Spin-orbit ab initio investigation of the photolysis of o-, m-, and p-bromotoluene.
The photodissociations of o-, m-, and p-bromotoluene were investigated by ab initio and spin-orbit ab initio calculations. The possible photodissociation mechanisms at 266 and 193 nm were clarified by multistate second order multiconfigurational perturbation theory (MS-CASPT2) calculated potential energy curves, vertical excitation energies, and oscillator strengths of low-lying states. The dissociation products with spin-orbit-coupled states of Br(*)((2)P(12)) and Br((2)P(32)) were identified by the MS-CASPT2 method 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.
Liu
Ya-Jun
YJ
College of Chemistry, Beijing Normal University, Beijing 100875, People's Republic of China. yanju.liu@bnu.edu.cn
Tian
Yan-Cong
YC
Fang
Wei-Hai
WH