Influence of molecular vibrations on dissociative adsorption

Abstract The influence of molecular vibrations on dissociative adsorption is studied by six-dimensional quantum dynamical calculations. For the system H 2 at Pd (100), which possesses non-activated pathways, it is shown that large vibrational effects exist and that they are not due to a strongly curved reaction path and a late dissociation-hindering minimum barrier, as was previously assumed. Instead, they are caused by the lowering of the H-H vibrational frequency during the dissociation and the multi-dimensionality of the potential energy surface. Still there are quantitative discrepancies between theory and experiment identified.