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Molecular Theory of Electronic Structure Design and Control of Reactions and Its Application

电子结构设计与反应控制的分子理论及其应用

基本信息

批准号：
02303002
负责人：
FUJIMOTO Hiroshi
金额：
$ 7.17万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Co-operative Research (A)
财政年份：
1990
资助国家：
日本
起止时间：
1990 至 1992
项目状态：
已结题

项目摘要

We have studied the following four subjects with a view to developing a molecular theory for the design of electronic structures and control of reactions.(i)By applying the ab initio molecular orbital theory,the accurate potential energy surfaces for chemical reactions of small molecules,radicals and ions have been determined. Reaction dynamics of radicals with oxygen molecules have been analyzed. An adiabatic channel model has been proposed for the reactions between vivrationally excited ions and molecules. The dynamics and spectroscopy of reactive transition states and highly vibrationally excited molecules have been investigated theoretically and experimentally.(ii)Effects of secondary orbital interactions have been analyzed to control the selectivity in cycloaddition reactions. Theoretical calculations have been performed on unsaturated molecules containing group 14 elements. Strains in small ring molecules have been interpreted in terms of geminal electron delocalization.(iii)Transition metal complexes which have potential ability of reducing carbon dioxide have been studied theoretically Rhodium complexes which are able to activate carbon-hydrogen and silicon-hydrogen bondshave been suggested. The mechanism of controlling the regio- and stereo-selectivities in olefin polymerization by zirconium complexes has been studied by means of theoretical calculations.(iv)Elongation theory of calculating the electronic structure of polymers has been developed. Theoretical treatments of solvent effects on chemical reactions and of calculating the potentials have been proposed.

我们研究了以下四个主题，以期建立一种设计电子结构和控制反应的分子理论。(1)应用从头算分子轨道理论，确定了小分子、自由基和离子化学反应的准确势能面。分析了自由基与氧分子的反应动力学。提出了一种热通道模型来描述振动激发离子与分子之间的反应。对反应跃迁态和高振动激发分子的动力学和光谱学进行了理论和实验研究。（ii）分析了二级轨道相互作用对控制环加成反应选择性的影响。对含有14族元素的不饱和分子进行了理论计算。小环分子中的应变已经用双电子离域来解释。(3)对具有潜在还原二氧化碳能力的过渡金属配合物进行了理论研究。铑配合物能够激活碳-氢键和硅-氢键。通过理论计算研究了锆配合物在烯烃聚合过程中控制区域选择性和立体选择性的机理。（四）发展了计算聚合物电子结构的伸长率理论。提出了溶剂对化学反应影响的理论处理方法和化学反应电位的计算方法。