MINIMUM ENERGY PATHS FOR THE REACTIONS OF THE CCL2 RADICAL WITH O2(1∑g ) AND O2(1∆g)

Abstract

The potential energy surfaces of the reactions CCl₂ +O₂(³Σ^-_g) and CCl₂ + O₂(¹Δ_g) were investigated by quantum-chemical calculations.  The geometry and energy of the reactives, intermediates and products were characterized employing different formulations of the density functional theory (DFT), with the Pople's basis set 6-311+G(3df). The mean value of the barrier height for the reaction CCl₂ + O₂(³Σ^-_g) is ΔE₀^# = (7,1 ± 2,7) kcal mol^-1, and the reaction of the CCl₂ with O₂(¹Δ_g) proceeds without a barrier. A crossing region of the triplet and singlet potential energy surfaces was found.