Scattered Ne+ and recoiled S- ion fractions resulting from 4 keV Ne+ and 4 keV Kr+ impingement, respectively, on both the Cd- and S-terminated surfaces of CdS{0001} have been measured. The absolute values of these ion fractions as well as their dependence on surface structure and electron density have been determined. Using a density functional approach, a clear correlation has been demonstrated between these Ne+ and S- ion fractions and the lateral variation of the electrostatic potential along the outgoing trajectories of the scattered and recoiled atoms. The observed anisotropy in the ion fractions is a result of the variations in surface to atom electron transfer rates due to tunneling barriers introduced by the electrostatic potentials. Both the Ne+ and S- ion fractions are higher on the Cd-terminated surface than on the S-terminated surface and their azimuthal patterns are different due to the spatial modulation of the electron tunneling rates on the surface caused by the electrostatic barriers. The azimuthal anisotropies of electrons ejected during the collision indicate that they are emitted only from collisions whose impact parameters are less than a threshold value, consistent with a kinetic electron emission mechanism.