FeGa3的晶体结构

本文用X射线粉末法测定了FeGa₃的晶体结构,FeGa₃属四方晶系。在20℃的点阵常数是:a=6.2628?,c=6.5559?。每晶胞包含四个化合式量。空间羣为D_4h¹⁴——P4₂/mnm。Fe原子占据在4(f)等效位置上,Ga原子占据在4(c)及8(j)等效位置上;参数为:x_f=0.343,x_j=0.157,z_j=0.264。从结构看来,这是金属互化物的一种新类型。     

An effective atomic charge model for infrared intensities

Infrared intensities, in particular the dipole derivatives with respect to internal (symmetry) coordinates derived from the intensities, can be explained in terms of an effective atomic charge model which includes both the equilibrium charges and their first-order fluxes. For diatomic molecules it is found that most of the intensity arises from the equilibrium charges in the case of the hydrogen halides, but conversely, in CO, most of the intensity is due to the charge flux. The parameters found can be nicely related to elementary bonding theory.In small symmetrical polyatomic molecules the number of parameters is sufficiently restricted by symmetry and charge conservation that the parameters would be uniquely determinate except for the ambiguity in sign of the experimental dipole derivatives. The examples of AB₂ (D_∞h and C_2v), AB₃ (D_3h and C_3v), and AB₄ (Td) are discussed in detail; a simple generalization for molecular ions is included.For nonpolar molecules, the effective equilibrium charges are determined by the motion (not the equilibrium value) of the electronic centroid.     

Wear-out of Al-Ta2O5/SiO2-Si structures under dynamic stress

Wear-out of Al-Ta₂O₅/SiO₂-Si stacked layers under dynamic current stresses was studied. It was found that a detrapping of negative charges occurs between the pulses, similarly to SiO₂ and SiO_xN_y films. Additional consumption of the SiO₂ interfacial layer results in a decrease of the gate voltage in some stages of the stress, depending upon the stress time and current density.     

ν7 and ν9 bands of formic acid near 16 μm

The ν₇ and ν₉ fundamental bands of formic acid were studied by Fourier transform spectroscopy with a resolving power of 0.020 cm^?1. Band centers obtained are ν₇ = 626.158 cm^?1 and ν₉ = 640.722 cm^?1. It was possible to determine rotational and centrifugal distortion parameters for both vibrational states v₇ = 1 and v₉ = 1 and also the two first-order Coriolis interaction parameters along z and x axes and the second-order Coriolis parameter along z axis. The stability of rotational and distortion parameters compared to ground state values confirms that a Watson type Hamiltonian is well adapted to such a problem.     

Intensity ratios of the KL1L1, KL23L23 oxygen Auger lines in different compounds

A simple model is proposed to interpret the relative intensities of the KLL oxygen Auger lines of several compounds. The basic assumption is that the intensity ratios depend on the atomic charges of the L₁ and L₂₃ orbitals localized at the oxygen site. The appropriate atomic charges can be calculated after Pauling's scale of electronegativity. The theoretical intensity ratios are compared with experimental results of different authors.     

Atomic orbitals and photoelectron intensity angular distribution patterns of MoS2 valence band

The ratio of atomic orbitals contributing to the valence band can be determined from the photoelectron intensity angular distribution (PIAD) by using linearly polarized light and display-type spherical mirror analyzer. The experiment was done for MoS₂ using a linearly polarized light at the photon energy of 45 eV perpendicularly incident to the sample surface. Atomic orbitals contributing to the bands near the Fermi level were investigated. The PIAD patterns around the Γ point showed splitting of intensity. The intensity at the top and bottom K points was strong, while the intensity was weak at the left and right side K points. The PIAD patterns from various kinds of atomic orbitals were calculated. By comparing the experimental PIAD patterns to the simulated ones, we concluded that at the Γ point Mo 4d_z2 and S 3p_z atomic orbitals are the main components and at the K points the Mo 4d_xy atomic orbital is dominant. The atomic orbital Mo 4d_x2−y2 also gives contribution to the PIAD pattern. These results were in good agreement with the coefficients of the atomic orbitals derived using ab initio band calculation.     

