Mechanistic Insights into Nonadiabatic Interband Transitions on a Semiconductor Surface Induced by Hydrogen Atom...

To understand the recently observed enigmatic nonadiabatic energy transfer for hyperthermal H atom scattering from a semiconductor surface, Ge(111)c(2 × 8), we present a mixed quantum-classical nonadiabatic molecular dynamics model based on the time-dependent evolution of Kohn-Sham orbitals and a classical path approximation. Our results suggest that facile nonadiabatic electronic transitions from the valence band to the conduction band occur selectively at the rest atom site, where surface states are doubly occupied, but not at the adatom site, where empty surface states are localized. This drastic site specificity can be attributed to the changes of the local band structure upon energetic H collisions at different surface sites, leading to transient near degeneracies and significant couplings between occupied and unoccupied orbitals at the rest atom but not at the adatom. These insights shed valuable light on the collision-induced nonadiabatic dynamics at semiconductor surfaces.