费托反应本征动力学中合成气分压对反应速率的影响

利用高通量动力学反应器测量了本征条件下钴基费托催化剂上反应物消耗速率rCO和产物生成速率rCH4随固定床床层的分布,并考察了它们在不同入口分压(p0CO,p0H2)条件下的变化.结果表明,入口氢碳比(H/C)0=p0H2/p0CO为影响速率的敏感外部变量,反应速率随(H/C)0的增加而加快;而合成气总压p0H2+CO则...     

Combinational simulations of free energy of polymer solution

It is conceptually proposed that the total entropy of polymer solution is contributed from two distinct parts: the positional and the oomformational. The former can be represented analytically, while the latter can be simulated with the random self-avoiding walk model on the simple cubic lattice for multichain systems. The obtained results indicated that both the conformational entropy and the mixing heat are consistent with the scaling laws wry well.     

An accurate numerical multicenter integration for molecular orbital theory

A powerful and accurate numerical three‐dimensional integration scheme was developed especially for molecular orbital calculations. A multicenter integral is decomposed into the sum of single‐center integrals using nuclear weight functions and calculated using Gaussian quadrature rules. The decomposed single‐center integrands show strong anisotropy. With a careful selection of the Gaussian quadrature rule according to the anisotropy, it is possible to obtain an accuracy of 13 digits with a small number of integration points for the overlap integrals, normalization integrals, and molecular integrals for the hydrogen molecule. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 72: 509–523, 1999     

自制光电比色计及其在中学化学实验中的应用

针对大多数中学缺乏光电比色计和分光光度计的现状,基于朗伯-比尔定律和3D打印技术自制光电比色计,测定透明有色溶液的吸光度和浓度。利用自制光电比色计测定了琥珀酸亚铁片中铁的含量和硫酸铜晶体中结晶水的含量,实验结果表明自制光电比色计的精度高、准确性好。将3D打印技术引入化学实验创新改进,体现了跨学科融合和创新设计的思想。     

The approximation of electron densities

This paper discusses the approximate representation of the electron density produced by an ab initio calculation. A linear combination of Gaussians is fitted to the density by minimizing a functional which is the consequent error in field-energy. The practical implementation of the procedure, following a Gaussian 80 calculation, is described and some of the complications are analysed.     

Importance of the Debye interaction in organic solutions: Henry's law constants for polar liquids in nonpolar solvents and vice versa

Henry's law constants have been determined for -butyrolactone (BL), ethyl acetate (EA), and 2-methyl-3-pentanol (MEP) in mixtures of iso-octane (ISO) and toluene (TOL), for BL, EA, TOL, and ISO in cinnamaldehyde (CIN) and for TOL and ISO in each other and in BL. From these data and published vapor pressures, the activity coefficients at infinite dilution and the standard molar Gibbs free energy of transfer, G ₂ ⁰ of the solutes from dilute solution in ISO to dilute solution in each solvent medium have been calculated. The different behavior patterns of BL and EA are attributed to differences in their abilities to exist in different conformations possessing different dipole moments. For polar solutes, G ₂ ⁰ decreases with increasing polarizability of the solvent and with increasing dipole moment of the solute, suggesting increased contributions from dipole-induced dipole (Debye) interactions. The sigmoidal plot of G ₂ ⁰ against the change in pair potential energy calculated from the classical expressions suggests that G ₂ ⁰ seriously underestimates the strength of the Debye interactions in comparison with the London interactions.     

Gaussian basis sets for calculation of spin densities in first-row atoms

Summary The suitability of Gaussian basis sets for ab initio calculation of Fermi contact spin densities is established by application to the prototype first-row atoms B-F having open shell p electrons. Small multiconfiguration self-consistent-field wave functions are used to describe relevant spin and orbital polarization effects. Basis sets are evaluated by comparing the results to highly precise numerical grid calculations previously carried out with the same wave function models. It is found that modest contracted Gaussian basis sets developed primarily for Hartree-Fock calculations can give semiquantitative results if augmented by diffuse functions and if further uncontracted in the outer core-inner valence region.     

帝国−封建和主权国家的知识转型：以欧洲法学史为中心的考察

欧洲从帝国体系向主权国家体系的近代转型,是一场深远影响欧洲和世界政治的大事件,但这场转型在法学领域是如何表现出来的,学术界并没有深入研究。罗马法研究主要集中在私法领域,历史学研究基本不触及法学问题,从而形成了一个理论空白点。本文通过挖掘欧洲罗马法解释传统,呈现出欧洲中世纪帝国−封建和近代主权国家两种政治模式的法学逻辑,肯定了注释、评注和人文主义法学家在欧洲政治转型中的关键作用,展现了罗马法在欧洲公法研究传统中的重要地位。