物理化学学报 >> 2015, Vol. 31 >> Issue (1): 51-55.doi: 10.3866/PKU.WHXB201411172

理论与计算化学 上一篇    下一篇

一种C50Cl10富勒烯氯化物新的生成机理的密度泛函理论计算

甘佐华, 陈姝璇, 谭凯   

  1. 厦门大学化学化工学院, 固体表面化学国家重点实验室, 福建省理论与计算化学重点实验室, 福建 厦门 361005
  • 收稿日期:2014-09-23 修回日期:2014-11-15 发布日期:2014-12-25
  • 通讯作者: 谭凯 E-mail:ktan@xmu.edu.cn
  • 基金资助:

    国家自然科学基金(21273177)和国家重点基础研究发展规划项目(973) (2011CB808504)资助

Alternative Formation Mechanismof C50Cl10 Fullerene Chloride Based on Density Functional Theory Calculations

GAN Zuo-Hua, CHEN Shu-Xuan, TAN Kai   

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces & Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China
  • Received:2014-09-23 Revised:2014-11-15 Published:2014-12-25
  • Contact: TAN Kai E-mail:ktan@xmu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21273177) and National Key Basic Research Programof China (973) (2011CB808504).

摘要:

过去广泛接受#271C50Cl10是由#271C50空笼直接氯化得到. 我们通过研究拓扑结构弄清了C50富勒烯之间的相互关系. 利用密度泛函理论(DFT)计算从最稳定C50富勒烯#270C50出发, 通过氯化和Stone-Wales (SW)转变获得#271C50Cl10. 结果表明: 氯化后最终产物是热力学最有利的, 并且在有氯存在下, SW转变的活化能垒会降低. 这些结果可以解释目前的相关实验事实, 暗示了#270C50空笼先氯化得到不同#270C50氯化物, 再进行两次SW旋转的路径, 由于活化能垒更低因而是一条更为可行的路线.

关键词: 密度泛函理论, Stone-Wales转变, 氯化

Abstract:

#271C50Cl10 is widely postulated to be a direct chlorination product of cage #271C50. We suggest an alternative formation mechanism of #271C50Cl10, based on the topological relationship of these C50 fullerenes. Density functional theory (DFT) calculations of the proposed cage transformation pathway in the chlorination of C50 were performed. The proposed pathway is stimulated by chlorination-promoted fullerene cage transformation, with a lowactivation barrier. DFTcalculations of the Stone-Wales (SW) transformation pathways revealed that the thermodynamically favored rearrangement of other C50 chlorofullerene into #271C50Cl10 requires a lower activation energy than that of the pristine carbon cage. This suggested that it is a more effective pathway of chlorinating C50 to #271C50Cl10.

Key words: Density functional theory, Stone-Wales transformation, Chlorination

MSC2000: 

  • O641