Electron-Nuclear Motion in the Cope Rearrangement of Semibullvalene: Ever Synchronous?

被引:10
作者
Bredtmann, Timm [1 ]
Paulus, Beate [1 ]
机构
[1] Free Univ Berlin, Inst Chem & Biochem, D-14195 Berlin, Germany
关键词
THERMOCHROMIC SEMIBULLVALENES; DELOCALIZED STATES; TRANSITION-STATES; ENERGY SURFACES; EXCITED-STATE; AB-INITIO; EQUILIBRIUM; HOMOAROMATICITY; 1,5-HEXADIENE; SPECTROSCOPY;
D O I
10.1021/ct400318z
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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).
引用
收藏
页码:3026 / 3034
页数:9
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