Electron Flow in Reaction Mechanisms-Revealed from First Principles
Electron Flow in Reaction Mechanisms-Revealed from First Principles
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DOI：
10.1002/anie.201410637
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发表时间：
2015-04-27
影响因子：
16.6
通讯作者：
Klein, Johannes E. M. N.
中科院分区：
文献类型：
--
作者：
Knizia, Gerald;Klein, Johannes E. M. N.
罗宾逊（Robinson）和英戈尔德（Ingold）提出的“弯箭头”是描述和解释反应机理的主要工具。尽管这种方法应用广泛且极其成功，但其物理基础从未得到阐明，与量子化学也从未建立起直接联系。在此我们报道，弯箭头所表示的键重排可以在从头算计算中直接观察到，表现为内禀键轨道（IBOs）沿着反应坐标的转变。我们的结果阐明了弯箭头是基于物理现实的——这是一个此前曾受到质疑的观点——并且展示了量子化学如何能够以直观的方式和前所未有的细节直接确定反应机理。
The "curly arrow" of Robinson and Ingold is the primary tool for describing and rationalizing reaction mechanisms. Despite this approach's ubiquity and stellar success, its physical basis has never been clarified and a direct connection to quantum chemistry has never been found. Here we report that the bond rearrangements expressed by curly arrows can be directly observed in ab initio computations, as transformations of intrinsic bond orbitals (IBOs) along the reaction coordinate. Our results clarify that curly arrows are rooted in physical reality-a notion which has been challenged before-and show how quantum chemistry can directly establish reaction mechanisms in intuitive terms and unprecedented detail.