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

The reaction F + Cl-2-->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 Cl-2 with an angle angle FClCl of 10 - 20 degrees (or 160 - 120 degrees). 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.