The Electronic Structures of trans and cis Isomers of Some Halogenoethylenes
The Electronic Structures of trans and cis Isomers of Some Halogenoethylenes
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一些卤代乙烯反式和顺式异构体的电子结构
DOI：
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发表时间：
1971
期刊：
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通讯作者：
T. Yonezawa
中科院分区：
文献类型：
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作者：
H. Kato;K. Hirao;H. Konishi;T. Yonezawa
本文用我们提出的适用于所有价电子体系的零微分重叠近似的闭壳层自洽场分子轨道方法，研究了反式和顺式取代乙烯（处理取代基= CH_3，Cl，Br和I）的电子结构。给出了这些异构体的π和价电子电荷以及总能量的计算值。本文结合光电子观测讨论了氯代乙烯的高占据分子轨道，特别是孤对分子轨道的性质。计算得到的最低π-π* 单重态跃迁能与实验值雅阁较好。至于转动能的变化，计算结果表明，在垂直构型下，所有处理化合物的三重态都是最低的，而这些化合物顺反异构化的中间态可能是两种异构体共有的。
By using the closed-shell SCF MO method with the zero-differential overlap approximation for all valence electron systems previously presented by us, the electronic structures of trans- and cis- substituted ethylenes (treated substituent=CH3, Cl, Br, and I) are studied. The calculated values of the π and valence electron charges, and the total energies of these isomers are presented. The natures of the higher occupied MO’s, especially the lonepair MO’s, of chlorinated ethylenes are discussed in connection with the photoelectron observation. The calculated lowest π–π* singlet transition energies accord well with the observed values. As to the rotational energy changes, the calculated results show that, at the perpendicular configurations, the triplet states for all the treated compounds are lowest, while the intermediate states for the cis-trans isomerizations of these compounds may be common to both the isomers.