化学学报 ›› 2011, Vol. 69 ›› Issue (18): 2075-2079.    下一篇

研究论文

C60与铈卟啉相互作用的密度泛函理论研究

严安平,孙涛,王一波*   

  1. (贵州大学化学系 贵州省高性能计算化学重点实验室 贵阳 550025)
  • 收稿日期:2011-02-22 修回日期:2011-04-26 出版日期:2011-09-28 发布日期:2011-05-27
  • 通讯作者: 王一波 E-mail:ybw@gzu.edu.cn
  • 基金资助:

    国家自然科学基金

DFT Study on the Interaction between Fullerere and Cerium Porphrin

YAN An-Ping, SUN Tao, WANG Yi-Bo   

  1. (Department of Chemistry, Guizhou University, Key Laboratory of Guizhou High Performance Computational Chemistry, Guiyang 550025)
  • Received:2011-02-22 Revised:2011-04-26 Online:2011-09-28 Published:2011-05-27

应用Perdew-Burke-Ernzerhof (PBE)密度泛函理论对5种可能存在的富勒烯与铈卟啉复合物进行了几何结构优化, 通过分子间距离及结合能数值, 确认了C60和铈卟啉可以通过非键相互作用形成超分子主-客体复合物, 且最有可能的作用位点为C60的C5:6键(相邻五元环与六元环共用碳-碳键). 应用扩展过渡态方法对结合能进行分解, 分解结果显示, 静电能对总吸引能的贡献约为60%, 说明静电作用是复合物稳定存在的最主要因素. 最后对复合物中的电子流向进行了研究, 结果表明复合物中电子的转移与主-客体间相互作用有一定联系, 且电子是从主体铈卟啉流向客体C60.

关键词: C60, 铈卟啉, 分子间相互作用, 能量分解

The 5 different configurations of fullerene-cerium-porphyrin complexes are optimized using the Perdew-Burke-Ernzerhof (PBE) density functional theory. Judged from the geometrical criteria, C60 and cerium porphrin can form supramolecular guest-host complexes. Binding energies also confirmed this conclusion. The most likely effect of orientation is the 5:6 C—C bond of C60. In an effort to comprehend the underlying basis of this interaction, a decomposition of the interaction energies is also carried out using the extended transition state method. The results indicate that the contribution of the electrostatic energies to the total attractive energy is about 60%, it shows that electrostatic interaction is one of the main factors for stabilizing complexes. Lastly, the electron flow for complexes is studied, the results show that the guest-host interactions are also associated with a charge transfer from the cerium porphyrin moiety to the fullerene guest.