Dynamics of Ar+CH4/Ni{111} collision-induced desorption

Abstract

Classical trajectory simulations were used to study Ar+CH4/Ni{111} collision-induced desorption and compared with experiment. To perform the simulations, analytic potentials were determined for Ar/CH4 and CH4/Ni{111}. An accurate form for the former potential was derived by carrying out a series of ab initio calculations at various levels of theory, while previously published ab initio calculations were used to develop the latter CH4/Ni{111} potential. Overall the simulation and experimental desorption cross sections are in excellent agreement, except at small incident angles θi (with respect to the surface normal) and low initial Ar translational energies, Ei, where the simulation cross sections are approximately a factor of 2 too large. Most of the desorption occurs by trajectories in which Ar first strikes CH4, but for both large θi and Ei, a small fraction of the desorption occurs by trajectories in which Ar first strikes the Ni surface. Excitation of the CH4 vibrational modes is negligible and CH4 rotation receives less than 10% of the available energy. Most of the available product energy is partitioned to CH4 translation and to the Ni surface and Ar atom. At low Ei, CH4 translation receives the majority of the available energy, with the effect greater for large θi. At high Ei, approximately 40% of the available energy goes to CH4 translation, independent of θi. The CH4 translational energy distribution is multimodal and its peaks may be associated with trajectories in which the Ar atom rebounds off or sticks to the Ni surface and collisions in which Ar strikes CH4 with small and large impact parameters.