Dissociation dynamics of fast neutral molecules scattered under glancing incidence conditions from crystal surfaces

Abstract

When fast ( v thermal ⪡ v < v Fermi) neutral or ionised atoms or molecules are scattered under glancing incidence conditions from atomically smooth metal single crystal surfaces, translational energy losses of 0.1–1 eV per femtosecond or per Å of the trajectory in the near surface region are not atypical. A large fraction of this energy appears in the electron-hole pair excitation channel. In addition, the orientation distribution of the internuclear co-ordinate of dissociatively scattered molecules is often sharply peaked about the surface normal. Such a distribution could arise if, coincident with vibrational excitation of the intra-molecular co-ordinate, the molecules were preferentially aligned about the surface normal. Alternatively, such a distribution may arise if, following dissolution of the intra-molecular bond, the difference in the surface normal momentum transfer to the two unbound atoms considerably exceeds the difference in the surface parallel momentum transfer. We investigate these two possibilities within a classical simulation of energy transfer from the translational to internal degrees of freedom of the molecule via repeated transitions between different electronic states of the molecule-surface system. These simulations suggest that in general, the observed surface-normal aligned final orientation of dissociatively scattered molecules is caused by strong vibrational excitation in the entrance channel region of the adiabatic ground state potential energy surface describing the interaction of the neutral molecule with the surface.