THEORETICAL-STUDY OF THE REACTION OF CD(S-1, P-3, P-1) WITH THE METHANE MOLECULE

The reaction pathways of the interaction of the methane molecule with the cadmium atom in the ground state (S-1) and the two lowest excited states (P-3, P-1) were determined using Hartree-Fock followed by multi reference configuration interaction plus second-order multireference M oller-Plesset calculations. No spontaneous activation of the methane m olecule was observed by these electronic states of the cadmium atom du e to the existence of activation barriers of 107.2, 27, and 17.3 kcal/ mol, respectively. The geometry and electronic structure of the HCdCH3 intermediate molecule and the CdH and CdCH3 products involved in the reaction were also determined, as well as the dissociation pathway of HCdCH3 towards the CdH + CH3 and H + CdCH3 products. We found that the HCdCH3 intermediate reaches the final products without any barriers a nd also that the initial reactants in the ground state need to be prov ided with 88.5 kcal/mol to obtain the CdH + CH3 products and with 99.8 kcal/mol to get the H + CdCH3 products. (C) 1993 John Wiley and Sons, Inc.