Features of atomic and electronic structure of oxides on porous silicon surface according to XANES data

Based on synchrotron research of the fine structure main parameters of SiL _{2, 3} X-ray absorption edges (X-ray absorption near edge structure (XANES)) in porous silicon on boron-doped Si(100) wafers, the thickness of the surface oxide layer and the degree of distortions of the silicon-oxygen tetrahedron in this layer were estimated. The thickness of the oxide layer formed on the amorphous layer coating nanocrystals of porous silicon exceeds the thickness of the native oxide on the surface of Si(100) : P and Si(100) : B single-crystal (100) silicon wafers by several times. Distortion of the silicon-oxygen tetrahedron, i.e., the basic unit of silicon oxide, is accompanied by Si-O bond stretching and an increase in the angle between Si-O-Si bonds.     

A complex first-principles study of the L2,3-edge XANES spectra and crystal field effects for divalent 3d ions in cubic ZnS

A detailed first-principles analysis of the L_2,3 X-ray absorption near edge structure (XANES) spectra, crystal field strength 10Dq, covalent effects and molecular orbitals (MO) position for all divalent 3d ions from Sc²⁺ to Cu²⁺ in cubic ZnS is performed in the present paper. The calculations were done in the framework of the first-principles fully relativistic discrete variational multi-electron (DVME) based on numerical solution of the Dirac equation with the local density approximation. As a result of the performed calculations, the L_2,3 XANES spectra for all considered ions were calculated and assigned in terms of the electron configurations involved into the absorption transitions; fairly good agreement with available experimental data for Ti²⁺, Mn²⁺, Fe²⁺, Co²⁺ and Ni²⁺ is demonstrated. Experimental XANES spectra for Sc²⁺, V²⁺, Cr²⁺, Cu²⁺ not reported previously were also calculated for the sake of completeness of the present study to enable a systematic analysis of all calculated results for the whole series considered. It was shown that the L₃ and L₂ bands shift to the higher energies on increasing a 3d ion atomic number. In addition, the separation between the L₃ and L₂ bands, the crystal field strength 10Dq and mixture between the 3d ion and sulfur wave functions increase along the considered series, from Sc²⁺ to Cu²⁺. On the other hand, all orbitals of the 3d ions systematically lower down in the same direction. The above formulated trends were confirmed by the experimental data on the crystal field splittings and nephelauxetic effect.     

Thermal evolution of the crystal structure of the correlated 4d post-perovskite CaRhO3

Thermal effect on the orthorhombic crystal structure (Cmcm) of the correlated 4d post-perovskite CaRhO₃ was investigated by an X-ray powder diffraction method between 60 K and 300 K. Anisotropic thermal evolution of the structure was observed over the temperature range, and in addition, an anomalous change of the lattice parameters was detected at the antiferromagnetic transition temperature of 90 K, indicating possible correlations between the lattice and the magnetic order.     

The relation between crystal structure and the formation and mobility of protonic charge carriers in perovskite-type oxides: A case study of Y-doped BaCeO3 and SrCeO3

Proton conductivity phenomena in 10% Y-doped barium and strontium cerate are investigated experimentally and by quantum molecular dynamics simulations. In particular the impact of deviations from the cubic perovskite structure on the formation and mobility of protonic charge carriers is investigated. For Y: SrCeO₃, which shows a larger deviation from the ideal cubic perovskite structure, the concentration and mobility of protonic defects is significantly lower than for Y: BaCeO₃. The first is due to the decay of the oxygen position into two sites, only one of which is involved in the formation of protonic defects. The symmetry reduction also leads to the formation of different one-dimensional proton diffusion paths, and unfavourable jumps between such paths are supposed to control the macroscopic proton diffusion coefficient in Y: SrCeO₃. The analysis suggests the formation of strong but transient hydrogen bonds and inter-octa-hedra proton transfer between vertices for SrCeO₃ in contrast to just intra-octahedra proton transfer for BaCeO₃. Whereas for BaCeO₃ the proton transfer step is identified to be rate-limiting at T= 1000 K, for SrCeO₃ both proton transfer and reorientation are found to be of similar magnitude.     

Dependence of crystal field in rare earth garnets on the structure of coordination dodecahedron

The superposition model is used to relate the crystal field parameters reported in various rare earth garnets to the structure of the coordination dodecahedron. The results obtained confirm the overall consistency of the model, reported by other authors, but they differ in the dependence of intrinsic parameters upon distance. Special attention is paid to the approximations inherent to the procedure and to the utility of the model in quantitative predictions.     

