The photodissociation dynamics of CF2Br2 has been studied using a two-dimensional photofragment ion image technique for the two excitation wavelengths 234 and 265 nm. At 234 nm, three dissociation channels, i.e., the radical CF2Br + Br (2P J ) (J = 1/2, 3/2), the three-body CF2 + 2Br (2P J ) (J = 1/2, 3/2), and the molecular elimination channel CF2 + Br2, were observed with quantum yields of 0.84, 0.15, and trace, respectively. The difference between β (CF2Br + Br (2P3/2)) = 0.65 and β (CF2Br + Br (2P1/2)) = 0.80 suggests that the excited A1 and B1 states are strongly correlated by avoided curve crossing with a probability of 0.78. At 265 nm, the radical channel, the observed major primary dissociation channel, shows several components due to the transition close to the curve crossing point. On the basis of observations at both wavelengths, we have proposed a photodissociation dynamics model of CF2Br2 after A-band excitation.
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