Quantum chemical calculations on the mechanism of the reaction between dicarbene C2(X 1I£ G + ) and molecular nitrogen

Quantum chemical calculations on the mechanism of the gas-phase reaction between dicarbene C-2(X I-1 pound (G) (+) ) and the nitrogen molecule have been carried out within the Moller-Plesset perturbation theory (MP2/aug-cc-pVDZ) for the linear, perpendicular, and parallel orientations of the reacting molecules in the collision complex. The last orientation is of greatest interest, since in this case the system passes, with a threshold energy of 37.2 kcal/mol, through a transition state shaped as a distorted tetrahedron, which then turns into vibrationally strongly excited cyanogen. The latter decomposes into two CN radicals in 10(-13)-10(-14)s.