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We derive a model for the dissociative chemisorption of methane on a Ni(100) surface, based on the reaction path Hamiltonian, that includes all 15 molecular degrees of freedom within the harmonic approximation. The total wavefunction is expanded in the adiabatic vibrational states of the molecule, and close-coupled equations are derived for wave packets propagating on vibrationally adiabatic potential energy surfaces, with non-adiabatic couplings linking these states to each other. Vibrational excitation of an incident molecule is shown to significantly enhance the reactivity, if the molecule can undergo transitions to states of lower vibrational energy, with the excess energy converted into motion along the reaction path. Sudden models are used to average over surface impact site and lattice vibrations. Computed dissociative sticking probabilities are in good agreement with experiment, with respect to both magnitude and variation with energy. The ν(1) vibration is shown to have the largest efficacy for promoting reaction, due to its strong non-adiabatic coupling to the ground state, and a significant softening of the vibration at the transition state. Most of the reactivity at 475 K is shown to result from thermally assisted over-the-barrier processes, and not tunneling.
Jackson et al. (Thu,) studied this question.