NQR and magnetic characteristics of the solid solution of NaClO3-KClO3

We measured the nuclear quadrupole resonance (NQR) of the solid solutions of NaClO₃-KClO₃ in the range of concentrations from 0 to 100% molar of KClO₃ in (NaClO₃ + + KClO₃). The thermal diagram of the measured samples showed, that the solubility of the components in each other is limited. It is shown that up to 88·6% molar of KlCO₃ it is possible to identify signals at a frequency which almost exactly corresponds to the NQR frequency of NaClO₃, from this concentration the signals belong to the NQR frequency of KClO₃. At the same time the width of the line shows anomalies in samples containing up to 10% KClO₃ or up to 10% NaClO₃. Broadening of the NQR line to the value 35 kHz in this region was interpreted as a result of prevalence of the size-effect, when the solid solution consists of a mixed crystal of one of the components with such a number of cations of the other component, which is sufficient to produce a chaotic order around the resonanting Cl³⁵ nucleus and such alterations of the electrical field gradient, that they will widen the line.We have also interpreted the deviations of the resonance frequency and linewidth corresponding to the monocrystalline, polycrystalline and melted modifications of the pure NaClO₃ and KClO₃ components.The dependence of the molar magnetic susceptibility of the solid solutions on the concentration of KClO₃ in NaClO₃ + KClO₃ is not linear, it has a peak at the concentration that belongs to the eutectic state, when the chaotic order of the ions Na¹⁺, K¹⁺, (ClO₃ ^1– around any of them is most perfect. At this concentration Van Vleck's polarization paramagnetism is minimum and because it is positive, the total negative value of susceptibility of the material is maximum.     

Far infrared optical properties of polycrystalline NaClO3, KClO3, NaBrO3 and KBrO3

The resonant frequencies, damping constants and oscillator strengths of far infrared lattice vibrations of polycrystalline NaClO₃, KClO₃, NaBrO₃ and KBrO₃ have been obtained through classical dispersion (CD) analysis of transmission data. Space group analysis has been applied for attribution assignments and to ascertain the translational and rotational character of the respective lattice bands. The damping constants were found to be unusually large indicating short lifetimes of the excited states in spite of an apparent absence of phonon-phonon coupling. The CD analysis of the spectra also provide reliable values of oscillator strength and resonant frequency.     

Ion bombardment induced amorphous layers on single crystal stainless steel-a combined rutherford backscattering and transmission electron microscopy study

Abstract

Decomposition reactions of NaClO₃, KClO₃, and KIO₄ induced by 3 keV Ar⁺ ions and 1254 eV X-rays are investigated by X-ray photoelectron spectroscopy (XPS). The reactions lead to the formation of binary halides with preferential losses of oxygen. The decomposition pattern, monitored at the various stages of reaction, indicates almost direct changeover to the final products with only a few intermediate species formed. Product abundancies are compared for the ion, X-ray, and electron induced reactions and discussed in relation to the various radiation induced reaction mechanisms.     

Chlorine-35 quadrupole resonance in impurity doped chlorates

The chlorine-35 quadrupole resonance was studied in NaClO₃, KClO₃ and Ba(ClO₃)₂ doped with the bromates and chlorates of various metal ions. Measurements were carried out at 78°K and at room temperature and with impurity concentrations c up to 1·3 mol%. The frequency and the linewidth of the chlorine resonance change linearly with c, but by different amounts at the two temperatures. The frequency shifts caused by the various impurities in the same matrix are proportional to the difference of the electronegativities of the impurity and the substituted host ion. In most of the samples studied no evidence was found for a contribution from elastic distortions. The observed shifts of the quadrupole resonance frequency are attributed to a charge-transfer from the impurity ion to the chlorate molecules.     

