物理化学学报 >> 2002, Vol. 18 >> Issue (03): 228-231.doi: 10.3866/PKU.WHXB20020308

研究论文 上一篇    下一篇

不饱和类卡宾H2C=CLiF的密度泛函研究

刘奉岭   

  1. 山东师范大学化学系,济南 250014
  • 收稿日期:2001-09-10 修回日期:2001-11-14 发布日期:2002-03-15
  • 通讯作者: 刘奉岭 E-mail:L2981735@sina.com

DFT Studies on the UnsaturatedCarbenoid H2C=CLiF

Liu Feng-Ling   

  1. Department of Chemistry,Shandong Normal University,Jinan 250014
  • Received:2001-09-10 Revised:2001-11-14 Published:2002-03-15
  • Contact: Liu Feng-Ling E-mail:L2981735@sina.com

摘要: 采用量子化学中的密度泛函方法,在B3LYP/6311G水平上全优化得到了不饱和类卡宾H2C=CLiF的平衡构型.结果表明,不饱和类卡宾H2C=CLiF只有2种平衡构型.对这2种平衡构型之间相互转化的过渡态进行计算,求得了转化势垒.根据计算得到的微观性质,采用统计热力学及过渡态理论,研究了2种平衡构型之间相互转化的热力学及动力学性质,进而讨论了2种平衡构型在不同温度下的稳定性问题.

关键词: 不饱和类卡宾H2C=CLiF, 密度泛函法(density functional theory), B3LYP/6-311G, 热力学函数, 动力学性质

Abstract: Configurations and properties of unsaturatedcarbenoid H2C=CLiF have been obtained by using DFT method at B3LYP/6311G level.The results show that H2C=CLiF has two equilibrium configurations 1 and 2(Fig.3).The transition state of isomerization of 1 to 2 has also been obtained (Fig.3).Thermodynamic and kinetic properties of isomerization of 1 to 2 have been calculated according to statistical mechanics and transition state theory.Thermodynamic properties show that 1 is more stable than 2 in the temperature range of 100~1000 K,and the kinetic properties show that the rate of transformation from 2 to 1 is very fast.So 1 is the only “stable equilibrium species” existed in unsaturatedcarbenoid H2C=CLiF.Vibrational frequencies and infrared intensities of stable equilibrium 1 at B3LYP/6311G level have been given.

Key words: Unsaturatedcarbenoid H2C=CLiF, DFT(density functional theory), B3LYP/6-311G, Thermodynamic property, Kinetic property