Ground state surface formation of Cl2 in the dissociation of CCl4 and CHCl3 and comparisons with Br species

The formation of molecular chlorine from the ground state dissociation of CCl4 and CHCl3 was investigated at the M06, MP2 and CCSD(T) levels of theory, all using the cc-pVTZ basis set. All levels of theory showed the presence of two transition states and an ion-pair isomer intermediate. The presence of the isomer in the dissociation pathway is in agreement with previous studies on the ground state dissociation of similar halocarbons.