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Photoemission from different alkali core levels (Na 2p, K 3p, Rb 4p, and Cs 4d) has been studied for thin alkali films deposited on four different 4d metal surfaces: Mo(110), Rh(111), Rh(110), and Pd(100). Alkali atoms at the interface, the bulk, and at the surface of the adsorbed alkali film are found to have different core-level binding energies. It is found that the core-level binding-energy shifts of the alkali metals induced by the 4d-metal substrate increase with increasing atomic number of the alkali metal and with increasing atomic number of the 4d metal. Thermodynamical quantities such as interface segregation energies and adhesion energies are deduced from the layer-resolved shifts. Estimates of the experimental binding-energy shifts are given using semiempirical calculations, and certain complications in doing that are discussed.

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©1994 The American Physical Society