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化学学报
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化学学报 ›› 2002, Vol. 60 ›› Issue (2): 267-271. 上一篇    下一篇

研究论文

丁烯和丁烷自由基阳离子的分子结构和超精细结构的 理论研究

刘亚军;黄明宝;郑世钧   

  1. 中国科学院研究生院化学部.南京(210008);河北师范大学计算量化研究所
  • 发布日期:2002-02-15

Theoretical study of the butene and butane radical cations: molecular and hyperfine structures

Liu Yajun;Huang Mingbao;Zheng Shijun   

  1. Nanjing Inst Geol & Palaeontol, Acad Sinica, Selective Oxidat.Nanjing (210008)
  • Published:2002-02-15

PDF

468

被引次数

10

用密度函数理论B3LYP方法和6-31G(d,p),6-311G(d,p)及6-311+G(d,p)基组，分别对1-C4H^+~8,2-C4H^+~8和C4H^+~10进行了构型优化和频率分析计算，预言1-C4H^+~8具有非平面构型，与以往报道的从头算和密度函数理论计算结果不同。在各自由基阳离子的B3LYP构型上，进行了B3LYP、MP2及MRSDCI方法的超精细偶合常数计算，得到了比以往更好的结果，特别是MP2/B3LYP计算值是至今与实验值符合得最好的理论计算结果。

关键词: 丁烯P, 丁烷P, 自由基阳离子, 分子结构, 精细结构, 超精细结构, 量子化学, 密度泛函理论

The DFT B3LYP study on 1-C4H^+~8, 2-C4H^+~8 and C4H^+~10 has been carried out. The molecular structures were optimized at the B3LYP/6- 31G(d, p), B3LYP/6-311G(d, p), and B3LYP/6-311+G(d, p) levels, and the frequency analysis calculations were performed at the B3LYP/6-311+G(d, p) levels, and the frequency analysis calculations were performed at the B3LYP/6-311G(d, p) level. Based on the B3LYP/6-311G(d, p) geometries, the proton isotropic hyperfine coupling constants (hfcc's) were calculated at the B3LYP/6-311G(d, p), MP2(full)/6-311G(d, p), and MRSDCI levels. 1-C4H^+~8 is predicted to have a nonplanar structure, which is in contrast to the previous conclusions based on the ab initio and DFT calculations. 2-C4H^+~8 is predicted to have stable cis and trans conformations with planar structures, and C4H^+~10 is predicted to have stable trans and gauche conformations. The calculated hfcc results are in good agreement with experiment and more accurate than the previous theoretical results.

Key words: BUTENE P, BUTANE P, MOLECULAR STRUCTURE, FINE STRUCTURE, QUANTUM CHEMISTRY

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