Exact quantum mechanical study of kinetic isotope effects in the col linear reaction CI + H₂ → HCI + H. the H₂D₂ and the H₂/T₂ isotope effects

Exact quantum mechanical probabilities for the collinear reaction of chlorine atoms with H₂, D₂, and T₂ in their ground and first vibrational excites states, were calculated for a semiempirical LEPS potential energy surface. These probabilities were used to calculate the kinetic isotope effects k_ci+H2/k_ci+D2 and k_Ci+H2/k_α+T2 wn'ch are compared with experimental data and with results of transition state theory calculations. The effect of the vibrational excitation of the hydrogen molecules on the rate of their reaction with chlorine atoms was also studied.