在 Ab initio 直接动力学研究中,研究了环基的环开放性
1Department of Chemistry and Institute for Scientific Computing, Wayne State University, Detroit, MI 48202, USA.
Journal of the American Chemical Society
|March 28, 2002
概括
模拟了环基环开放的立体化学. 虽然预测是旋转的,但观察到的是旋转的途径,这表明基产物中的能量再分配不完全.
科学领域:
- 化学动力学 化学动力学
- 量子化学 是一个量子化学.
- 反应机制 反应机制
背景情况:
- 环基的电环开放是有机化学的一个基本反应.
- 了解其立体化学结果对于预测产品形成至关重要.
研究的目的:
- 为了研究环基的电循环环开放反应的立体化学.
- 使用计算方法探索产品的动态和分布.
主要方法:
- 进行了近乎经典的直接动力学模拟.
- 使用了CASSCF{3,3)/6-31G{d) 级理论.
- 轨迹是从过渡状态 (TS) 开始使用博尔兹曼分布.
主要成果:
- 内在反应坐标计算预测了反旋转立体化学.
- 然而,43%的模拟轨迹遵循的是旋转轨道.
- 观察到四种不同的轨迹类型在200 fs动态的基产物.
结论:
- 最初的反应立体化学主要是旋转的,但旋转途径是显著的.
- 在200 fs的范围内,分子内振动能量再分配和内部旋转是不完整的.
- 在这个时间尺度上,没有实现基异构体的统计分布.
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