Bonding and vibrational dynamics of a large π-conjugated molecule on a metal surface

Abstract

The interplay between the substrate bonding of a large π-conjugated semiconductor molecule and the dynamical properties of the metal–organic interface is studied, employing the prototypical PTCDA/Ag(111) monolayer as an example. Both the coupling of molecular vibrations to the electron–hole-pair continuum of the metal surface and the inelastic scattering of tunnelling electrons by the molecular vibrations on their passage through the molecule are considered. The results of both types of experiment are consistent with the findings of measurements which probe the geometric and electronic structure of the adsorbate–substrate complex directly; generally speaking, they can be understood in the framework of standard theories for the electron–vibron coupling. While the experiments reported here in fact provide additional qualitative insights into the substrate bonding of our π-conjugated model molecule, their detailed quantitative understanding would require a full calculation of the dynamical interface properties, which is currently not available.