Variations of the elastic constants of InSb near the covalent-metallic transition

Abstract

The pulse-echo-overlap method was used to measure the longitudinal and transverse wave velocities in single-crystal (100) and (111) samples of InSb up to 3 GPa at room temperature. The peculiar variations of the elastic constants were observed near the covalent-metallic transition.     

TSC defect level in silicon produced by irradiation with muons of GeV-energy

Deep level transient spectroscopy has been used to observe the reduced concentrations of vacancy-related defects in γ-irradiated n-type Si containing hydrogen atoms. Data are presented on the efficiency and depth of this damage reduction as a function of the duration and temperature of the exposure to the plasma used to introduce the atomic hydrogen. A 3-hour exposure in an H plasma at 300°C prior to irradiation reduced the concentrations of the O-V, V-V and P-V centres by half or more to a depth of ～20 μm, compared to the control samples.     

Full rate constant matrix contraction method for obtaining branching ratio of unimolecular decomposition

The branching ratio of unimolecular decomposition can be evaluated by solving the rate equations. Recent advances in automated reaction path search methods have enabled efficient construction of the rate equations based on quantum chemical calculations. However, it is still difficult to solve the rate equations composed of hundreds or more elementary steps. This problem is especially serious when elementary steps that occur in highly different timescales coexist. In this article, we introduce an efficient approach to obtain the branching ratio from a given set of rate equations. It has been derived from a recently proposed rate constant matrix contraction (RCMC) method, and termed full‐RCMC (f‐RCMC). The f‐RCMC gives the branching ratio without solving the rate equations. Its performance was tested numerically for unimolecular decomposition of C₃H₅ and C₄H₅. Branching ratios obtained by the f‐RCMC precisely reproduced the values obtained by numerically solving the rate equations. It took about 95 h to solve the rate equations of C₄H₅ consisting of 234 elementary steps. In contrast, the f‐RCMC gave the branching ratio in less than 1 s. The f‐RCMC would thus be an efficient alternative of the conventional kinetic simulation approach. © 2016 Wiley Periodicals, Inc.     

A new approach in modeling of constant temperature boundary condition in thermal lattice‐Boltzmann method

The lattice‐Boltzmann method is being applied to a diversity of fluid flow and heat transfer problems nowadays. Because of its microscale nature, strict attention should be paid when introducing macroscopic inputs to the model. One of the challenging issues dealing with macroscale and microscale treatment is the implementation of boundary conditions. In this regard constant‐temperature boundaries are frequently used in energy transfer problems. Such boundaries are simply modeled in Navier–Stokes based solvers, but they are not so harnessed in lattice‐Boltzmann models. One of the problems is that the calculated tangential heat flux is not zero along such boundaries in most of the previous models. In the present paper, a model has been developed, which has the capability of controlling tangential heat flux along the constant‐temperature boundaries. It aims to set the heat flux nearly zero along the boundary in midplane grid schemes. Copyright © 2012 John Wiley & Sons, Ltd.     

Dihedral angle study in Hesperidin using NMR Spectroscopy

Hesperidin is flavonoid molecule found in citrus fruits (Citrus reticulata), especially difficult to extract, classify and characterize. Present work is to study the unresolved relative configuration of Hesperidin through the dihedral angle, coupling constant and different NMR techniques. The Karplus equation and its modifications have been originated from the valence bond theory and associated with dihedral angle and coupling constant. The result data set of calculated dihedral angle can probe significant method to assign the virtual configuration of natural products and also resolved stereochemistry of Hesperidin at C‐2 position in. Copyright © 2016 John Wiley & Sons, Ltd.     

