低热固相合成化学

本文介绍了固相化学反应,概述了高热、中热、低热固相反应在合成化学中的地位,重点阐述了低热固相反应的特征及其在无机、有机、材料化学中的应用,列举已在工业生产中使用的低热固相反应实例,阐明低热固相合成确实是工业生产中一条节能、高效、减污的理想通道。     

Application of an adiabatic precision calorimeter in the field of organic reactions

Adiabatic calorimetry is a suitable method for investigations of reactions because the generated heat remains completely in the reactor. For the investigation of organic reactions, the adiabatic precision calorimeter ACTRON 5 is used. The alcoholyses of phenyl isocyanate and 1,2-butyleneoxide were investigated. The temperature-time course was estimated by means of the nonlinear program TA-kin. Inclusion of the concentration-time course in the estimation procedure led to an increase in the reliability of the parameters. Probes were taken during isoperibolic measurements and were analysed by means of HPLC.     

纳米钙钛矿型LaFe1-xNixO3(x=0~1.0)的制备及其在紫外光激发下的电化学性能

本文采用溶胶-凝胶法制备了LaFe1-xNixO3(x=0,0.2,0.4,0.6,0.8,1.0)纳米晶粉末,利用XRD、TEM和电化学测试方法对LaFe1-xNixO3材料的相结构、形貌、成分组成和其在碱液中的充放电性能以及电化学动力学性能等方面进行了表征和分析,同时对电极受紫外光激发前后的电化学行为进行了对比研究。XRD和TEM分析表明,用硝酸盐作为原材料和溶胶-凝胶方法可制备出单一相结构的纳米晶钙钛矿型LaFe1-xNixO3复合氧化物,随Ni替代量x的增大,LaFe1-xNixO3的相结构由正交结构向菱面体结构转变,其分子体积和晶粒尺寸呈现减小的趋势。电化学研究结果表明,紫外光激发前,LaFe1-xNixO3电极的放电容量随x的增加而逐渐增大;光激发后,电极的放电容量和交换电流Io与未激发前相比显著提高,当x=0.4时其放电容量具有最大值483.1mAh·g-1,Io值由光激发前的3.54～11.58 mA·g-1大幅增加至激发后的8.37～40.11 mA·g-1。     

Theoretical computation of low‐lying electronic states of HCNS: A CASPT2 study

Complete active space self‐consistent field (CASSCF) and complete active space second‐order perturbation theory (CASPT2) calculations in conjunction with the aug‐cc‐pVTZ basis set have been used to investigate the low‐lying electronic states of thiofulminic acid (HCNS), HCNS⁺, and HCNS^?. The result of geometry optimization using CASPT2/aug‐cc‐pVTZ shows that theoretically determined geometric parameters and harmonic vibrational frequencies for the HCNS ground state X¹Σ⁺(X¹A′) are in agreement with previous studies. The ionization energies, the electron affinity energies, the adiabatic excitation energies, and vertical excitation energies have been calculated and the corresponding cation and anion states are identified. By calculating adiabatic electron affinity, the states of HCNS^? have been identified to contain both π orbital states (X²A′ and 1²A″) and dipole‐bond states (1⁴A′ and 1⁴A″). © 2012 Wiley Periodicals, Inc.     

Approximate Atomic Green Functions

In atomic and many-particle physics, Green functions often occur as propagators to formally represent the (integration over the) complete spectrum of the underlying Hamiltonian. However, while these functions are very crucial to describing many second- and higher-order perturbation processes, they have hardly been considered and classified for complex atoms. Here, we show how relativistic (many-electron) Green functions can be approximated and systematically improved for few- and many-electron atoms and ions. The representation of these functions is based on classes of virtual excitations, or so-called excitation schemes, with regard to given bound-state reference configurations, and by applying a multi-configuration Dirac-Hartree-Fock expansion of all atomic states involved. A first implementation of these approximate Green functions has been realized in the framework of Jac, the Jena Atomic Calculator, and will facilitate the study of various multi-photon and/or multiple electron (emission) processes.     

