Reaction Mechanism Investigation Using Vibrational Mode Analysis for the Multichannel Reaction of CH_3O+CO

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分离变量法与等腰直角三角形波导的边值问题

根据叠加原理，讨论等腰直角三角形波导边值问题的IE波解和TM波解，纠正有关文献中的错误解法，指出分离变量法的适用条件。     

基于单端半导体光放大器的可调谐超短光脉冲源理论与实验研究

超短光脉冲源是光时分复用(OTDM)系统中的关键器件.提出了一种基于单端半导体光放大器(SOA)的注入型主动锁模光纤激光器产生超短光脉冲的方案，建立了该方案的理论模型.实验实现了高消光比稳定的重复频率10—40GHz皮秒级光脉冲的输出，输出波长在30nm范围内连续可调. 关键词： 超短光脉冲 单端半导体光放大器 主动锁模     

负关联噪声驱动下单模激光的定态分析

研究了负关联的加法和乘法高斯白噪声驱动下单模激光损失模型的定态情况。文中推导了负关联情况下，定态时的激光场幅的几率分布，光强的平均值，光强的协方差以及光强的偏斜率。并和文献〔１，２〕中正关联时的定态分析作了比较，发现了有意义的新现象。     

Identifying potential binding modes and explaining partitioning behavior using flexible alignments and multidimensional scaling

A method is described for the rapid and automatic analysis of flexible molecular alignments using multidimensional scaling and a normalized scoring scheme. A projection scheme was devised to separate orientational and conformational effects. It is shown that the approach can be utilized for the identification of common binding orientations or to the study of differences in partioning behavior. It is suggested that the method can be employed as a novel approach exploring molecular similarity as a dynamic property, so that it includes aspects of motion (by way of mutual orientations), conformations and molecular properties.     

Effects of delayed linear electrical perturbation of the Belousov-Zhabotinsky reaction: a case of complex mixed mode oscillations in a batch reactor

Delayed feedbacks are quite common in many physical and biological systems and in particular many physiological systems. Delay can cause a stable system to become unstable and vice versa. One of the well-studied non-biological chemical oscillators is the Belousov-Zhabotinskii (BZ) reaction. This gives relaxation oscillations for a considerable period of time under batch conditions. This paper deals with the effect of perturbing the limit cycle oscillation of BZ reaction by employing a delayed electrical feedback to the system under batch conditions. The parameters chosen to study are external resistance and delay. For various resistances and delays the system was electrically perturbed and found to exhibit various complex mixed mode oscillations. The dynamic features are accounted for by the Oregonator model, with time delay incorporated in one of the variables. This revised version was published online in June 2006 with corrections to the Cover Date.     

不饱和类锗烯H2C=GeNaBr的密度泛函理论研究

应用密度泛函理论DFT方法,在B3LYP/6-311G(d,p)水平上研究了不饱和类锗烯H2C=GeNaBr的结构及异构化反应.结果表明,不饱和类锗烯H2C=GeNaBr有3种平衡构型,其中非平面的p-配合物型构型能量最低,是其存在的主要构型.并对平衡构型间异构化反应的过渡态进行了计算,求得了转化势垒,预言了最稳定构型的振动频率和红外强度.     

Mechanism of the cyclization of dimethyl diethynyl silane with selenium tetrabromide: Computational and structural studies, and monitoring

The structure of 2,4-dibromo-2-dibromomethyl-3,3-dimethyl-1-selena-3-silacyclopentene-4, formed by regioselective electrophilic addition of SeBr₄ to dimethyl diethynyl silane, has been determined using X-ray analysis technique. Quantum chemistry methods were used to study elementary stages of the reaction. It was found that the first stage consisted of SeBr₄ conversion into bimolecular complex Br₂?SeBr₂, initiated by dimethyl diethynyl silane. Possible formation of five-membered and six-membered heterocycles involves different cyclization mechanisms. The formation of only five-membered heterocycle is explained by kinetically preferable ring closure through four-center transition state. The conclusions obtained by calculations were confirmed by monitoring of the reaction using ¹H NMR method.     

Sol-gel polyimide-silica composite membrane: gas transport properties

The effect of introduction of silica particles prepared by the sol-gel technique on the gas transport properties of a polyimide film was studied. The sorption and permeation of N₂, O₂, CO₂, H₂ and CH₄ were studied and correlated with morphological changes in the polymer structure. From sorption isotherms, we observed that the composite membrane presents higher solubility coefficients than the polyimide one. The solubility coefficient ratio between the composite and the polyimide is about 1.5–2.0. The isotherms were analyzed in terms of the dual mode sorption. The Henry's coefficient and the Langmuir's affinity and saturation constants were obtained allowing to calculate the Langmuir to Henry concentration ratios as function of the gas pressure. These ratios decrease until zero within a certain pressure range as long as the Langmuir's mode is acting and they are higher for the polyimide membrane when compared with the composite one. This study was completed with calorimetric measurements during the sorption. The gas interaction energy in kJ/mol decreases within the same pressure range as previously described. The measured energies are higher for the polyimide film when compared with the composite one because the polyimide membrane presents a stronger energetic effect caused by a higher Langmuir's contribution. From permeation studies at 3.15⁵ Pa, the composite membrane showed higher permeability coefficients and permselectivities than the polyimide one. All these results were explained, taking into account the difference on the imidization degree of both membranes and the morphological changes which may be induced by the silica nodules in the organic/inorganic interphases.     

Chromatographic performance of deuterated solvents in reversed phase micro high performance liquid chromatography

The chromatographic performance of the deuterated solvents, CD₃OD and D₂O, has been investigated in reversed-phase micro high performance liquid chromatography. The chromatographic performance of CD₃OD is only slightly superior to that of CH₃OH. However, the performance of D₂ is significantly superior to that of H₂O, separation of aromatics being improved by about 30%. D₂ is a particularly powerful solvent for the separation iof deuterated and non-deuterated compounds.