小而且NaAlH₄的弹性常数要大于KAlH₄的弹性常数,对此给予了解释. 关键词： 配位金属氢化物 电子结构 弹性性质     

First principle study of structural,elastic and electronic properties of APt3 (A=Mg,Sc, Y and Zr)

We report results obtained from first principle calculations on APt₃ compounds with A=Mg, Sc, Y and Zr. Our results of the lattice parameter a are in good agreement with experimental data, with deviations less than 0.8%. Single crystal elastic constants are calculated, then polycrystalline elastic moduli (bulk, shear and Young moduli, Poisson ration, anisotropy factor) are presented. Based on Debye model, Debye temperature ?_D is calculated from the sound velocities V_l, V_t and V_m. Band structure results show that the studied compounds are electrical conductors, the conduction mechanism is assured by Pt-d electrons. Different hybridisation states are observed between Pt-d and A-d orbitals. The study of the charge density distribution and the population analysis shows the coexistence of ionic, covalent and metallic bonds.     

Electron tunneling into thin films of Y1Ba2Cu3O7

We have fabricated tunnel junctions on thin films of Y₁Ba₂Cu₃O₇ which were epitaxially grown by magnetron sputtering on (100) and on (110) oriented SrTiO₃ substrates. These junctions of the type Y₁Ba₂Cu₃O₇/barrier/Pb or In showed with high reproducibility in the conductance a gap-like structure with the maxima near±16mV. We supplied experimental arguments that this structure reflects properties of the quasi particle excitation spectrum of Y₁Ba₂Cu₃O₇. The gap-like structure was found to disappear atT _c mainly by weakening and not by a shift of the peaks to lower voltages.     

Analysis of the nuclear quadrupole interaction of Disulfur Dichloride, S2Cl2

Pure rotational spectra of S₂³⁵Cl₂ and S₂³⁵Cl³⁷Cl have been observed using a Fourier-transform microwave spectrometer. An analysis of the hyperfine structure made by considering the nuclear spin statistics showed that S₂Cl₂ has C₂symmetry, where the hyperfine splittings due to the two Cl nuclei were analyzed precisely. The nuclear quadrupole coupling constants including the off-diagonal (χ_ab, χ_ac, χ_bc) components and the nuclear spin–rotation interaction constants associated with the two Cl nuclei have been determined for the first time. We have shown that the nuclear quadrupole interaction plays an important role in the ortho–para mixing.     

A Mössbauer study of some new compounds with the Fe-Me [Me=Mo,Ni, Cu,Co, Hg,Zn, Cd,Mn, Fe] bond

The reaction of trans-(Co)₃Fe(PPh₂Py)₂ with MeXn gave nine new compounds of trans-(CO)₃Fe(PPh₂Py)₂MeXn (MeXn=Co(SCN)₂, Ni(SCN)₂, Fe(SCN)₃, Cd(SCN)₂, Mn(SCN)₂, Zn(SCN)₂, Mo(CO)₃, Hg(SCN)₂ and CuBr). The compositions of the compounds were determined through elemental analysis. The structural determination was made by IR, FD-MS and³¹P-NMR. Mössbauer spectra were taken at 78 K. The solid-state structure of the complex has been determined by a single-crystal X-ray diffraction study. The crystal data for trans-(CO)₃Fe(Ph₂PPy)₂Hg(SCN)₂ are:a=16.369(5) Å,b=13.754(3) Å,c=17.749(2) Å,r=108.95(2)°, monoclinic space group P21/n,Z= 4. The determination of ESCA demonstrated the change in the Fe value. In the present paper, the effect of the ligands on Fe-metal bonds is discussed.     

Low-lying states of 6He studied via the 6Li(t,3He)6He reaction

We present the recent experimental results on the ⁶He structure studied by the ⁶Li(t, ³He)⁶He reaction at 336 MeV. Above the conspicuous peaks for ground and first excited states for ⁶He, we have observed a broad structures at E _x∼ 5 MeV, and E _x∼ 15 MeV. The angular distribution of this structure exhibits the dominance of a ΔL = 1 transition, indicating the existence of intruder dipole states at low excitation energies in ⁶He. A slight admixture of positive-parity states in this structure has been indicated as well. Received: 1 May 2001 / Accepted: 4 December 2001     

Magnetic, electrical, and crystallographic properties of thin La1−x SrxMnO3 films

A study is reported of the magnetic, electrical, and crystallographic properties of La_1−x Sr_xMnO₃ (0.15⩽x⩽0.23) epitaxial films grown on single-crystal substrates of (001)ZrO₂(Y₂O₃) having the fluorite structure and (001)LaAlO₃ having the perovskite structure. It was found that films with close compositions for x=0.15 and 0.16, grown on different substrates, have different properties, namely, the film on a fluorite substrate is semiconducting and has a coercive strength 30 times that of the film on a perovskite substrate; the temperature dependence of electrical resistance of the latter film has a maximum around the Curie point T _C and follows metallic behavior for T<T _C. These differences are explained as due to different structures of the films. The x=0.23 film on the perovskite substrate has been found to exhibit a combination of giant magnetoresistance at room temperature with a resistance of ≈300 Ω which is useful for applications. The maxima in resistance and absolute value of negative magnetoresistance are accounted for by the existence of two-phase magnetic states in these films. Fiz. Tverd. Tela (St. Petersburg) 40, 290–294 (February 1998)     

