物理化学学报 >> 2002, Vol. 18 >> Issue (12): 1081-1086.doi: 10.3866/PKU.WHXB20021206

研究论文 上一篇    下一篇

戊烯自由基阳离子的密度泛函理论研究

赵彦英;刘亚军;郑世钧;黄明宝;孟令鹏   

  1. 河北师范大学计算量化研究室,石家庄 050091;中国科学院研究生院化学部,北京 100039
  • 收稿日期:2002-03-19 修回日期:2002-06-13 发布日期:2002-12-15
  • 通讯作者: 郑世钧 E-mail:sjzheng@hebtu.edu.cn

DFT Study of the Pentene Radical Cations: Molecular and Hyperfine Structures

Zhao Yan-Ying;Liu Ya-Jun;Zheng Shi-Jun;Huang Ming-Bao;Meng Ling-Peng   

  1. Research Institute of Computational Quantum Chemistry, Hebei Normal University, Shijiazhuang 050091;1Department of Chemistry, Graduate School, Chinese Academy of Sciences, Beijing 100039
  • Received:2002-03-19 Revised:2002-06-13 Published:2002-12-15
  • Contact: Zheng Shi-Jun E-mail:sjzheng@hebtu.edu.cn

摘要: 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2-C5H10+和1-C5H10+的各种构象进行了几何构型优化,并用B3LYP/6-311G(d,p)进行了频率分析计算.计算预言1-C5H10+具有非平面构型,与以往报导的从头算计算结论相反.在两个自由基阳离子的各种构象的B3LYP几何构型上,进行了B3LYP和UMP2(full)方法的超精细偶合常数计算,得到了比以往更好的结果.

关键词: 戊烯自由基阳离子, 密度泛函理论, 超精细结构

Abstract: The density function theory(DFT) B3LYP study on the 2-C5H10+ and 1-C5H10+ radical cations has been carried out. The molecular geometries for various conformations of the two 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 1-C5H10+ ion was predicted to have a nonplanar structure, which is in contrast to the previous conclusions based on ab initio calculations. Based on the B3LYP/6-311G(d, p) geometries, the proton isotropic hyperfine coupling constants (HFCCs) were calculated at the B3LYP/6-311G(d, p) and MP2(full)/6-311G(d, p) levels. The calculated HFCCs results are in good agreement with experiment and more accurate than the previous theoretical results.

Key words: Pentene radical cations, DFT B3LYP, Hyperfine structures