Parametric excitation of beams moving over supports

Studied in this work are the formulation of equations of motion and the response to parametric excitation of a uniform cantilever beam moving longitudinally over a single bilateral support. The equations of motion are generated by using assumed modes to discretize the beam, by regarding the support as a kinematic constraint, and by employing an alternate form of Kane's method that is particularly well suited to systems subject to constraints. Instability information is developed using the results of perturbation analysis for harmonic longitudinal motions of small amplitude and with Floquet theory for general periodic motions of any amplitude. Results demonstrate that definitive instability information can be obtained for a beam moving longitudinally over supports based on the frequencies of free transverse vibration of a beam that is longitudinally fixed.     

An Optimal Nonlinear Feedback Control Strategy for Randomly Excited Structural Systems

A strategy for optimal nonlinear feedback control of randomlyexcited structural systems is proposed based on the stochastic averagingmethod for quasi-Hamiltonian systems and the stochastic dynamicprogramming principle. A randomly excited structural system isformulated as a quasi-Hamiltonian system and the control forces aredivided into conservative and dissipative parts. The conservative partsare designed to change the integrability and resonance of the associatedHamiltonian system and the energy distribution among the controlledsystem. After the conservative parts are determined, the system responseis reduced to a controlled diffusion process by using the stochasticaveraging method. The dissipative parts of control forces are thenobtained from solving the stochastic dynamic programming equation. Boththe responses of uncontrolled and controlled structural systems can bepredicted analytically. Numerical results for a controlled andstochastically excited Duffing oscillator and a two-degree-of-freedomsystem with linear springs and linear and nonlinear dampings, show thatthe proposed control strategy is very effective and efficient.     

Similarity solutions for non-Newtonian power-law fluid flow

The problem of the boundary layer flow of power law non-Newtonian fluids with a novel boundary condition is studied.The existence and uniqueness of the solutions are examined,which are found to depend on the curvature of the solutions for different values of the power law index n.It is established with the aid of the Picard-Lindel¨of theorem that the nonlinear boundary value problem has a unique solution in the global domain for all values of the power law index n but with certain conditions on the curvature of the solutions.This is done after a suitable transformation of the dependent and independent variables.For 0 n 1,the solution has a positive curvature,while for n 1,the solution has a negative or zero curvature on some part of the global domain.Some solutions are presented graphically to illustrate the results and the behaviors of the solutions.     

端部激励相位差下斜拉索的非线性振动

斜拉桥中拉索承受着多种端部激励,可激发大幅空间振动．以斜拉索为对象,探究不同端部激励间相位差对其非线性振动的影响．首先,推导斜拉索无量纲离散控制方程,引入考虑相位的三向端部激励得到一般化模型;然后,针对拉索下端存在的纵桥向、竖向和横桥向激励的两两组合,受大幅或小幅激励,及其在主共振区或主参数共振区几组因素,共计12种工况,采用数值分析法分别研究了各工况下不同激励相位差时的斜拉索稳态响应．研究发现：激励相位差能加剧与激励频率相近的面内、外模态振动;在任意端部激励组合下,激励相位差不仅可使斜拉索非线性振动出现定量变化,还可改变内共振的表现形式．面内、外激励组合下,相位差对拉索响应幅值的影响以π为周期变化,且当相位差趋于π/2 + kπ (k = 0, 1, 2…)时影响最为突出;而面内激励组合下,以2π为变化周期,当相位差为π + 2kπ (k = 0, 1, 2, …)时其对稳态幅值的影响最显著．其原因是：面外激励关于拉索所在的竖直面对称,故其本质上以π为周期;而面内激励无此对称性,仍以2π为周期．因此,有无面外激励参与决定了激励间相位差对斜拉索响应的影响规律．     

线性随机桁架结构的平稳随机响应分析

研究了随机桁架结构的平稳随机响应问题。同时考虑结构的物理参数、几何尺寸的随机性，从结构平稳随机响应在频域上的表达式出发，利用求解随机变量函数矩的方法，导出了随机桁架结构在平稳随机激励下位移响应均方值的均值、均方差和变异系数的计算表达式。通过算例考察了随机荷载激励下结构物理参数、几何尺寸的随机性对结构随机响应的影响。