The o-, m-, and p-benzyne radical cations: a theoretical study.
On the basis of the CASPT2 (multiconfigurational second-order perturbation theory) geometry optimization calculations, the ground states of the o-C6H4+ (C2v), m-C6H4+ (C2v), and p-C6H4+ (D2h) radical cations were determined to be 1 2B1, 1 2A2, and 1 2B1u, respectively. For o-C6H4+ and m-C6H4+, the first excited states (1 2A2 and 1 2A1, respectively) lie very close to the respective ground states. The small distance value of 1.419 A between the two dehydrocarbons in the ground-state geometry of m-C6H4+ indicates that there is a real chemical bond between the two dehydrocarbons (the distance in the 1 2A1 geometry of m-C6H4+ is very long as in the m-C6H4 molecule). The (U)B3LYP isotropic proton hfcc (hyperfine coupling constant) calculation results imply that the ground and first excited states of o-C6H4+ will have similar ESR spectrum patterns while the ground and first excited states of m-C6H4+ will have completely different ESR spectrum patterns.
Li
Hua
H
College of Chemistry and Chemical Engineering, Graduate University, Chinese Academy of Sciences, P.O. Box 4588, Beijing, 100049, People's Republic of China.
Huang
Ming-Bao
MB