Collision induced dissociative chemisorption of CH4 on Ni(111) by inert gas atoms: The mechanism for chemistry with a hammer

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Abstract
The dissociation of CH4 physisorbed on Ni(111) at 46 K is observed to be induced by the impact of incident inert gas atoms. The dynamics and mechanism of this new process, collision induced dissociative chemisorption, are studied by molecular beam techniques coupled with ultrahigh vacuum electron spectroscopies. The absolute cross section for collision induced dissociation is measured over a wide range of kinetic energies (28–109 kcal/mol) and incident angles of Ne, Ar, and Kr atom beams. The cross section displays a complex dependence on the energy of the impinging inert gas atom characteristic of neither total nor normal energy scaling. Quantitative reproduction of the complex dependence of the cross section on the Ar and Ne incident energy by a two‐step, dynamical model establishes the mechanism for collision induced dissociation. Collision induced dissociation occurs by the impulsive transfer of kinetic energy upon collision of Ar or Ne with CH4, followed by the translationally activated dissociative chemisorption of the CH4 upon its subsequent collision with the Ni surface. The dependence of the probability of activated dissociation on the resultant CH4 normal energy derived from the fit of the model to the experimental cross section is in excellent agreement with the results of a previous study of the translationally activated dissociative chemisorption of CH4 on Ni(111). Collision induced activation and translational activation are shown to be consistent mechanisms for providing energy to CH4 to surmount the barrier to dissociative chemisorption.