Theoretical study of local crystal structure in KZnF3:Fe system

An analysis of the relationship between the EPR trigonal-field parameters and the local crystal structure of KZnF₃:Fe³⁺system is presented by diagonalizing the complete energy matrices for a d⁵ configuration ion in a trigonal crystal field. We propose a two-layer-ligand model, in which the ligands consist of six nearest-neighbor F⁻ ions in the first layer and eight next nearest-neighbor K⁺ ions in the second layer. The calculation indicates that the local structure distortion of KZnF₃:Fe³⁺system is due to the displacement of a K⁺ ion along C₃ axis towards the Fe³⁺ ion, which leads to the shift of the F⁻ ions away from C₃ axis. By simulating the EPR low-symmetry parameters D and (a−F), the distorted angles between the Fe³⁺-F⁻ bonds and C₃ axis are determined, Δθ₁=2.58°, Δθ₂=−1.4° at room temperature (300 K) and Δθ₁=2.84°, Δθ₂=−1.4° at low temperature (77 K). Those results are in good agreement with the experimental findings Δθ₁=2.8±0.3°and Δθ₂=−1.1±0.3°.     

Dependence of the structure of ion-modified NiTi single crystal layers on the orientation of irradiated surface

The composition and structure of Si layers implanted into titanium nickelide single crystals with different orientations relative to the ion beam propagation direction have been studied using Auger electron spectroscopy and transmission electron microscopy. The role of the “soft” [111]_B2 and “hard” [001]_B2 NiTi orientations in the formation of the structure of ion-modified surface layer, as well as the defect structure of the surface layers of the single crystals, has been revealed. Orientation effects of selective sputtering and channeling of ions, which control the composition and thickness of the oxide and amorphous layers being formed, ion and impurity penetration depth, as well as the concentration profile of the Ni distribution over the surface, have been detected.     

A theoretical study of the structure and stability of borohydride on 3d transition metals

The adsorption of borohydride on 3d transition metals (Cr, Mn, Fe, Co, Ni and Cu) was studied using first principles calculations within spin-polarized density functional theory. Magnetic effect on the stability of borohydride is noted. Molecular adsorption is favorable on Co, Ni and Cu, which is characterized by the strong s–d_zz hybridization of the adsorbate-substrate states. Dissociated adsorption structure yielding one or two H adatom fragments on the surface is observed for Cr, Mn and Fe.     

Syntheses, crystal structure and luminescence property of novel 4f-3d heterometallic one-dimensional coordination polymers

Two 4f-3d heterometallic one-dimensional coordination polymers [ZnEu₂(Fur)₈·2H₂O]n and [ZnTb₂(Fur)₈·2H₂O]n (HFur=α-furancarboxylic acid) with good solubility were synthesized and characterized by infrared spectra, X-ray single crystal and powder diffractions, thermogravimetric and differential thermal analysis, and excitation and emission spectra. The X-ray diffraction analyses revealed that the two complexes are isomorphous. The Zn and Ln atoms are linked into one-dimensional chains by furancarboxylate ligands and the metal atoms are arranged in the ···Zn···Ln···Ln···Zn···Ln···Ln···order. Under the excitation of UV light, these coordination polymers emit intense characteristic luminescence of Eu³⁺ or Tb³⁺ ion, respectively. The influence of Zn²⁺ ion on the luminescence properties was also discussed here.     

Fully relativistic calculations of the L2,3-edge XANES spectra for vanadium oxides

Fully relativistic multielectron method based on the numerical solution of the Dirac equation was used to calculate the L_2,3-edge X-ray absorption near edge structure (XANES) spectra of VO₂, V₂O₃, and V₂O₅ crystals. The key-points of the method are: i) usage of the molecular orbitals (MO); ii) absence of any fitting parameters; iii) wide area of application: to any ion in any symmetry; iv) possibility of numerical analysis of the MO composition. The calculated spectra are in a satisfactory agreement with experimental data available in the literature, including the absolute values of the transitions energy, the shape of the absorption bands, and polarization dependence. The assignment of the absorption bands in terms of the electronic configurations was done. The structure of the absorption bands is attributed to the splitting of the vanadium p- and d-orbitals; the magnitude of this splitting is estimated from the spectra. Covalency effects were considered for all hosts; it was shown that the contribution of the oxygen wave functions increases with increasing the vanadium oxidation state. Dependence of the relative positions of the vanadium 3d and oxygen 2p levels and energies of the “ligand–metal” charge transfer transitions on the vanadium oxidation state was analysed.     

Some aspects of auger electron spectra of 3d transition metal oxides

Auger electron spectra of the transition metals Cr, Mn, Fe, Co and Ni as well as their oxides have been investigated in the energy range between 0–100 eV. In each case of the clean metal surface the observed spectrum consists essentially of one Auger line identified asM _2,3 VV transition. After oxidation a line doublet is observed revealing two transitions instead of one. Additional new Auger peaks appear in the low energy range between 0–30 eV. The “splitting” of the Auger line can be explained as resulting from aM _2,3 V _dV_d and aM _2,3 V _pV_p transition. The latter is characteristic for the compound and can in a simple way be interpreted as a cross transition.     

Dependence of luminescent properties and crystal structure of Li-doped ZnO nanoparticles upon Li content

This study examines the effect of Li content on the luminescent and structural properties of Li_xZn_1?xO nanoparticles by scanning electron microscopy, x-ray diffraction, photoluminescence (PL) and Raman scattering measurements. A dependence of luminescent properties and crystal structure upon Li content was found. The intensity of the band-edge luminescence of Li_0.10Zn_0.90O nanoparticles was nearly 10 times higher than that of the ZnO nanoparticles. This is because of the combined effect of the improved crystallinity and a decrease in the probability of nonradiative recombination. However, the incorporation of excess Li into ZnO degrades the PL intensity due to the combined effect of the weakened crystallinity and the increased probability of nonradiative recombination.     

