F Cl_2→ClF Cl和Cl′F Cl→Cl′ ClF的反应机理

用密度泛函理论(DFT)B3LYP方法,取6-311G基组,计算研究了F＋Cl2→ClF＋Cl的反应机理.求得1个线形和2个三角形过渡态,反应能垒分别为1.24、46.37和105.09kJ·mol－1；同时发现F以∠FClCl为10～20°（或120～160°）进攻Cl2时,反应无能垒.此外,求得对称反应Cl′F＋Cl→Cl′＋ClF的能垒为40.57kJ·mol－1的1个过渡态.

Mechanism of the Reactions F＋ Cl2→ClF ＋ Cl and Cl′ F＋ Cl→Cl′ ＋ ClF

The reaction F＋ Cl2 ClF＋ Cl was investigated by density functional theory (DFT) at the B3LYP/6-311G level. The reaction can occur via a linear transition states with a reaction barrier of 1.24 kJ· mol－ 1,and can also via two triangle transition states with reaction barriers of 46.37 and 105.09 kJ· mol-1,respectively.In addition,we also found that there is no energy barrier when F attacks Cl2 with an angle ∠ FClCl of 10－ 20° (or 160－ 120° ).The energy barrier of the symmetrical reaction Cl′ F＋ Cl→Cl′ ＋ ClF was calculated to be 40.57 kJ· mol-1.All transition states were confirmed by vibrational analyses and the possible reaction paths were obtained by IRC calculations.