高等学校化学学报

高等学校化学学报 ›› 1989, Vol. 10 ›› Issue (1): 72.

• 研究论文 • 上一篇    下一篇

硝基苯基甲基多硅烷体系UV谱的理论研究

李志儒, 吴岩火, 孙家锺   

  1. 吉林大学理论化学研究所
  • 收稿日期:1987-07-21 出版日期:1989-01-24 发布日期:1989-01-24
  • 基金资助:

    国家自然科学基金

Theoretical Study of UV Spectra for Nitrophenylpolysilanes

Li Zhiru, Wu Yanhuo, Sun Jiazhong   

  1. Institute of Theoritical Chemisty, Jilin University, Changchun
  • Received:1987-07-21 Online:1989-01-24 Published:1989-01-24

PDF (PC)

被引次数

2

摘要： 按照CI的酉群方法,以Gelfand基构造多电子波函数,采用四轨道模型,进行了对位及间位硝基苯基甲基多硅烷体系的EHMO-CI计算,得到的第1、第2及第3跃迁能与实验值接近。对位硝基苯基甲基多硅烷体系的第1吸收带随硅原子数增加(或支化)呈现的红移现象是LUMO中硅的d轨道以πd(si)的形式与苯环π-π*跃迁。

关键词: 硝基苯基甲基多硅烷, EHMO-CI, 硅的d轨道

Abstract: The UV spectra of p-NO2-m-(SiMem-3)n(SiMe3)nand m-NO2-ph (SiMem-3) (SiMe3)msystems (m= 1, n=0,1,2; m=2n= 1) are analyzed by means of the EHMO-CI-SPIN-FREE method with four orbital model. The first, second and third absorpt on bands arise in essence from π→π* transitions. Furthermore, the d atomic orbital of silicon chain may play an important role in the red shift of first absorption bands of p-NO2-ph(SiMe3-m)n, (SiMe3)msystem. This can be considered due to two effects. One of them is the conjugation of d orbital (πd(Si)) with π*(ph) in LUMO. The other is the changing of electronic repulsion by changing d orbital and NO2group components in LUMO.

Key words: Nitrophenylpo lysilanes, EHMO-Cl, d-Orbital (Si)

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