CASSCF and CAS+1+2 studies on the potential energy surface and the rate constants for the reactions between CH2 and O2

CAS(14,12)/cc-pvdz calculations are reported for the reaction of (CH2)-C-3+O-3(2)-->products. On the sin-let potential energy surface, a transition state has been located with an energy barrier of 1.65 kcal/mol, which is in good agreement with the experimental estimation of 1.0-1.5 kcal/mol. The rearrangement and metathesis of the singlet intermediates have been also investigated at the same level of theory. For the triplet case, the formation of CH2OO has an energy barrier of 5.79 kcal/mol, and the formed triplet CH2OO could be further decomposed into CH2O+O((3)p) with an energy barrier of 2.92 kcal/mol. The geometries of some key points have been relocated at the CAS(8,6)+1+2/cc-pvdz level of theory for comparison. The present theoretical results for the total reaction rates, at the CAS(8,6)+1+2/cc-pvdz level, can be expressed by the three-parameter expression: k(T) = 4.273 x 10(-18)T(2.245)exp(-185/T) within +/-5% error at the temperature range 295-2600 K.