Renormalization of Molecular Quasiparticle Levels at Metal-Molecule Interfaces: Trends across Binding Regimes

When an electron or a hole is added into an orbital of an adsorbed molecule the substrate electrons will rearrange in order to screen the added charge. This polarization effect reduces the electron addition and removal energies of the adsorbed molecule relative to those of the free molecule. Using a microscopic model of the metal-molecule interface, we illustrate the basic features of this renormalization mechanism through systematic GW, Hartree-Fock, and Kohn-Sham calculations for the molecular energy levels as function of the model parameters. We identify two different polarization mechanisms: (i) polarization of the metal (image charge formation) and (ii) polarization of the molecule via charge transfer across the interface. The importance of (i) and (ii) is found to increase with the metal density of states at the Fermi level and metal-molecule coupling strength, respectively.