Theoretical Study of the Photochemical Reaction Mechanism of Bicyclo [4.1.0] heptane1

The photochemical reaction of bicyclo[4.1.0] heptane was studied at the complete active space SCF(CASSCF) level with a 6-31G* basis set. A multireference MP2 algorithm that has been implemented in the Gaussian program was used to correct the energetics for the dynamic correlation. Starting from the Franck-Condon excitation of bicyclo [4.1.0] heptane, the reaction is via two bonds' breakage to give rise to 1,6-heptdiene. One internal conversion (IC) and two intersystem crossing points (ISC) were located and are discussed separately. The reaction proceeds to its own characteristic product on the ground state.