物理化学学报 >> 1995, Vol. 11 >> Issue (10): 896-901.doi: 10.3866/PKU.WHXB19951008

研究论文 上一篇    下一篇

环芳类化合物分子轨道相互作用的研究

刘韩星   

  1. 武汉工业大学新材料研究所,武汉 430070
  • 收稿日期:1994-12-17 修回日期:1995-03-11 发布日期:1995-10-15
  • 通讯作者: 刘韩星

Molecular Orbital Interactions in Cyclophanes

Liu Han-Xing   

  1. Advanced Materials Research Institute,Wuhan University of Technology,Wuhan 430070
  • Received:1994-12-17 Revised:1995-03-11 Published:1995-10-15
  • Contact: Liu Han-Xing

摘要:

建立模型分子描述环芳类分子中二苯环、二乙炔的π轨道间的相互作用,应用多重散射Xα自洽场方法对模型分子的电子结构进行计算,得到分子轨道通过空间相互作用的大小随二苯环、二乙炔间距离的增加呈指数下降.在环芳类化合物分子电子结构研究基础上,分析了分子轨道通过键的相互作用.结果表明,分子轨道通过空间相互作用与通过健相互作用相互抵消.采用过渡态方法计算环芳类化合物分子前线分子轨道电离能,与实验符合较好

关键词: 环苯类化合物, 分子轨道相互作用, 光电子能谱, 多重散射Xa自治场方法

Abstract:

The molecular orbital interactions in cyclophanes were studied by empolying the model molecules with the assistance of the improved MS-Xa method. The results show that the through-space interactions are exponential flareout with increasing of the distance of two orbitals, and both through-space and through-bond interactions are sizable but these two interactions oppose each other causing the net splltting to be small. Transition-state procedure has been used to calculate ionization potentials, the results are in agreement with the PE-spectra.

Key words: Cycophanes, Orbital interactions, Photoelectron spectra, MS-Xa method