Composite SiO2/TiO2 and amine polymer/TiO2 nanoparticles produced using plasma-enhanced chemical vapor deposition

Plasma-enhanced chemical vapor deposition was used to conformally coat commercial TiO₂ nanoparticles to create nanocomposite materials. Hexamethyldisiloxane (HMDSO)/O₂ plasmas were used to deposit SiO₂ or SiO_xC_yH_z films, depending on the oxidant concentration; and hexylamine (HexAm) plasmas were used to deposit amorphous amine-containing polymeric films on the TiO₂ nanoparticles. The composite materials were analyzed using Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). These analyses reveal film composition on the nanoparticles was virtually identical to that deposited on flat substrates and that the films deposit a conformal coating on the nanoparticles. The performance of the nanocomposite materials was evaluated using UV-vis spectroscopy to determine the dispersion characteristics of both SiO_x and HexAm coated TiO₂ materials. Notably, the coated materials stay suspended longer in distilled water than the uncoated materials for all deposited films.     

231Pa Mössbauer resonance in Pa metal

The Mössbauer resonance of the 84.2 keV transition in ²³¹Pa has been measured for an absorber of Pa metal at 4.2 K with respect to a source of ThO₂ at 4.2 and 65 K. The resulting nuclear parameters are compared with calculations based on the Nilsson model. The electric field gradient in Pa metal is |eq_z| = (2.05 ± 0.15)} 10¹⁸ V/cm².     

Spin-glass-like behavior in ZnxCryAlzSe4

The magnetic and electrical properties of the Al-doped polycrystalline spinels Zn_xCr_yAl_zSe₄ (0.13≤z≤0.55) with the antiferromagnetic (AFM) order and semiconducting behavior were investigated. A complex antiferromagnetic structure below a Néel temperature T_N≈23 K for the samples with z up to 0.4 contrasting with the strong ferromagnetic (FM) interactions evidenced by a large positive Curie-Weiss temperature θ_CW decreasing from 62.2 K for z=0.13 to 37.5 K for z=0.55 was observed. Detailed investigations revealed a divergence between the zero-field-cooling (ZFC) and field-cooling (FC) susceptibilities at temperature less than T_N suggesting bond frustration due to competing ferromagnetic and antiferromagnetic exchange interactions in the compositional range 0.13≤z≤0.4. Meanwhile, for z=0.55 a spin-glass-like behavior of cluster type with randomly oriented magnetic moments is observed as the ZFC-FC splitting goes up to the freezing temperature T_f=11.5 K and the critical fields connected both with a transformation of the antiferromagnetic spin spiral via conical magnetic structure into ferromagnetic phase disappear.     

Synthesis and crystal structure of [3,5-(CH3)2C6H3NH3]4P4O12·3H2O

Chemical preparation and crystal structure are given for a new cyclotetraphosphate: [3,5-(CH₃)₂C₆H₃NH₃]₄P₄O₁₂·3H₂O. This compound is triclinic P with the following unit-cell parameters: a=8.298(3), b=8.299(3), c=17.242(7)Å, α=97.13(3), β=102.72(3), γ=64.55(3)°, Z=1 and V=1045.2(8)ų. The crystal structure has been solved and refined to R=0.040 using 6086 independent reflections. The atomic arrangement can be described as layers organization. Layers built by P₄O₁₂ ring anions, ammonium groups and water molecules parallel to the plan (001), between which the organic groups are located. Characterization by X-ray diffraction, IR absorption, and thermal analysis are described.     

A study by E.S.R. of Mn2+ in potassium chromate

Divalent manganese ions are found in potassium chromate single crystals after heating at 600°C in the presence of iodine. These ions occupy three differently oriented sites with the same spin Hamiltonian parameters: g_z = 2·000, g_x = 2·008, g_y = 2·015; A_z = ?88·4 G, A_x = A_y = ?91 G; D = 190 and E = ?30 G.The authors suggest that Mn²⁺ occupies a substitutional (K⁺) position rather than an interstitial one. The influence of iodine is discussed.     

