Distortion Modes of Heavy Ethylenes and Their Anions: π-σ* Orbital Mixing Model
Distortion Modes of Heavy Ethylenes and Their Anions: π-σ* Orbital Mixing Model
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DOI：
10.1021/om200609d
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发表时间：
2011-08-22
期刊：
影响因子：
2.8
通讯作者：
Kira, Mitsuo
中科院分区：
文献类型：
--
作者：
Kira, Mitsuo
利用PMO理论，根据广义pi-sigma* 轨道混合模型，讨论了乙烯、二硅烯和二锗烯及其阴离子的三种扭曲模式：反式和顺式弯曲和扭曲。该模型预测，反式和顺式弯曲的几何形状的中性二金属可以从平面几何形状，但具有非常小的能量增益，这些几何形状应该在很大程度上稳定与显着的弯曲角和稳定能量的二金属阴离子。在双金属烯的双键周围扭转可以降低阴离子的能量。在B3 LYP/6-311++G（3df，3 pd）水平上对上述预测进行了验证.
Three distortion modes, trans and cis bending and twisting, of ethylene, disilene, and digermene and their anions are discussed in terms of a generalized pi-sigma* orbital mixing model using PMO theory. The model predicts that trans- and cis-bent geometries of neutral dimetallenes may be stabilized from the planar geometry but with very small energy gains and that these geometries should be largely stabilized with significant bend angles and stabilization energies in dimetallene anions. Twisting around the double bonds of dimetallenes may lower the energy of the anions. The above prediction is verified by the potential energy surface calculations at the B3LYP/6-311++G(3df,3pd) level.