Ab initio through space/bond interaction analysis on the stereoelectronic effect by modifying the exponents of the basis set

Akira Imamura, Hiroyuki Sugiyama, Yuuichi Orimoto, Yuriko Aoki

    研究成果: Contribution to journalArticle査読

    18 被引用数 (Scopus)

    抄録

    The concept of the stereoelectronic effect has been widely used for the elucidation of organic reaction mechanisms. However, a detailed analysis of this effect has not been developed, especially at the level of the ab initio molecular orbital method. In the present article, the through space/bond interaction analysis was applied to the stereoelectronic effect at the level of the ab initio molecular orbital method. To obtain a reliable result for the through space/bond interaction analysis, we introduced a novel procedure to cut off a specific through space/bond interaction, that is, cutting off a specific integral is performed by increasing the absolute magnitude of the exponent in a Gaussian function. By this procedure, we can easily find a balance in cutting off the nuclear-electron attractions, the nuclear-nuclear repulsions, and the electron-electron repulsions. By using the above-mentioned procedure, we carried out a through space/bond interaction analysis to the stereoelectronic effect for aminomethanol as a model molecule. As a result, the diagonal terms for the electron transfer play a more important role than do the off-diagonal terms. Since the diagonal term corresponds to the conventional steroelectronic effect, the obtained result is in accordance with the conventional model for the stereoelectronic effect. This result may give a novel insight into the stereoelectronic effect.

    本文言語英語
    ページ(範囲)761-768
    ページ数8
    ジャーナルInternational Journal of Quantum Chemistry
    74
    6
    DOI
    出版ステータス出版済み - 1999

    All Science Journal Classification (ASJC) codes

    • Atomic and Molecular Physics, and Optics
    • Condensed Matter Physics
    • Physical and Theoretical Chemistry

    フィンガープリント 「Ab initio through space/bond interaction analysis on the stereoelectronic effect by modifying the exponents of the basis set」の研究トピックを掘り下げます。これらがまとまってユニークなフィンガープリントを構成します。

    引用スタイル