Semiclassical treatment of charge transfer in molecule-surface scattering

Abstract

We have treated the ionization probability of iodine molecules scattered from diamond by a semiclassical surface hopping scheme, namely Tully’s fewest-switches algorithm [J. Chem. Phys. 93, 1061 (1990)]. The interaction is described by a model potential that has been adjusted to empirical data. We start with a one-dimensional two-state model in which just the molecular distance from the surface and the neutral and negatively charged state of I2 are considered. We determine the ionization probability within the adiabatic and diabatic representation and compare it with exact quantum calculations. For this particular problem we find that the diabatic picture shows too little coherence, while the adiabatic representation yields satisfactory results. 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 freedom damps out the Stückelberg 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 dependence is not given by the electronic coupling per se, but rather due to energy transfer to substrate and internal degrees of freedom during the scattering event. Finally, we are also able to reproduce the measured dissociation probability which can be explained in a centrifugal model.