Modern Valence-Bond Description of Homoaromaticity,The Journal of Physical Chemistry A

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Modern Valence-Bond Description of Homoaromaticity
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2016-10-25 00:00:00 , DOI: 10.1021/acs.jpca.6b09426
Peter B. Karadakov ₁ , David L. Cooper ₂

Affiliation

Spin-coupled (SC) theory is used to obtain modern valence-bond descriptions of the electronic structures of local minimum and transition-state geometries of three species that have been considered to exhibit homoconjugation and homoaromaticity: the homotropenylium ion, C₈H₉⁺, the cycloheptatriene neutral ring, C₇H₈, and the 1,3-bishomotropenylium ion, C₉H₁₁⁺. The resulting compact SC wave functions are of comparable quality to complete-active-space self-consistent field constructions that are based on the same “N electrons in M orbitals” active spaces, but they are much easier to interpret directly. Analysis of the forms of the SC orbitals and of the overlaps between them, as well as an examination of the compositions of the associated resonance patterns, strongly suggest that both of the homotropenylium and 1,3-bishomotropenylium ions are homoaromatic at their local minimum geometries, with all of the other cases that were considered being nonaromatic. The SC results also show that the differences between “no-bond” and “bond” homoconjugated systems are very likely to be much smaller than previously thought.

中文翻译：

均价的现代价键描述

自旋耦合（SC）理论用于获得现代价键描述的三个物种的局部最小和过渡态几何结构的电子结构，这些物种被认为具有同构共轭和同芳香性：同型偏二烯鎓离子C ₈ H ₉⁺，环庚三烯中性环C ₇ H ₈和1,3-双茂金属离子C ₉ H ₁₁⁺。由此产生的紧凑型SC波函数的质量与完全活动空间自洽场构造（基于M中相同的N个电子）具有可比的质量轨道”的活动空间，但直接解释起来要容易得多。分析SC轨道的形式以及它们之间的重叠，以及检查相关的共振模式的组成，有力地表明，同向异戊烯基离子和1,3-双顺反丁烯二鎓离子在它们的局部最小几何形状上都是同芳香族的，而所有其他情况都被认为是非芳香族的。SC结果还表明，“无键”和“键”均共轭体系之间的差异很可能比以前认为的要小得多。

更新日期：2016-10-25

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