A molecular orbital calculation of chemically interacting systems. Interaction between two radicals.
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概要
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The reaction path of radical-radical recombination and disproportionation has been studied by means of a perturbational method with a clear orbital interaction concept, and the mechanism of these reactions has been elucidated theoretically. It has been confirmed that these termination reactions do not have a common transition state. The recombination is found to take the path which gives the maximum interaction between the singly occupied molecular orbitals (SOMO's) of two radical species, whereas the disproportionation is shown to take the route which gives the significant charge transfer interaction from the particular doubly occupied (DO) MO of one radical to the SOMO of the other radical. The DOMO localized at the C–H bond donates electrons to the SOMO to cause the hydrogen abstraction. In the process of disproportionation, one radical which abstracts a hydrogen atom acts as an electron-acceptor and the other radical with the hydrogen atom to be abstracted as an electron-donor. The difference between the mechanism of the recombination and that of the disproportionation is clarified in terms of the mode of the orbital interaction.
- 公益社団法人 日本化学会の論文
著者
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Yamabe Shinichi
Department Of Chemistry Nara University Of Education
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Fukui Kenichi
Faculty of Engineeering Kyoto University
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FUKUI Kenichi
Faculty of Engineering, Kyoto University
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Fujimoto Hiroshi
Faculty of Engineering, Kyoto University
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Minato Tsutomu
Faculty of Engineering, Kyoto University
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