Premium
Model study of the abrupt excess‐energy dependence of radiationless decay in benzene and azabenzenes
Author(s) -
Sobolewski A. L.,
Lim E. C.,
Siebrand W.
Publication year - 1991
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560390309
Subject(s) - benzene , singlet state , excited state , atomic physics , chemistry , ground state , singlet fission , reaction rate constant , triplet state , reaction coordinate , physics , computational chemistry , kinetics , quantum mechanics , organic chemistry
Model studies are reported aimed at accounting for the abrupt dependence of radiationless decay‐rate constants on excess energy (known as channel‐three decay in the case of S 1 benzene) in singlet and triplet manifolds of benzene and azabenzenes. The favored model involves L a (ππ*) state, strongly distorted along an out‐of‐plane coordinate, crossing the ground‐state potential at an energy close to the minimum of the lowest excited state. The results are compared with experimental observations on benzene and three azabenzenes. Implications for photochemical reactions are also discussed.