XPS investigation of diffusion of two-layer ZrO2/SiO2 and SiO2/ZrO2 sol–gel films

Two-layer ZrO₂/SiO₂ and SiO₂/ZrO₂ films were deposited on K9 glass substrates by sol–gel dip coating method. X-ray photoelectron spectroscopy (XPS) technique was used to investigate the diffusion of ZrO₂/SiO₂ and SiO₂/ZrO₂ films. To explain the difference of diffusion between ZrO₂/SiO₂ and SiO₂/ZrO₂ films, porous ratio and surface morphology of monolayer SiO₂ and ZrO₂ films were analyzed by using ellipsometry and atomic force microscopy (AFM). We found that for the ZrO₂/SiO₂ films there was a diffusion layer with a certain thickness and the atomic concentrations of Si and Zr changed rapidly; for the SiO₂/ZrO₂ films, the atomic concentrations of Si and Zr changed relatively slowly, and the ZrO₂ layer had diffused through the entire SiO₂ layer. The difference of diffusion between ZrO₂/SiO₂ and SiO₂/ZrO₂ films was influenced by the microstructure of SiO₂ and ZrO₂.     

XPS study of the supported phase — SiO2 interaction in Mo/SiO2 and CoMo/SiO2 hydrodesulphurization catalysts in their oxidic precursor form

XPS results on two series of catalysts, namely Mo/SiO₂ and CoMo/SiO₂ in the oxidic form, are reported. In the first series the molybdenum oxide content deposited on SiO₂ ranges from 2.8 to 20.6 weight %. The second series was obtained by cobalt impregnation of the first series; in this case the atomic ratio Co/(Co + Mo) was fixed at 0.36.XPS binding energy and intensities measurements enable estimation of the interaction and dispersion between the oxide phase and the support to be made.In the case of molybdenum deposited alone on the support, the binding energies of the Mo and O levels both increase with MoO₃ content. When cobalt is also present on the support, the binding energies of the Mo and O levels remain constant. The relative intensities I_Mo/I_Si and I_Co/I_Si remain constant up to 12% active phase and then drastically increase for higher amounts of oxide.These results confirm the existence of a relatively strong Mo/SiO₂ interaction. This interaction is substantially weaker when Co is supported on the MoSiO₂ solid, leading to the formation of CoMoO₄ at the expense of the Mo/SiO₂ interaction. Furthermore, it is shown that at high content of oxide the active phase is deposited on the outer surface of the particle and not inside the pores.     

The magnetic structures of LaTiO3 and CeTiO3

The basic features of the magnetic structures of LaTiO₃ and CeTiO₃ were determined by powder neutron diffraction. LaTiO₃ (T_N = 125 K) is a type G antiferromagnet with a moment on Ti (III) of 0.45(5)μ_B at 10 K. As bulk magnetic measurements indicate a weak ferromagnetic moment, a G_zF_x or G_xF_z configuration is implied. CeTiO₃ (T_N) = 116 K) shows more complex behaviour. At 81 K only G and F type reflections are observed. The most consistent interpretation is to assign G-type configuration to Ti(III) and an induced F_z on Ce(III). Moments are 0.36μ_B on Ti(III) and 0.4(1)μ_B on Ce(III). It is also possible to assign both G and F components to Ti(III). This demands a “canting angle” of 34° to explain the F moment. Below 80 K a C-type component develops. A model assuming a G_zF_x configuration for Ti(III) and a C_yF_x configuration for Ce(III) provides a good fit to the data. This assignment is consistent with Bertaut's symmetry considerations. Other models which violate Bertaut's rules also fit the data.     

Higher-order fine structure of the a4Πu state of O2+

It is shown that the quality of the fit of frequencies for the (4, 4) band of the b⁴Σ_g^?-a⁴Π_u transition of O₂⁺, obtained in an ion-beam experiment, can be significantly improved by the inclusion of a fine structure term of the form L_zS_z³ in the effective Hamiltonian for the a⁴Π_u state, where L_z and S_z are respectively the components of the total orbital and spin angular momenta along the internuclear axis. The various contributions to this term in the Hamiltonian are assessed from a general standpoint by the use of a new order-of-magnitude scheme. The separate contributions to the parameter involved, η, are then considered in detail by means of a perturbation treatment of the spin-orbit and spin-spin interactions through third order. Attempts to interpret the parameter values determined for the a⁴Π_u state of O₂⁺ are severely limited by the present lack of detailed knowledge of the properties of the various electronic states of O₂⁺.     