Inelastic intermolecular exchange of vibrational quanta and relaxation of vibrationally excited states in binary solid systems

The processes of molecular relaxation in the binary nitrate–perchlorate solid systems LiNO₃–LiClO₄, NaNO₃–NaClO₄, and KNO₃–KClO₄ have been investigated using Raman spectroscopy. It has been found that the relaxation time of the ν₁(A) vibration of the NO₃ ^- anion in the binary solid system is shorter than that in the pure metal nitrates. It has been shown that an increase in the relaxation rate is caused by the existence of an additional mechanism of relaxation of vibrationally excited states of the nitrate ion in the system. This mechanism is associated with the excitation of a vibration of another anion (ClO₄ ^-), as well as with the “creation” of a lattice phonon. It has been established that the condition for the realization of the relaxation mechanism is that the difference between the frequencies of the aforementioned vibrations should correspond to the range of sufficiently high densities of states of the phonon spectrum.     

The elastic constants of isomorphous sodium bromate and sodium chlorate from 77 to 350 K

The elastic constants of NaBrO₃ and NaClO₃ are evaluated from ultrasonic velocity measurements using pulse superposition techniques. The values of C₁₁, C₁₂ and C₄₄ for NaBrO₃ at 298°K are 5.57₈, 1.70₅, 1.51₀ (x 10¹⁰ N/m²) and for NaClO₃ the values are 4.89₇, 1.38₉, 1.17₄. The values at 77°K are respectively 6.35, 1.98 and 1.65 for NaBrO₃ and 6.15, 2.16 and 1.32 for NaClO₃.     

Isotope effects in the temperature dependence of the pure quadrupole resonance spectra of Cl35 and Cl37 in trichloracetic acid

Elastic and thermoeleastic constants, abrasive hardness and indentation hardness were measured on AgClO₃, NaClO₃ and NaBrO₃. The differences in the elastic behaviour of AgClO₃ and NaClO₃ correspond to those of AgCl and NaCl. They agree with similar effects in isotypic crystal groups if main group elements are replaced by subgroup elements. The mechanical properties of these three crystals are in a close relationship to those of NaCl.     

Band structures of a series of alkali metal chlorates and perchlorates

Calculations of the band structures and densities of electronic states have been carried out for cubic NaClO₄, CClO₄, RbClO₄, CsClO₄, NaClO₃, and rhombohedral RbClO₃ with one formula unit per unit cell using the empirical pseudopotential method with a basis of a plane wave expansion of localized Slater orbitals. The valence bands of these compounds are comparatively narrow and are formed by states of anion origin. The conduction bands are separated into two subbands which have predominantly anion and cation character respectively. A qualitatively different character of the anion-cation hybridization of the upper filled and lower free states was established in the chlorates and perchlorates. A comparison of the data found with experimental photoelectic and optical spectra has been carried out. Kemerovo State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 59–64, October, 1996.     

Elastic properties of mono- and polycrystalline ( and Lu) under pressure effect

The structural and elastic properties of perovskite-type RCRh₃, with R=Sc, Y, La and Lu, under pressure effects have been investigated using the pseudo-potential plane-wave method based on the density functional theory within the generalized gradient approximation. For monocrystalline RCRh₃, the optimized lattice constants, elastic constants and directional elastic wave velocities are calculated and analyzed in comparison with the available experimental and theoretical data. An increase in the lattice constant has been found with increasing atomic size of the R element and a corresponding decrease in the hardness. The anisotropic elastic constants and directional elastic wave velocities increase linearly with increasing pressure. A set of elastic parameters and related properties, namely bulk and shear moduli, Young’s modulus, Poisson’s ratio, Lamé’s coefficients, average sound velocity and Debye temperature are predicted in the framework of the Voigt–Reuss–Hill approximation for polycrystalline RCRh₃. We have found that the toughness of RCRh₃ compounds can be improved at high pressure.     

Measurement of temperature and temperature gradient in?millimeter samples by chlorine NQR

A mini-thermometer based on the ³⁵Cl nuclear quadrupole resonance (NQR) frequency temperature dependence in the chlorates KClO₃ and NaClO₃ was built and successfully tested by measuring temperature and temperature gradient at 77 K and higher in about 100 mm³ active volume of a mini Joule–Thomson refrigerator. In the design of the tank-circuit coil, an array of small coils connected in series enabled us (a) to achieve a suitable ratio of inductance to capacity in the NQR spectrometer input tank circuit, (b) to use a single crystal of KClO₃ or NaClO₃ (of 1–2 mm³ size) in one coil as a mini-thermometer with a resolution of 0.03 K and (c) to construct a system for measuring temperature gradients when the spatial coordinates of each chlorate single crystal within an individual coil are known.     

