化学学报 ›› 1995, Vol. 53 ›› Issue (7): 661-664. 上一篇    下一篇

研究论文

FC≡CF→F~2C=C:重排反应的动态学理论研究

冯文林;吴俊南;李宗和   

  1. 北京师范大学化学系量化室
  • 出版日期:1995-07-15 发布日期:1995-07-15

A theoretical study on kinetics of the rearrangement reaction FC≡CF→F~2C=C:

FENG WENLIN;WU JUNNAN;LI ZONGHE   

  • Online:1995-07-15 Published:1995-07-15

本文用从头算方法, 在RHF/3-21G分子轨道从头算法的水平上, 得到了重排反应F-C≡C-F→F~2C=C:的内禀反应坐标(IRC)。沿着IRC, 计算了体系各简正模所对应的频率(ω)以及沿IRC运动与垂直于IRC运动的简正模之间的耦合常数(BK,F); 根据传统过渡态理论、变分过渡态理论及相应的隧道效应校正, 计算了本重排反应的反应速率常数。

关键词: 重排反应, 反应速度常数, 内禀反应坐标法, 二氟代乙炔, 国家科委专项资助

In this paper, the intrinsic coordinate (IRC) of the F shift rearrangement reaction F-C≡C-F→F~2C=C: has been traced at the SCF/3-21G level. Along the IRC, the vibrational frequencies of normal modes and the coupling constants (BK,F) between the IRC and other normal modes which are orthogonal to the IRC have been calculated. The reaction rate constants have been calculated according to conventional transition state theory, variational transition state theory and tunneling corrections respectively.

Key words: REARRANGEMENT REACTION, REACTION RATE CONSTANT, IRC

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