Crystal structure determination of Pb2Sr2YCu3O8+δ (δ=0, 1.67) by powder neutron diffraction

Crystal structures of Pb₂Sr₂YCu₃O_8+δ(δ=0.0 and 1.67) were determined by powder neutron diffraction. For δ=0, it had been indicated by powder X-ray diffraction that the structure was a monoclinic one. The R factors of the present analysis for the monoclinic structure were about of those for the previous orthorhombic ones. The structure was almost the same as the previous X-ray result except z(O(2)). For the annealed phase, the tetragonal and the orthorhombic structures had been presented by X-ray diffraction and by neutron diffraction, respectively. The R factors of the present analysis for the orthorhombic structure were about of those for the tetragonal structure. The distance between the Pb plane and the oxygen-deficient Cu plane was found to become larger in proportion to δ, though there occurs a phase separation in the low-δ region.     

Structure, dielectric and magnetodielectric properties of Bi1-xGdxFeO3 Ceramics

Different magnetodielectric effects were observed in Bi1-xGdxFeO3 ceramics depending on gadolinium content. A positive one was observed in the samples with x ≤0.10 at 295K and 16K, and a negative one in the sample with x = 0.4 at 16 K. Structure analysis by x-ray diffraction (XRD) reveals that the samples crystallize in the R3c structure (ferroelectrics) for x<0.08 and in the Pbnm structure (paraelectrics) for x≥0.3 at room temperature. Temperature-dependent dielectric response and x-ray diffraction confirm the occurrence of a structural transition in the Pbnm phase at low temperature for the samples with x ≤0.4. While the positive magnetodielectric effects can be attributed to a coupling of magnetic and crystallographic structures of the R3c phase, the observed negative magnetodielectric effect in the Pbnm phase can be associated with a low-temperature modification of the Pbnm structure. The observed dualsigned magnetodielectric effects suggest that the Bi1-xGdxFeO3 oxides are a good prototype for understanding the magnetodielectric coupling mechanism in this kind of materials.     

The electronic structure of Ca-intercalated superconducting graphite CaC6

We have measured Ca-intercalated graphite superconductor CaC₆ (T_c = 11.2 K) by soft X-ray photoemission spectroscopy in order to understand the electronic structure. For the valence band, we observed several structures that correspond to those of calculated density of states with the partial density of states of Ca 3d at the Fermi level (E_F). We also observed core level spectra that are a very large asymmetric Ca 2p and asymmetric C 1s for CaC₆, suggesting the existence of conduction electrons derived from Ca 3d and a charge transfer from Ca to graphene layer. These results provide spectroscopic evidence for PDOS of Ca 3d at E_F. From a comparison of electronic structure of CaC₆ and other graphite intercalation compounds (GICs), we found the difference between CaC₆ and other superconducting GICs, which provides deeper understanding of the superconductivity of CaC₆.     

Dependence of property, crystal structure and electric conductivity on substitution content and synthetic process of T′-La2−xRExCuO4−δ (RE = Sm and Tb)

We synthesized T′-La_2−xRE_xCuO_4−δ (RE = Sm and Tb) by a co-precipitation method and sintering in vacuum at various temperatures, and investigated relationship among the crystal structure, average valence of Cu, oxygen content and electric conductivity. From X-ray diffraction measurements, it was confirmed that a main phase of the product was T′ structure (S. G.: I4/mmm) regardless of the rare earth element and its concentration, although an impurity phase was observed in a part of samples. In the samples with low average valence of Cu, the resistivity showed a metallic behavior and remarkably decreased at low temperature. Rietveld analyses using synchrotron X-ray diffractions suggested that the electric conductivity was improved by decreasing a bond length of Cu–O1 in the case of La_2−xSm_xCuO_4−δ.     

DFT studies on a high-energy density cage compound 1, 3, 5, 7, 9, 11-hexo(N(CH3)NO2)-2, 4, 6, 8, 10, 12-hexaazatetracyclo[5, 5, 0, 0, 0] dodecane

The infrared and Raman spectra, heat of formation (HOF) and thermodynamic properties were investigated by B3LYP/6-31G^** method for a new designed polynitro cage compound 1,3,5,7,9,11-hexo(N(CH₃)NO₂)-2,4,6,8,10,12-hexaazatetracyclo[5,5,0,0,0]dodecane. The detonation velocity (D) and pressure (P) were predicted by the Kamlet–Jacobs equations based on the theoretical density and condensed HOF. The bond dissociation energies and bond orders for the weakest bonds were analysed to investigate the thermal stability of the title compound. The computational result shows that the detonation velocity and pressure of the title compound are superior to those of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), but inferior to those of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) and hexanitrohexaazaisowurtzitane (HNIW). And the analysis of thermal stability shows that the first step of pyrolysis is the rupture of the N₇–NO₂ bond. The crystal structure obtained by molecular mechanics belongs to the P2₁ space group, with the lattice parameters Z = 2, a = 11.8246 Å, b = 10.4632 Å, c = 15.9713 Å, ρ = 1.98 g cm^?3.