Vacuum level alignment at organic/metal junctions:: "Cushion" effect and the interface dipole -: art. no. 263502

The electronic level alignment of various organic molecules on metal surfaces has been determined by a combined experimental and theoretical effort. Using ab initio electronic structure calculations, it is demonstrated that the commonly observed interface dipole is largely due to a quantum-mechanical phenomenon resulting from exchange repulsion. Surprisingly, this physical effect, also referred to as Pauli repulsion dominates even in the case of aromatic molecules on Cu and Au surfaces, i.e., on interfaces that are of key importance in molecular electronics.