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化学学报
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化学学报 ›› 2005, Vol. 63 ›› Issue (13): 1236-1240. 上一篇    下一篇

研究简报

CH2＝CClF  hν >•CH＝CClF＋H光解反应的理论研究

王彩霞，刘鲲，李宗和*   

  1. (北京师范大学化学系 北京 100875)
  • 投稿日期:2004-09-20 修回日期:2005-03-16 发布日期:2010-12-10
  • 通讯作者: 李宗和

Theoretical Study on Photodissociation of CH2＝CClF  hν >•CH＝CClF＋H

WANG Cai-Xia, LIU Kun, LI Zong-He*   

  1. (Department of Chemistry, Beijing Normal University, Beijing 100875)
  • Received:2004-09-20 Revised:2005-03-16 Published:2010-12-10
  • Contact: LI Zong-He

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采用UHF, CIS和CASSCF方法, 在aug-cc-pvdz基组水平上对CH2＝CClF  hν >•CH＝CClF＋H的光解反应通道及其后续反应作了研究. 计算表明: 分子吸收一个光子后, 在第一电子激发态(S1)经过一个过渡态解离与Cl原子同侧的C—H键, 这与用CIS方法计算垂直激发得到的π→σ*C—H跃迁及其对Frank-Condon点的计算中分子的单占轨道和键电荷密度变化所预测的结果是一致的. 光解产物•CH＝CClF(基态)还可再发生反应, 经过渡态解离C—Cl键或是C—F键.

关键词: 1-氟-1-氯乙烯, Frank-Condon点, CIS, CASSCF

The mechanism of photodissociation of CH2＝CClF  hν >•CH＝CClF＋H and its following reactions have been investigated using the unrestricted Hartree-Fock (UHF), CI-Singles (CIS) and Complete Active Space Multiconfiguration SCF (CASSCF) methods with the aug-cc-pvdz basis set. The results show that the elimination of H atom on the same side of Cl atom occurs at the π→σ*C—H excited state when the molecule absorbs a photon. This finding has been further supported by the calculations of the electron transition using CIS method and by one electron density at Frank-Condon point using CASSCF methods, respectively. C-Cl and C-F bond fission reactions from the photodissociation product •CH＝CClF were also found.

Key words: 1-chloro-1-fluoroethylene, Frank-Condon point, CI-Singles, Complete Active Space Multiconfiguration SCF