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.
|ジャーナル||International Journal of Quantum Chemistry|
|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