从头算分子动力学研究O-与CH_3F反应的产物通道

在B3LYP/6-31+G(d,p)理论水平下采用基于波恩-奥本海默近似的从头算分子动力学方法重新研究了O-与CH3F反应经抽氢生成OH-和生成H2O的两条产物通道.反应轨线从反应初始过渡态开始,采用300K时的热取样确定初始条件,同时为对比不同的初始碰撞平动能条件下产物通道的变化,分别限定过渡矢量上的能量为2.1、36.8及62.8kJ·mol-1进行轨线计算,所有轨线计算的结果表明抽氢生成OH-的过程始终为主要的产物通道.我们的计算不仅进一步证实了以往实验的结论,而且描绘了抽氢生成OH-和生成H2O这两个产物通道在反应出口势能面上的动态反应路径,更为深刻地揭示了该反应的微观机理.     

诱导含硫三电子键自由基的生成机理研究

运用248 nm激光光解瞬态吸收光谱，研究了     

离子对生成反应的LCAC-SW量子散射理论研究＊

LCAC-SW method has been extended to study the reaction dynamics for ion-pair formation processes.M+X₂M⁺+X^-₂ reaction system involves two potential energy surfaces,i.e.,the covalence state(M+X₂) and the ionic state(M⁺+X^-₂) and their crossing effect.The working equations for calculating state-to-state probability have been derived based on the above two-state model.The selected-state reaction probabilities of collinear ion-pair formation process M+I₂M⁺+I^-₂(M=Na,K,Cs) on Aten-Lanting-Los two-state potential energy surface have been calculated.The results show that the reaction probabilities are of resonance effect.     

Modeling the coupling of reaction kinetics and hydrodynamics in a collapsing cavity

We introduce a model of cavitation based on the multiphase Lattice Boltzmann method (LBM) that allows for coupling between the hydrodynamics of a collapsing cavity and supported solute chemical species. We demonstrate that this model can also be coupled to deterministic or stochastic chemical reactions. In a two-species model of chemical reactions (with a major and a minor species), the major difference observed between the deterministic and stochastic reactions takes the form of random fluctuations in concentration of the minor species. We demonstrate that advection associated with the hydrodynamics of a collapsing cavity leads to highly inhomogeneous concentration of solutes. In turn these inhomogeneities in concentration may lead to significant increase in concentration-dependent reaction rates and can result in a local enhancement in the production of minor species.     

Random yield supply chain with a yield dependent secondary market

This paper considers a simple supply chain with one supplier and one retailer where the supplier’s production is subject to random yield and the retailer faces uncertain demand. There exists a secondary market for acquiring or disposing products by the supplier. We study both the centralized and decentralized systems. In the decentralized system, a no risk sharing contract and a risk sharing minimum commitment contract are analyzed. The supply chain with the risk sharing contract is further analyzed with a constant secondary market price and a yield dependent secondary market price. We present both the supplier’s and the retailer’s optimal strategies and provide insights for managers when making decisions under random yield risk and demand uncertainty. We find that the secondary market generally has a positive impact on supply chain performance and the actual effect of random yield risk on the supply chain performance depends on cost parameters and supply chain contract settings. Under certain conditions, reducing yield randomness may weaken the double marginalization effect and improve the chain performance. From the numerical study, we also show that there exists an optimal commitment level for the supply chain.     

Automation of the Photodegradation Spectrophotometric Method for the Determination of Diethylstilbestrol by Flow Injection

ABSTRACT

An spectrophotometric determination of diethylstilbestrol is proposed on the basis of on-line photo-degradation and measurement at 330 nm. The procedure is accomplished by means of flow-injection assembly including a photo-reactor formed by a PTFE 168 cm long coil around a low-pressure mercury lamp 6 w; this photo-reactor was nested between the injection valve and the spectrophotometric flow-cell. The sample solution was injected into a carrier stream of aqueous di-potassium hydrogen ortophosphate flowing at 5.0 ml min^?1. Influence of the physic-chemical and hydrodynamic parameters was studied and optimised. The calibration graph was linear up to 65 mg l^?1, and the procedure presented a reproducibility (rsd of the calibration slope) 1.4%, and a sample throughput of 52 h^?1. The influence of foreign compounds was tested.     

类硅烯H_2SiLiF二聚反应的理论研究

从理论上研究了类硅烯H2SiLiF的三元环构型为反应物的二聚反应2H2SiLiF→H2SiSiH2+2LiF。在MP2/6-31G(d)和QCISD(T)/6-31G(d)水平下的计算结果表明,H2SiLiF的二聚反应经过两个阶段:阶段I,先形成过渡态TS1,经过中间体Int,形成一个四元环的中间产物Pro1,同时消去一个LiF;阶段Ⅱ,Pro1继续反应形成过渡态TS2,进而解离生成产物H2SiSiH2和一个LiF。从能量上看,反应易停留在中间产物阶段。本文对反应物、过渡态以及产物的结构、稳定性等方面进行了讨论,很好解释了实验结果。     

High‐molecular‐weight AB‐type benzoxazines as new precursors for high‐performance thermosets

Novel high‐molecular‐weight polybenzoxazine precursors, namely AB‐type benzoxazine precursors, were synthesized from aminophenols and formaldehyde. Both ¹H NMR and IR confirmed the structure of the precursors, indicating the presence of a cyclic benzoxazine structure in the backbone of the precursors. The weight‐average molecular weight was estimated by size exclusion chromatography to be to in the range of 1300–4500. The precursors gave self‐standing thin films when their solutions were cast in dioxane over glass plates and dried, and upon a gradual thermal cure up to 250 °C, they afforded polybenzoxazine films. The viscoelastic analyses showed that the glass transition temperatures of the polybenzoxazine films obtained from these novel precursors were as high as 260–300 °C. Thermogravimetric analysis results indicated that the onset of decomposition and the char yield of the thermosets derived from these AB‐type precursors were higher than those of traditional polybenzoxazine. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1878–1888, 2007.     

Numerical solution of a fast diffusion equation

In this paper, the authors consider the first boundary value problem for the nonlinear reaction diffusion equation: in , a smooth bounded domain in with the zero lateral boundary condition and with a positive initial condition, (fast diffusion problem), and . Sufficient conditions on the initial data are obtained for the solution to vanish or become infinite in a finite time. A scheme for the discretization in time of this problem is proposed. The numerical scheme preserves the essential properties of the initial problem; namely existence of an extinction or a blow-up time, for which estimates have been obtained. The convergence of the method is also proved.

     

Instantaneous Fluorescence Quantum Yield—A New Quantity with Characteristic “Fingerprints” for Excited-State Processes

The instantaneous fluorescence quantum yield _ins—a new quantity for fluorescence studies defined as the ratio of the fluorescence intensity to the optical density, both measured at the moment of the maximum of the exciting pulse—proves to be a very sensitive function for excited-state processes. Dependent on the excitation intensity _ins exhibits characteristic features (maxima/minima) indicating, for example, excited-state absorptions and annihilation processes. _ins is therefore more informative as the intensity dependence of the usually utilized fluorescence yield, the information content of which is restricted because this function is hardly structured. In the paper the influences of specific molecular parameters (excited-state absorption cross section, annihilation constant) on _ins are given, problems of the experimental accessibility of _ins are discussed, and an experimental setup for determination of this new quantity is presented. The application of the method is demonstrated for identification of excited-state absorptions of organic molecules in solution.