Metal work-function changes induced by organic adsorbates: A combined experimental and theoretical study

The role of molecular dipole moment, charge transfer, and Pauli repulsion in determining the work-function change (??) at organic-metal interfaces has been elucidated by a combined experimental and theoretical study of (CH3S)2/Au(111) and CH3S/Au(111). Comparison between experiment and theory allows us to determine the origin of the interface dipole layer for both phases. For CH3S/Au(111), ?? can be ascribed almost entirely to the dipole moment of the CH3S layer. For (CH3S)2/Au(111), a Pauli repulsion mechanism occurs. The implications of these results on the interpretation of ?? in the presence of strongly and weakly adsorbed molecules is discussed.