ABINITIO CALCULATIONS OF THE POTENTIAL-ENERGY SURFACE OF THE REACTION OF SINGLET METHYLENE WITH THE HYDROGEN MOLECULE

The potential energy surface for the insertion of singlet methylene into H2 has been computed on the ab initio SCF level as well as with inclusion of electron correlation by means of the CEPA method. The results are compared with those of previous semiempirical, ab initio SCF and CI calculations. The system is a prototype of a reaction where an allowed and a symmetry-forbidden path can compete. The electron correlation energy was found to be very different for different regions of the surface, but did not have much influence on the optimum reaction path. From the computed heat of the reaction, the heat of formation of singlet methylene was estimated to be 101.5 kcal/mol. According to the calculations the reaction does not need any activation energy. © 1979 Springer-Verlag.