An exploratory study of reactant vibrational effects in CH3 + H2 and its isotopic variants

Abstract

An empirically calibrated potential energy surface, obtained previously [J. Chem. Phys. 61, 21 (1974)], was used in a trajectory study of the effect of reactant energy partitioning on cross section for CH₃ + H₂ → CH₄ + H. Artificial variations in the barrier position, and artificial and naturally occuring changes in the H masses, were also made. For natural CH₃ + H₂, H₂ vibration enhances and CH₃ out‐of‐plane bending depresses the cross section, at constant (25 kcal) translational energy of approach. The isotope substitution and barrier position effects are more complex and not predictable from triatomic A + BC generalizations. The relationship of these results to experimental ones is discussed.