Theoretical study of Na-atom emission from NaCl (100) surfaces

Several models for the elementary processes causing the emission of alkali atoms by electronic excitation of NaCl (100) surfaces have been investigated theoretically. First, the desorption of a Na atom neighboring an electronically excited F center on the surface is simulated using a quantum-mechanical embedded-cluster technique. It is shown that emission of a Na atom is energetically favorable. The kinetics of this process is shown to be controlled by the probability of a nonradiative transition between the two states: the excited state of the F center and that corresponding to a Na atom desorbing from the surface. The potential barrier for desorption of an excited Na atom from the excited F-center state is found to be 2.1 eV. It is also found that the energy for emission of a Na atom from a cluster of F centers (the ${\mathit{F}}_3$ center) is considerably reduced (for a certain configuration of the defect) with respect to the similar energy for a single F center. The energy barrier for emission of a Na atom neighboring an F’ center on the surface is calculated to be 1 eV. It is shown that the electronic excitation of kinklike sites, with a Na atom at the edge, can lead to a barrierless emission of a Na atom, leaving a ${\mathit{V}}_{\mathit{k}}$-type defect behind. The results of calculations are discussed critically on the basis of existing experimental data.