The experimental measurement of slow F − ions (v < 0.1 a.u.) scattered from a clean and flat LiF(001) surface at a grazing angle of incidence shows that there is a large fraction of F − projectile destruction. Here, from detailed energy defect and transition probability calculations, we find that the large F − destruction observed was due to the formation of a local pre-existing surface bandgap electronic state, Li 2 + (1 2 Σ u + ,R = a LiF /√2) (a LiF = lattice constant of the LiF crystal), via a nearly resonant charge transfer between the F − projectile and two nearest-neighbor Li + lattice ions along the ⟨110⟩ or ⟨1̅ 10⟩ channel at the LiF(001) surface. In combination with the related energy loss, the physical pictures of the producing mechanism of various products for 1 keV F + incidence based on this state are also presented. An internuclear distance of R = 2.84 Å makes the efficient and controllable preparation of this state on a LiF surface possible, paving the way for atomic-scale microdevice fabrication.