An Energy Interconversion Principle Applied in Reaction dynamics for the determination of equilibrium standard states

Chemical and other reaction theories involving thermodynamical equilibrium states utilize statistical mechanical equilibrium density distributions. Here, a definition of heat-work transformation termed thermo-mechanical coherence is first made, and it is conjectured that most molecular bonds have the above heat-work transformation property, which models a chemical bond as a “centrifugal heat engine”, where the internal energy state need not correspond to any of the standard equilibrium densities. Expressions are derived for the standard Gibbs free energy, enthalpy, and entropy where the bond coordinates need not conform to a non-degenerate Boltzmann state, since bond breakdown and formation are processes that have direction, whereas equilibrium distributions are derived when the Hamiltonian is of fixed form, which is not the case for chemical reactions using localized Hamiltonians. The empirically determined Gibbs free energy from a known molecular dynamics simulation of a dimer reaction , accords rather well with the theoretical estimate. A relation connecting the rate of reaction with the equilibrium constant and other kinetic parameters is derived and could place the commonly observed linear relationship between the logarithms of the rate constant and equilibrium constant on a firmer theoretical footing. These relationships could include analogues of the Hammett correlations used extensively in physical organic chemistry, as well as others which are temperature dependent. One prediction of the principles developed here is that the equilibrium standard reaction free energy is more dependent on the height of the intermolecular potential than its depth, so that the sign of the ΔG ^θ can change for varying barrier height with fixed well depth, which may appear counter-intuitive. All the above developments can be tested directly in simulations and therefore provides a fertile ground for further research with significant implications on how standard states are determined in relation to the direction of chemical reaction.This work treats the molecular bond using standard thermodynamics as if it were a system, and it is anticipated that with the advent of single-molecule science and experiment, that might be one direction in which molecular statistical thermodynamics would develop.     

Existence results for generalized vector equilibrium problems with applications

By a coincidence theorem, some existence theorems of solutions are proved for four types of generalized vector equilibrium problems with moving cones. Applications to the generalized semi-infinite programs with the generalized vector equilibrium constraints under the mild conditions are also given. The results of this paper unify and improve the corresponding results in the previous literature.     

激光诱导击穿空气等离子体光谱及半经验理论模拟

利用Nd∶YAG激光器输出的1 064 nm激光进行了激光诱导击穿空气光谱实验,测量了空气等离子体的时间分辨光谱。基于局域热动力学平衡模型,建立了模拟激光诱导击穿光谱的方法。对700~900 nm波段的空气等离子体光谱进行了模拟。通过模拟结果与实验结果的比较,进一步估算出了空气中氮、氧和氩的相对含量。     

基于变分不等式的生态工业链网络均衡问题研究

以变分不等式为基础提出生态工业链网络均衡模型。生态工业链是通过仿照自然生态系统中的物质循环方式与生物群体之间的竞争与共生模式,使不同企业之间形成共享资源和互换副产品从而实现园区各企业经济与环境效益的最大化。针对生态工业链网络的多产品(主副产品和废弃物)多层次的网络结构,模仿自然生态系统中的生产者、消费者和分解者,分别对各层决策者的独立优化决策行为及其相互作用进行分析,利用变分不等式分析各层均衡条件进而构建生态工业链网络均衡模型,得到系统达到均衡的条件并给出相应的经济解释。在证明系统变分不等式的解存在的基础上,通过数值算例验证模型的合理性与有效性。     

Versatile code DLAYZ for investigating population kinetics and radiative properties of plasmas in non-local thermodynamic equilibrium

A versatile code DLAYZ based on collisional-radiative model is developed for investigating the population kinetics and radiative properties of plasmas in non-local thermodynamic equilibrium. DLAYZ is implemented on the detailed level accounting (DLA) approach and can be extended to detailed configuration accounting (DCA) and hybrid DLA/DCA approaches. The code can treat both steady state and time-dependent problems. The implementation of the main modules of DLAYZ is discussed in detail including atomic data, rates, population distributions and radiative properties modules. The complete set of basic atomic data is obtained using relativistic quantum mechanics. For dense plasmas, the basic atomic data with plasma screening effects can be obtained. The populations are obtained by solving the coupled rate equations, which are used to calculate the radiative properties. A parallelized version is implemented in the code to treat the large-scale rate equations. Two illustrative examples of a steady state case for carbon plasmas and a time-dependent case for the relaxation of a K-shell excited argon are employed to show the main features of the present code.     

