含有的物种的电子,化物和化物亲和关系:计算研究
Robert Damrauer1, April J Crowell, Colleen F Craig
1Chemistry Department, University of Colorado at Denver, Denver, CO 80217-3364, USA. robert.damrauer@cudenver.edu
Journal of the American Chemical Society
|August 28, 2003
概括
替代显著影响碳基电子亲和力 (EAs). 对于短距离,EA很大,但随着含有的离子循环转化为五坐标结构,EA迅速减少.
科学领域:
- 计算化学计算化学
- 量子化学 是一个量子化学.
- 有机化学 有机化学
背景情况:
- 了解电子亲和力 (EA) 对于预测化学反应性和稳定性至关重要.
- 替代对有机基性质的影响尚未完全理解,特别是关于电子附着.
- 之前的研究已经探讨了的影响,但像循环化这样的特定结构变化的影响需要进一步调查.
研究的目的:
- 研究替代对碳基的电子亲和力的距离依赖影响.
- 分析含离子的结构变化,特别是五度协调,以及它们对EA的影响.
- 通过将计算的EA值与相关物种的实验数据进行比较来验证计算方法.
主要方法:
- 利用计算化学方法研究SiH3(CH2) nCH2和SiH2F(CH2) nCH2系统中的电子亲和力.
- 计算了各种链条长度 (n) 的电子亲和度和垂直附着能量.
- 分析了几何变化,包括五坐标离子的形成,具有三角形双金字塔几何.
主要成果:
- 当n=0时,两个研究系统的电子亲和度都很大.
- 对于n > 1,离子经过循环转化到五坐标结构,显著改变EA.
- 对非循环离子和垂直附着能量的计算EA表明,n > 1的EA迅速减弱,接近甲基 (CH3) 的EA减弱.
结论:
- 替代强烈影响碳基的电子亲和力,其影响取决于距离.
- 离子中的五坐标导致了深刻的几何变化,使EA解释复杂化.
- 对实验数据进行验证的计算方法显示,随着链条长度超过n=1.1,EA值迅速减少.
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