Semiclassical treatment of charge transfer in molecule-surface scattering

We have treated the ionization probability of iodine molecules scattered fr om diamond by a semiclassical surface hopping scheme, namely Tully's fewest -switches algorithm [J. Chem. Phys. 93, 1061 (1990)]. The interaction is de scribed by a model potential that has been adjusted to empirical data. We s tart with a one-dimensional two-state model in which just the molecular dis tance from the surface and the neutral and negatively charged state of I-2 are considered. We determine the ionization probability within the adiabati c and diabatic representation and compare it with exact quantum calculation s. For this particular problem we find that the diabatic picture shows too little coherence, while the adiabatic representation yields satisfactory re sults. In the second part we have successively increased the complexity of the simulation by additionally taking a surface oscillator coordinate, the molecular rotation and vibration into account. Including more degrees of fr eedom damps out the Stuckelberg oscillations present in the one-dimensional model. Our results qualitatively reproduce the observed dependence of the ionization probability on the incident energy of the molecules. This depend ence is not given by the electronic coupling per se, but rather due to ener gy transfer to substrate and internal degrees of freedom during the scatter ing event. Finally, we are also able to reproduce the measured dissociation probability which can be explained in a centrifugal model. (C) 2001 Americ an Institute of Physics.