Radiation-induced paramagnetic centres in glass-ceramics derived from the MgO-Al2O3-SiO2-TiO2 system

MgO-Al₂O₃-SiO₂-TiO₂ glass-ceramics have been γ-irradiated and examined by electron spin resonance. The spectra observed arise from two principle sites; Ti⁴⁺ ions radiochemically reduced to Ti³⁺ and holes trapped at the π-type orbitals of oxygen ions bridging between SiO₄ and AlO₄ units. The Ti³⁺ line, although very similar to its form in the parent glasses, is in general a composite of two distinct lineshapes, each of which is associated with one of the two major crystalline phases Cordierite or Enstatite. The hole centre has a characteristic hyperfine interaction similar to that of the Boron Oxygen Hole Centre of Borate glasses. The Hamiltonian parameters of this centre are $\text{S =}\text{1}\text{2}$, $\text{I =}\text{5}\text{2}$, g₁ = 2.0023, g₂ = 2.0148, g₃ = 2.035 and |A₁| = |A₂| = |A₃| = 8.41 × 10^-4cm^-1.     

Ferromagnetic resonance in FeCl2 and FeBr2

We have used far-i.r. radiations from a HCN laser (336.55 and 310.88 μm) in conjunction with a pulsed magnetic field (0–350 kOe) to observe the ferromagnetic resonance absorption in FeCl₂ and FeBr₂ monocrystals. The resonant lines were obtained for high magnetic field (? 100 kOe) well above the metamagnetic transition field and correspond to the excitation of ferromagnetic magnons at k = 0. From experimental results we found that the g_z spectroscopic tensor component of both FeCl₂ and FeBr₂ is g_z = 3.7 ± 0.05 and that the gap energies of antiferromagnetic magnons in zero field are respectively 16 and 17.3 cm_-1 for FeCl₂ and FeBr₂.     

Spin autocorrelation of Ni in K2Mn0.975Ni0.025F4 studied by nuclear spin-lattice relaxation

From the nuclear spin-lattice relaxation of the out-of-layer ¹⁹F nuclei in magnetic fields perpendicular to the c-axis the low-frequency component of the autocorrelation function 〈S^z(t)S^z(O)〉 of Ni in ordered K₂Mn_0.975Ni_0.025F₄ is found to be substantially reduced relative to the Mn host. The experimental rates vs temperature are in accord with those for relaxation involving two spin excitations calculated with local Green's functions.     

Infrared optical properties of Ba(Zr0.20Ti0.80)O3 and Ba(Zr0.30Ti0.70)O3 thin films prepared by sol-gel method

Ba(Zr_xTi_1−x)O₃ (BZT) (x = 0.20 and 0.30) thin films are deposited on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrate by sol-gel method. X-ray diffraction patterns show that the thin films have a good crystallinity. Optical properties of the films in the wavelength range of 2.5-12 μm are studied by infrared spectroscopic ellipsometry (IRSE). The optical constants of the BZT thin films are determined by fitting the IRSE data using a classical dispersion formula. As the wavelength increases, the refractive index decreases, while the extinction coefficients increase. The effective static ionic charges are derived, which are smaller than that in a purely ionic material for the BZT thin films.     

Magnetic properties of the novel nanocomposite (Zn0.15Ni0.85Fe2O4)0.15/(SiO2)0.85 at room temperature

The value of the effective magnetic anisotropy constant of the ferrimagnetic nanoparticles Zn_0.15Ni_0.85Fe₂O₄ embedded in a SiO₂ silica matrix, determined through ferromagnetic resonance (FMR), is much higher than the magnetocrystalline anisotropy constant. The higher value of the anisotropy constant is due to the existence of surface anisotropy. However, even if the magnetic anisotropy is high, the ferrimagnetic nanoparticles with a 15% concentration, which are isolated in a SiO₂ matrix, display a superparamagnetic (SPM) behavior at room temperature and at a frequency of the magnetization field equal to 50 Hz. The FMR spectrum of the novel nanocomposite (Zn_0.15Ni_0.85Fe₂O₄)_0.15/(SiO₂)_0.85, recorded at room temperature and a frequency of 9.060 GHz, is observed at a resonance field (B_0r) of 0.2285 T, which is substantially lower than the field corresponding to free electron resonance (ESR) (0.3236 T). Apart from the line corresponding to the resonance of the nanoparticle system, the spectrum also contains an additional weaker line, identified for a resonance field of ∼0.12 T, which is appreciably lower than B_0r. This line was attributed to magnetic ions complex that is in a disordered structure in the layer that has an average thickness of 1.4 nm, this layer being situated on the surface of the Zn_0.15Ni_0.85Fe₂O₄ nanoparticles that have a mean magnetic diameter of 8.9 nm.