Exact quantum mechanical study of kinetic isotope effects in the collinear reaction Cl plus; H2rarr; HCl plus; H. The H2sol;D2and the H2sol;T2isotope effects

摘要

Exact quantum mechanical probabilities for the collinear reaction of chlorine atoms with H2, D2, and T2in 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 effectskClplus;H2sol;kClplus;D2andkClplus;H2sol;kClplus;T2which 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.