Pure through-bond state in organic molecules for analysis of the relationship between intramolecular interactions and total energy
Pure through-bond state in organic molecules for analysis of the relationship between intramolecular interactions and total energy
复制标题
有机分子中的纯通键态，用于分析分子内相互作用与总能量之间的关系
DOI：
10.1002/qua.10523
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发表时间：
2003
影响因子：
2.2
通讯作者：
Y. Aoki
中科院分区：
文献类型：
--
作者：
Y. Orimoto;Y. Aoki
从头算构型相互作用通过空间/键相互作用分析被用来研究特定的分子内相互作用，包括电子关联的影响。为了验证该方法的有效性，我们将其应用于乙烷中的旋转势垒。我们的测试结果表明，乙烷势垒对几何松弛的不敏感性与通过轨道重叠和其他因素消除相互作用密切相关。轨道重叠包括交换排斥和超共轭；其他因素包括经典的库仑相互作用和键轨道能量的变化。没有势垒的旋转态(纯贯通键态)不仅可以通过删除属于不同甲基的CH键之间的“邻近”相互作用，而且可以通过删除甲基中的“双基”相互作用来实现。我们对分子轨道的混合分析支持了超共轭交错构象的优越性。此外，我们的处理不仅可以应用于激发态，也可以应用于基态，包括电子相关效应。©2003威利期刊公司Int J Quantum Chem，2003
Ab initio configuration interaction through-space/bond interaction analysis was proposed for the examination of specific intramolecular interactions including the effect of electron correlations. To test the effectiveness of our method, we applied it to rotational barrier in ethane. The results of our test suggest that the insensitivity of the ethane barrier to geometric relaxations is intimately connected with the cancellation of interactions through orbital overlaps and other factors. The orbital overlaps include exchange repulsion and hyperconjugation; other factors include classic Coulomb interaction and changes in bond orbital energy. The rotational state without the barrier (pure through-bond state) can be achieved by deleting not only the “vicinal” interactions between the CH bonds that belong to different methyl groups but also the “geminal” interactions within the methyl groups. Our mixing analysis of molecular orbitals supports the superiority of the staggered conformer by hyperconjugation. Moreover, it was demonstrated that our treatment could be applied to excited states as well as to the ground state, including electron correlation effects. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003