基于MIV-BP型网络实验的房地产项目风险识别研究

为了更准确更客观地识别房地产项目中的风险,为房地产项目投资决策提供科学依据和参考,有效地规避风险,本研究在BP神经网络 (Back-Propagation Neural Network)建模的基础上,采取MIV(Mean Impact Value)算法对BP神经网络模型进行变量筛选的网络优化和改良,从而形成新的优化后的MIV-BP(Mean Impact Value Back-Propagation Neural Network)神经网络,并以此用于评价房地产项目中的风险度以及各因素在风险度中的影响作用大小;同时选取目前相关的房地产项目数据进行仿真实证分析和验证。验证实验结果表明,MIV-BP型神经网络对于房地产项目风险度识别具有良好的适应性和准确性,实验结果客观,达到专家评价的要求,并在风险因素作用度分析上具有良好的应用价值。     

无机化学中的一题多解

无机化学计算中采取一题多解可开拓学生的思维,加深对化学基本原理的理解和掌握,有利于巩固和提高所学知识,并加以灵活运用,做到触类旁通。文章以无机化学教学中化学平衡、电极电势2类问题的计算给予说明。     

Structural, electronic and vibrational properties of indium oxide clusters

Geometric, electronic and vibrational properties of the most stable and energetically favourable configurations of indium oxide clusters In_mO_n (1≤m, n≤4) are investigated using density functional theory. The lowest energy geometries prefer the planar arrangement of the constituent atoms with a trend to maximize the number of ionic In-O bonds. Due to the charge transfer from In to O atoms, the electrostatic repulsion occurs between the atoms with the same kind of charge. The minimization of electrostatic repulsion and the maximization of In-O bond number compete between each other and determine the location of the isometric total energy. The most stable linear In-O-In-O structure of In₂O₂ cluster is attributed to the reduced electrostatic repulsive energy at the expense of In-O bond number, while the lowest energy rhombus-like structure of In₂O₃ cluster reflects the maximized number of In-O bonds. Furthermore, the vibrational frequencies of the lowest energy clusters are calculated and compared with the available experimental results. The energy gap and the charge density distribution for clusters with varying oxygen/indium ratio are also discussed.     

Equilibrium equations for 3D critical buckling of helical springs

In most cases,the research on the buckling of a helical spring is based on the column,the spring is equivalent to the column,and the torsion around the axial line is ignored.A three-dimensional(3D) helical spring model is considered in this paper.The equilibrium equations are established by introducing two coordinate systems,the Frenet and the principal axis coordinate systems,to describe the spatial deformation of the center line and the torsion of the cross section of the spring,respectively.By using a small deformation assumption,the variables of the deflection can be expanded into Taylor’s series,and the terms of high orders are ignored.Hence,the equations can be simplified to the functions of the twist angle and the arc length,which can be solved by a numerical method.The reaction loads of the spring caused by the axial load subjected to the center point are also discussed,giving the boundary conditions for the solution to the equilibrium equations.The present work is useful to the research on the behavior of the post-buckling of the compressed helical spring.     

Asymmetric simple exclusion processes with complex lattice geometries: A review of models and phenomena

We summarize the findings of a large number of studies concerning the totally asymmetric simple exclusion process (TASEP) with complex lattice geometries. The TASEP has been recognized as a paradigm in modeling and analyzing non-equilibrium traffic systems. The paper surveys both the observed physical phenomena and several popular meanfield approaches used to analyze the extended TASEP models. Several interesting physical phenomena, such as phase separation, spontaneous symmetry breaking, and the finite-size effect, have been identified and explained. The future investigations of the extended TASEP with complex lattice geometries are also introduced. This paper may help to obtain a better understanding of non-equilibrium systems.