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化学学报
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化学学报 ›› 2002, Vol. 60 ›› Issue (11): 1957-1964. 上一篇    下一篇

研究论文

已烯自由基阳离子的密度泛函理论研究

赵彦英;刘亚军;吴育飞;郑世钧   

  1. 河北师范大学计算量子化学研究所,石家庄(050091)
  • 发布日期:2002-11-15

A DFT Study of the Hexene Radical Cations-Molecular and Hyperfine Structures

Zhao Yanying;Liu Yajun;Wu Yufei;Zheng Shijun   

  1. Research Institute of Computational Quantum Chemistry, Hebei Normal University,Shijiazhuang(050091)
  • Published:2002-11-15

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被引次数

1

使用密度泛函理论B3LYP方法和6-31G(d,p),6-31+G(d,p),6-311G(d,p)及6- 311+G(d,p)基组，分别对1-C_6H_(12)~+,2-C_6H_(12)~+和3-C_6H_(12)~+的各种构 象进行了几何构型优化，并在B3LYP/6-311G(d,p)水平上进行了频率分析计算，在 各优化构型上，使用B3LYP和MP2(full)方法进行了超精细结构的计算。计算的3- C_6H_(12)~+的超精细偶合常数比以往的计算结果更好；1-C_6H_(12)~+和2-C_6H_ (12)~+的超精细偶合常数目前尚无实验数据报道，本计算预言了它们的超精细偶合 常数和最稳定构型。

关键词: 己烯, 密度泛函理论, 游离基, 构型, 精细结构, 偶合常数

A DFT B3LYP study on the 1-C_6H_(12)~+, 2-C_6H_(12)~+ and 3-C_6H_ (12)~+ radical cations has been carried out. The molecular geometries for various conformations of the three cations were optimized at the B3LYP/6-31G(d,p) B3LYP/6-31+G(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/6-311G(d,p) level. The most stable conformations are predicted for the three cations. 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) and MP2 (full)/6-311G(d,p) levels. The calculated hfcc results for 3-C_6H_(12) ~+ are in good agreement with experiment and more accurate than the previous theoretical results. No experimental hfcc data are available for either 1-C_6H_(12)~+ or 2-C_6H_(12)~+. The hfcc's values and the most stable structures for both 1-C_6H_(12)~+ and 2-C_6H_(12)~+ are predicted in the present work.

Key words: HEXENE, DFT B3LYP, FREE RADICAL, CONFIGURATION, FINE STRUCTURE, COUPLING CONSTANTS

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