排序方式: 共有59条查询结果,搜索用时 31 毫秒
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本文用WIGNER-KIRKWOOD微扰展开法来推导分子阻障内旋转配分函数的近似表示式,准确到h[2]项,所得公式只包含两个参量(即分子自由旋转配分函数Qf和势垒高度UO与kT之比值)并可用BESSEL函数来表示,数值计算结果表明,在内旋转转动惯量较大,温度较高这一实用上最为重要的范围内,根据本文中所得公式,对任意的Qf值和U0/kT值,可直接算得阻障势能所产生的熵的修正值(Sir-Srir)/k,比用数值求解法较为简单而准确,如计及微扰展开的高次项,还可以在整个温度范围内取得良好的数值结果。不仅如此,本文所得出的解析公式容易推广到多维运动的情况中去,因此较PITZER的数值求解法具有更普遍的意义。 相似文献
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N-4-甲基-4-戊烯基硝酮分子内环加成反应可以生成氧桥型(Pa)和碳桥型(Pb)两种产物, 其实验产率比约为8:1。而在N-4位未取代的情况下, Pa与Pb的实验产率比约为1:2。可见N-4-甲基使得区域选择性发生了很大的变化。本文用AM1 MO方法和过渡状态理论研究了N-4-甲基-4-戊烯基硝酮分子内环加成反应的机理。计算了两个平行反应(a, b)的速率常数的比值, 得到与实验吻合的结果。计算表明, N-4-甲基取代后, a, b两反应的活化熵的相对变化是区域选择性改变的主要因素, 活化焓的相对变化只是一个次要因素。 相似文献
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《Quaestiones Mathematicae》2013,36(2):229-248
Several investigations have been made on singularly perturbed integral equations. This paper aims at presenting an algorithm for the construction of asymptotic solutions and then provide a proof for asymptotic correctness to singularly perturbed systems of Volterra integro-differential equations. 相似文献
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《Composite Interfaces》2013,20(7-9):751-768
The aim of this study was to investigate the effects of electron beam (EB) irradiation on the morphological properties, crystallinity and surface area of henequen fiber and on the mechanical and thermal properties of henequen fiber reinforced polypropylene (PP) composites. The structure of henequen fiber was characterized by X-ray diffraction, mercury porosimetry and BET surface area analysis. The EB irradiation of 10 kGy led to the increasing of crystalline and surface pore area of henequen fiber, which contributed to the number of interlocking places with PP. From the results of tensile and impact strength tests, the highest value was observed for the composite reinforced with the henequen fiber treated with EB dose of 10 kGy, decreasing overall as EB dose increased. This tendency was also shown by coefficient of thermal expansion (CTE) measurements, but the value of CTE decreased until 50 kGy, meaning that a large total surface area can provide many interlocking places and so improve adhesion between fiber and matrix. Therefore, it can be concluded that the optimum pore surface area by 10 kGy irradiation contributes to successful mechanical interlocking between fiber and matrix and consequently enhances the mechanical and thermal properties of the composites. 相似文献
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用量热滴定法于298.15K测定了除钪、钷以外的全部十五种稀土(III)高氯酸盐与苯并-15-冠-5在乙腈溶液中的配位作用。借助计算机算出了配合物的稳定常数和配位焓, 进而算出了配位自由能和配位熵。结果表明:十五种稀土(III)离子与苯并-15-冠-5都可以配位, 配位焓为正值;La^3^+配合物最稳定, Ce^3^+次之, 其余稀土(III)离子配合物稳定性变小, 但彼此差别不大, 在Tb处有突变;熵在配合物形成时起稳定化作用。 相似文献
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