Spin-orbit ab initio investigation of photolysis of o-, m-, and p-iodotoluene

The multistate second order multiconfigurational perturbation theory in conjunction with spin-orbit interaction through complete active space state interaction (MS-CASPT2/CASSI-SO) was employed to calculate the potential energy curves for the ground and low-lying excited states of o-, m-, and p-iodotoluene along the assumed photolysis reaction coordinates. The mechanism and channels leading to products I(P-2(3/2)) and I-*(P-2(3/2)) for o-, m-, and p-iodotoluene photolysis at 266 and 304 nm were elucidated with the computed potential energy curves and the surface crossing points. The effects of methyl substituent and heavy atom on the photodissociation mechanism were discussed by the comparison to related alkyl and aryl halides.