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

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)761-768
Number of pages8
JournalInternational Journal of Quantum Chemistry
Volume74
Issue number6
DOIs
Publication statusPublished - Jan 1 1999
Externally publishedYes

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exponents
Electrons
Molecular orbitals
interactions
molecular orbitals
electrons
Molecules
attraction
electron transfer
cut-off
molecules

All Science Journal Classification (ASJC) codes

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

Cite this

Ab initio through space/bond interaction analysis on the stereoelectronic effect by modifying the exponents of the basis set. / Imamura, Akira; Sugiyama, Hiroyuki; Orimoto, Yuuichi; Aoki, Yuriko.

In: International Journal of Quantum Chemistry, Vol. 74, No. 6, 01.01.1999, p. 761-768.

Research output: Contribution to journalArticle

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