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

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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.