Transfering spin into an extendedπorbital of a large molecule

Abstract

By means of low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS), we have investigated the adsorption of single Au atoms on a PTCDA monolayer physisorbed on the Au(111) surface. A chemical reaction between the Au atom and the PTCDA molecule leads to the formation of a radical that has an unpaired electron in its highest occupied orbital. This orbital is a $\ensuremath{\pi}$ orbital that extends over the whole Au-PTCDA complex. Because of the large Coulomb repulsion in this orbital, the unpaired electron generates a local moment when the molecule is adsorbed on the Au(111) surface. We demonstrate the formation of the radical and the existence of the local moment after adsorption by observing a zero-bias differential conductance peak that originates from the Kondo effect. By temperature dependent measurements of the zero-bias differential conductance, we determine the Kondo temperature to be ${T}_{\mathrm{K}}=(38\ifmmode\pm\else\textpm\fi{}8)\phantom{\rule{0.16em}{0ex}}\mathrm{K}$. For the theoretical description of the properties of the Au-PTCDA complex we use a hierarchy of methods, ranging from density functional theory (DFT) including a van der Waals correction to many-body perturbation theory (MBPT) and the numerical renormalization group (NRG) approach. Regarding the high-energy orbital spectrum, we obtain an excellent agreement with experiments by both spin-polarized DFT/MBPT and NRG. Moreover, the NRG provides an accurate description of the low-energy excitation spectrum of the spin degree of freedom, predicting a Kondo temperature very close to the experimental value. This is achieved by a detailed analysis of the universality of various definitions of ${T}_{\mathrm{K}}$ and by taking into account the full energy dependence of the coupling function between the molecule-metal complex and the metallic substrate.