Computational studies of nonadiabatic effects in gas—surface encounters

Model studies are presented, each of which employs a different approach to solving the problem of nonadiabatic dynamics occurring at a solid surface. The jumping wave packet-type approach involving dynamics on two potential energy surfaces punctuated by Franck—Condon transitions was applied to the dynamics of CO desorbed from Ru following energetic electron bombardment. Classical dynamics was also employed in this system to gain a more detailed understanding of the factors important to the final molecular state distribution. To study charge transfer from an alkali-halide surface to a scattering atom, we have used full multi-surface quantum dynamics. A simple, but effective, analysis method was used to make a more detailed connection between the potential energy surfaces and the dynamics. To study the fate of the transferred electron and to model how this depends on substrate and projectile species, we have used a four-dimensional wave packet implementation in which two of the dimensions explicitly account for the electron dynamics. Finally, we consider the famous electron—hole pair excitation problem, from a density functional theory perspective. Spin nonadiabaticity is found to be a new important feature in gas—metal surface interactions.