高等学校化学学报

高等学校化学学报 ›› 2003, Vol. 24 ›› Issue (4): 682.

• 论文 • 上一篇    下一篇

富勒烯衍生物(C36OH)+异构体间的相互转化机理──羟基(OH)的分子内迁移

许秀芳, 杨作银, 王贵昌, 尚贞峰, 吴本湘, 潘荫明, 赵学庄   

  1. 南开大学化学系, 天津 300071
  • 收稿日期:2002-04-22 出版日期:2003-04-24 发布日期:2003-04-24
  • 通讯作者: 赵学庄(1933年出生),男,教授,博士生导师,主要从事理论化学研究.E-mail:zhaoxzh@nankai.edu.cn E-mail:zhaoxzh@nankai.edu.cn
  • 作者简介:d:\PDF\.pdf
  • 基金资助:

    国家自然科学基金(批准号:20073022)资助

Ab initio Investigation of the Rearrangement Between the Isomers of C36 Fullerene Derivative(C36OH)+──Intramolecular OH shift

XU Xiu Fang, YANG Zuo Yin, WANG Gui Chang, SHANG Zhen Feng, WU Ben Xiang, PAN Yin Ming, ZHAO Xue Zhuang   

  1. Department of Chemistry, Nankai University, Tianjin 370001, China
  • Received:2002-04-22 Online:2003-04-24 Published:2003-04-24

PDF (PC)

摘要： 用从头算HF/STO-3G方法对(C36OH)+的3种异构体之间的重排机理进行了理论研究.计算结果表明,异构体2的热力学稳定性最强;从动力学角度考虑,由异构体1和3转化为2比反方向转化容易得多.结合电荷在碳笼表面的分布,预计动力学上最终在C7和C26位置上发生羟基加成的几率最大,该结论与热力学上预计的跨赤道六元环内羟基1,4-加成所得到的C36(OH)2异构体最稳定的结果一致.

关键词: Abinitio, 富勒烯衍生物(C36OH)+, 转化机理

Abstract: The mechanism of the rearrangement between the isomers of (C36OH)+, one of C 36 fullerene derivatives, has been investigated by ab initio calculation at HF/STO-3G level. The result shows that isomer 2 is thermodynamically the most stable, and kinetically it is much easier to convert isomers 1 and 3 into 2 than to convert 2 into 1 and 3 judging from the calculated energy barriers. On the other hand, the distribution of the charges on the cage of the (C36OH)+ isomers implies relatively more probability for the addition of OH group to the 1,4 sites in the six membered ring locating at the equatorial belt of the C 36 cage than to the other sites, which agrees with the themodynamic stability of the C36 (OH)2 isomers.

Key words: Ab initio, Fullerene derivative (C36OH)+, Rearrangement mechanism

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