Dependence of the ice-forming activity of dioxinaphthalenes on the structure of the hydrate shell of a crystal

Using the¹N NMR method of frozen suspensions, we studied the structure of hydrate shells in powders of dioxinaphthalenes (DON). We show that for the 1.5-DON isomer, which has a high ice-forming activity, on a DON/ice interface a thinner (in comparison with the nonactive 2,6- and 2,7-DON isomers) layer of water is formed which is bound with the surface. Moreover, in frozen, 1,5-DON suspensions a great quantity of ice is present, which has an extremely high mobility of water molecules. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 4, pp. 557–561, July–August, 1998.     

Core-hole effect on XANES and electronic structure of minor actinide dioxides with fluorite structure

The authors investigated theoretically core-hole effects on X-ray absorption near-edge structures (XANES) of Np and Am L_III in neptunium dioxide (NpO₂) and americium dioxide (AmO₂) with CaF₂-type crystal lattices using the all-electron full-potential linearized augmented plane-wave (FP-LAPW) method. The peak creation mechanism of XANES was shown by examining the electronic structures of these oxides, which indicated that core-hole screening was more marked for AmO₂ than for NpO₂ because of the difference in the charge transfer between these oxides. Furthermore, the results of charge density analysis suggested that the white line was assigned to the quasi-bound state composed of the localized Np d or Am d components and O components, and that the tail structure was created as a result of delocalized standing waves between the Np or Am atoms.     

The crystal structure of the prototypic ceramic superconductor BaPbO3: An X-ray and neutron diffraction study

The structure of the distorted perovskite BaPbO₃ was studied with high-resolution X-ray diffraction at 300 K and 26 K and with neutron diffraction at 300 K. Simultaneous refinement of the neutron and X-ray data sets (300 K) using the Rietveld method yields a monoclinic structure with the space groupI 2/m and lattice parametersa=6.0278 (1) Å,b=6.0664(1) Å,c=8.5109(1) Å, and =90.083 (2)^o. The tilting of the oxygen octahedra is given asa ^– a ^– c ⁰ in Glazer's notation [11]. The monoclinic angle corresponds to the angle between the cubic directions [110] _c and _c . This is in contrast to the observations in BaBiO₃. The structure of BaBiO₃ has the same space groupI 2/m, the similar dimensions of the unit cell and the same tilt system, but = ([110] _c , [001] _c ) as the monoclinic angle. As a consequence there is only one type and size of, PbO₆ octahedra but two types of octahedra in BaBiO₃. This fact may influence the occurrence of superconductivity in solid solutions (Ba(Pb_1–x Bi _x )O₃ containing a large fraction of lead by enhancing valence fluctuations.     

Dynamic relaxation process of a 3D super crystal structure in a Cu:KTN crystal

In this Letter,we report the existence and relaxation properties of a critical phenomenon on called a 3D super crystal that emerges at T=TC?3.5℃,that is,in the proximity of the Curie temperature of a Cu:KTN sample.The dynamics processes of a 3D super crystal manifest in its formation containing polarized nanometric regions and/or polarized clusters.However,with strong coupling and interaction of microcomponents,the characteristic relaxation time measured by dynamic light scattering demonstrates a fully new relaxation mechanism with a much longer relaxation time.As the relaxation mechanism of a relaxator is so-far undetermined,this research provides a novel perspective.These results can help structure a fundamental theory of ferroelectric relaxation.     

A study of final state structure in the x-pe spectra of the rare earth oxides,Part III: Ionisation of a 4d electron

Metal 4d photoelectron spectra of the lanthanoid oxides Ln₂O₃ are reported. The 4d signals are complex, showing subsidiary structure due both to electrostatic interactions within the 4d⁹4?ⁿ configurations and to accompanying O 2p → Ln 4? charge-transfer excitations (shake-up). The effects of electrostatic coupling, including configuration interaction in the final state, are analysed in terms of a simple model.     

铁电液晶螺旋结构的理论近似研究

由铁电液晶（FLC）手性近晶C相下螺旋结构的理论近似计算得出FLC一个螺距内平均折射率的表达式,根据表达式可得出一个螺距内的FLC分子作为一个整体可以看成一个向列相液晶分子模型的结论.当FLC沿螺旋轴方向的厚度等于FLC螺距的整数倍时,液晶盒内垂直取向的FLC分子可看作向列相液晶模型组成的集合.ZLI-3654型FLC与5CB型向列相液晶的实验结果验证了上述结论,理论结果和实验结果一致.这一理论可为畸变螺旋FLC和垂直排列畸变螺旋FLC器件的制备以及FLC的应用提供理论指导和更深的认识. 关键词： 铁电液晶 螺距 平均折射率 向列相液晶