Isotope effects in Raman spectra of crystalline alkali-metal chlorates and bromates

Halogen and oxygen atom isotope effects have been observed in Raman spectra of single crystal NaClO₃, KClO₃, NaBrO₃, and KBrO₃. Orientational splitting of ³⁵Cl¹⁶O₂¹⁸O^? and ³⁷Cl¹⁶O₂¹⁸O^? ion vibrational modes was observed in KClO₃. Splitting of the v₁ mode of ⁷⁹Br and ⁸¹Br isotopes of singly substituted ¹⁷O and ¹⁸O bromate ions in NaBrO₃ and KBrO₃ is on the order of 1.5 cm^?1 in agreement with a calculation of isotopic frequencies. However, the predicted splitting between v₁ of the major isotopes, ⁷⁹Br¹⁶O₃^? and ⁸¹Br¹⁶O₃^?, was not observed, and the results of a band contour analysis suggest that a single k = 0 phonon is derived from the totally symmetric stretching mode of both species.     

Indirect electronic transitions in alkali halate crystals-I (sodium and potassium chlorate crystals)

The long wavelength tail of the fundamental absorption in NaClO₃ and KClO₃ crystals has been analysed based on the theory of band to band transitions of Bardeen et al.[8] developed in the case of semi-conducting crystals. Evidence of phonon involvement in the transitions giving an indirect band gap is observed. The energies of the phonons involved in the process are the same for both the crystals, and agree well with combinations of prinicple frequencies of ClO₃^? ion, their overtones and also lattice phonons. The indirect band gap in these crystals varies with temperature more or less linearly and the rate of variation is ?3·8 × 10^?4 eV/K and ?5·0 × 10^?4 eV/K for sodium chlorate and potassium chlorate respectively.     

旋声晶体NaBrO3与NaClO3的弹性研究

用中子相干非弹性散射、沿三个主晶轴方向测量了同构异质晶体NaBrO₃和NaClO₃的声子色散关系。从小波矢区的实验结果获得了沿晶体这些方向的弹性波速及三个独立的弹性常数C₁₁,C₁₂,C₄₄。实验结果表明,尽管这两种晶体在旋声方面表现出十分不同的特性,但是,它们的左旋和右旋圆偏振声子的声速都是在一个特定的平均速度v_(TD)上下均衡的分布,这个平均速度可由 关键词：     

Study of first principles on anisotropy and elastic constants of Y3Al2 compound

In this work primarily structural parameters of the Y₃Al₂ was optimized. In the calculations, PBE type Exchange-Correlation function was selected in the GGA approximation and ultra-soft pseudopotential was used. Crystalline lattice parameters a = 15.581 Bohr, c / a = 0.923. Total energy was calculated by small deformations in volume. These values were fitted to the equation of state and the bulk modulus was calculated as 58.4 GPa. The working structure has elastic constants as C₁₁, C₁₂, C₁₃, C₃₃, C₄₄ and C₆₆. These constants have been calculated under ambient pressure. Using the elastic constants, bulk, shear, Young modulus and Poisson ratio (in Voigt approach) were obtained as 58.12, 34.31, 86.01 GPa and 0.25, respectively. Melting temperature of the material was guessed from the elastic constant. The results were compared with the current experimental and theoretical data.     

Theoretical investigation of new type of ternary magnesium alloys AMgNi4 (A=Y,La, Ce,Pr and Nd)

New ternary magnesium alloys AMgNi₄ (A=Y, La, Ce, Pr and Nd) have been studied by First-Principles calculations within the generalized gradient approximation. The optimized structural parameters were in good agreement with the available experimental data. The calculated cohesive energies and formation enthalpies showed that these alloys had strong structural stability. Then the elastic constants C_ij of these AMgNi₄ alloys were calculated, and the bulk modulus B, shear modulus G, Young's modulus E, Poisson's ratio ν and anisotropy value A of polycrystalline materials were derived from the elastic constants, the related mechanical properties were further discussed. The electronic structures were also calculated to reveal the underlying mechanism for the structural stability and the elastic property.     