On the long‐range relativistic effects in the 15N NMR chemical shifts of halogenated azines

Long‐range β‐ and γ‐relativistic effects of halogens in ¹⁵N NMR chemical shifts of 20 halogenated azines (pyridines, pyrimidines, pyrazines, and 1,3,5‐triazines) are shown to be unessential for fluoro‐, chloro‐, and bromo‐derivatives (1–2 ppm in average). However, for iodocontaining compounds, β‐ and γ‐relativistic effects are important contributors to the accuracy of the ¹⁵N calculation. Taking into account long‐range relativistic effects slightly improves the agreement of calculation with experiment. Thus, mean average errors (MAE) of ¹⁵N NMR chemical shifts of the title compounds calculated at the non‐relativistic and full 4‐component relativistic levels in gas phase are accordingly 7.8 and 5.5 ppm for the range of about 150 ppm. Taking into account solvent effects within the polarizable continuum model scheme marginally improves agreement of computational results with experiment decreasing MAEs from 7.8 to 7.4 ppm and from 5.5 to 5.3 ppm at the non‐relativistic and relativistic levels, respectively. The best result (MAE: 5.3 ppm) is achieved at the 4‐component relativistic level using Keal and Tozer's KT3 functional used in combination with Dyall's relativistic basis set dyall.av3z with taking into account solvent effects within the polarizable continuum solvation model. The long‐range relativistic effects play a major role (of up to dozen of parts per million) in ¹⁵N NMR chemical shifts of halogenated nitrogen‐containing heterocycles, which is especially crucial for iodine derivatives. This effect should apparently be taken into account for practical purposes.     

LiBr分子基态光谱常数和分子常数研究

采用高精度的量子化学从头计算多参考组态相互作用方法和相关一致基, 计算了LiBr分子基态的光谱常数和势能曲线. 为获得更准确的结果, 计算中还考虑了二阶Douglas-Kroll-Hess相对论修正对LiBr分子基态的平衡键长、谐振频率和离解能影响. 将计算得到的势能曲线拟合为Murrell-Sorbie解析势能函数形式, 并进一步计算得到LiBr分子基态的其它光谱常数,ωeχe, αe, Be, D0. 比较发现它们与实验值符合的非常好. 通过求解核运动径向Schrodinger方程, 找到了LiBr分子基态的全部振动态. 还计算了每一个振动态的振动能级、经典转折点和惯性转动常数, 这些结果与已有的实验值一致.     

Potentiometric and Thermodynamic Studies of Some Metal–Cysteine Complexes

A new and simple potentiometric method is developed to determine the stability constants of cysteine complexes with Mn(II), Cu(II), Zn(II), Cd(II), and Ce(III) metal ions using a modified Bjerrum method. Potentiometric titrations were performed in water and water/dioxane mixtures at five different temperatures. The least and highest stable complexes were those of Cu(II) and Zn(II), respectively. Furthermore, by conducting the experiments at temperatures of 15, 20, 25, 35, and 45 °C, the thermodynamic parameters ΔH°, ΔS°, and ΔG° for the pertinent complexes were calculated. The results show that the ΔH° values of the complexes are positive except for Zn(II). Negative values of ΔG° are evidence for the spontaneity of the reactions.     

Study on properties of flame‐retardant cyanate esters modified with DOPO and triazine compounds

Ternary flame‐retardant modified cyanate ester blends (CEPG and CEPA) are formed by combining triazine compounds (TGIC or TAIC) and 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide with cyanate ester resin. The curing behaviors, thermal and mechanical properties, and the flame‐retardant properties are investigated. The results show that the CEPG and CEPA blends result in lower curing temperatures and glass transition temperatures than those of neat CE. Both of CEPG and CEPA blends significantly improve the flame‐retardant properties of CE resins, and UL‐94V‐0 rate is achieved for CEPG‐1.0 and CEPA‐0.5. The dielectric constant and loss of CEPA blends are lower than those of CEPG blend with the same phosphors content, and both of them are lower than those of neat CE. Therefore, the ternary flame‐retardant modified cyanate ester blends provide 2 ways for composites of producing printed circuit board with high flame‐retardant property and low dielectric constant and loss.