Electron-Nuclear Motion in the Cope Rearrangement of Semibullvalene: Ever Synchronous?
Electron-Nuclear Motion in the Cope Rearrangement of Semibullvalene: Ever Synchronous?
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DOI：
10.1021/ct400318z
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发表时间：
2013-07-01
影响因子：
5.5
通讯作者：
Paulus, Beate
中科院分区：
文献类型：
--
作者：
Bredtmann, Timm;Paulus, Beate
利用非含时量子化学方法研究了原子核运动对半牛瓦烯简并科普电子重排的同步性的影响.我们发现，对应于同步核重排的势能面上的不同路径沿着涉及从旧键到新键的异步电子通量，而同步电子通量则需要异步核重排。为了证明结果的鲁棒性，使用各种高级量子化学方法，包括使用三重zeta基组（RS 2/cc-PVTZ）的二阶多参考微扰理论的全结构优化，随后在理论的RS3/cc-pVTZ和MRCI+Dav/cc-pVTZ水平上进行改进，用于求解电子薛定谔方程。这些基准结果。扩展了先前关于半牛瓦烯的简并科普重排的量子化学数据并针对较低水平的方法进行了测试（例如，使用B3 LYP和B3 PW 91泛函的密度泛函理论计算）。
The effect of nuclear motion on the synchronicity of the pincer motion type electronic rearrangement associated with bond making and bond breaking and vice versa is investigated for the degenerate Cope rearrangement of semibullvalene using a time-independent quantum chemical approach. We find that distinct paths along the potential energy surface corresponding to synchronous nuclear rearrangement involve asynchronous electronic fluxes out of the old and into the new bond while synchronous electronic fluxes entail asynchronous nuclear rearrangement. In order to demonstrate the robustness of the results, various high-level quantum chemical :methods including full structure optimizations up to second order multireference perturbation theory using triple-zeta basis sets (RS2/cc-PVTZ), which are subsequently refined at the RS3/cc-pVTZ and MRCI+Dav/cc-pVTZ levels of theory, are used for solving the electronic Schrodinger equation.. These benchmark results. extend previous' quantum chemical data for the degenerate Cope rearrangement of semibullvalene and are tested against lower level methods (e.g., density functional theory calculations using the B3LYP and B3PW91 functionals).