Indirect electronic transitions in alkali halate crystals-II (sodium bromate and iodate) crystals

In the case of NaClO₃ and KClO₃ crystals, analysis of the long wavelength tail of their fundamental absorption revealed the active participation of the internal vibrations of the chlorate ion (Part I). In order to test the validity of the above interpretation the absorption spectra of two more halates with different anions namely sodium bromate and sodium iodate are analysed in a manner similar to that given in Part I. It is found that the principle internal vibrations of bromate and iodate ions are involved in the indirect transitions. The variation of indirect band gap with temperature is found to be ?2·5 × 10^?4 eV/K and ?2·9 × 10^?4 eV/K for sodium bromate and sodium iodate respectively.     

过渡金属Tc及其氮化物TcN，TcN$lt;sub$gt;2$lt;/sub$gt;，TcN$lt;sub$gt;3$lt;/sub$gt;与TcN$lt;sub$gt;4$lt;/sub$gt;低压缩性的第一性原理计算研究

采用基于密度泛函理论的第一性原理计算方法研究了Tc及其氮化物的弹性性质、电子结构、原子布局数等,并分析和计算了它的氮化物的理论硬度. 结果表明随着Tc中氮的掺入量的渐增,出现层状结构,它们的弹性模量并非单调增加,其中TcN的体弹模量最大而剪切模量最小;层状结构的TcN₃的剪切模量最大而体弹模量最小,TcN₄的理论计算硬度最大. 说明在Tc的氮化物中,其体弹模量与材料的晶体结构、平均每个原子上的电荷密度和材料的质量密度有关;化学键的共价性结构和氮元素的含量对理论计算硬度有正作用;而剪切模量的极大值则与其层状结构及体系中一定量的方向基本一致的N—N键相关. 关键词： 第一性原理 弹性性质 电子结构     

The mechanical,thermodynamic and electronic properties of Al3Nb with DO22 structure: A first-principles study

The lattice constants, elastic properties, electronic structure and thermodynamic properties of Al₃Nb with DO₂₂ structure have been investigated by the first-principles calculation. The calculated lattice constants were consistent with the experimental values, and the structural stability was also studied from the energetic point of view. The single-crystal elastic constants (C_ij) as well as polycrystalline elastic parameters (bulk modulus B, shear modulus G, Young's modulus E, Poisson's ratio υ and anisotropy value A) were calculated, and brittleness of Al₃Nb was discussed in detail. Besides, the electronic structure of tetragonal Al₃Nb was studied, which indicates a mixture of metallic bond and covalent bond in Al₃Nb and reveals the underlying mechanism of the stability and elastic properties of Al₃Nb. Finally, the thermodynamic properties of Al₃Nb were calculated and the physical properties such as heat capacity and Debye temperature were predicted within the quasi-harmonic approximation.     

SCF CI calculations of the K-shell ionization potential of carbon in methane and in the fluoromethanes

The vertical ionization potentials of the K-shell of carbon have been calculated in CH₄, CH₃F, CH₂F₂, CHF₃ and CF₄. The ab initio SCF CI approach has been used for the first three compounds with an attempt to rationalize the choice of the atomic orbital basis sets. The ionization potentials of CHF₃ and CF₄ have been extrapolated from the proceeding results. The effect of the CI cannot be neglected in either of these compounds, but it can in CH₄.     

α-AlPO4晶体弹性温度特性的研究

研究了用缓慢升温法生长的α-AlPO₄晶体的弹性温度特性。测量采用传输法,测温范围为-30—150℃;用最小二乘法拟合弹性-温度曲线;用电子计算机处理数据。给出了弹性常数c_ij和s_ij(i,j=1,2,…,6)的温度特性方程以及T₀=25℃时的一级、二级和三级温度系数。 关键词：