The first stage of formation of the CaF2-Si(111) and Ca-Si(111) interfaces is studied through the employment of the surface linear-muffin-tin-orbital approach in the atomic-sphere approximation. The interfaces are simulated by monolayers of F-Ca and Ca on Si(111), respectively. Both valence- and core-electron states have been calculated: their analysis gives important information about the nature of the Ca-Si and Ca-F bonds. These results are successfully compared with the available experimental data. The importance of considering the Madelung contribution in the interpretation of surface-core-level shifts is pointed out
