Theoretical investigation on o-, m-, and p-chlorotoluene photodissociations at 193 and 266 nm.
Photodissociations of the o-, m-, and p-chlorotoluene at 193 and 266 nm were investigated by ab initio calculations with and without spin-orbit interaction. The experimentally observed photodissociation channels were clearly assigned by multistate second order multiconfigurational perturbation theory (MS-CASPT2) calculated potential energy curves. The dissociation products with spin-orbit-coupled states of Cl*(2P1/2) and Cl(2P3/2) were identified by MS-CASPT2 in conjunction with spin-orbit interaction through complete active space state interaction (MS-CASPT2/CASSI-SO) calculations. The effects of methyl rotation and substituent on the photodissociation mechanism were discussed in detail.
College of Chemistry, Beijing Normal University, Beijing 100875, People's Republic of China.
Yan-Cong
YC
Tian
Ya-Jun
YJ
Liu
Wei-Hai
WH
Fang