Exploring the bonding of large hydrocarbons on noble metals: Diindoperylene on Cu(111), Ag(111), and Au(111)

Abstract

We present a benchmark study for the adsorption of a large $\ensuremath{\pi}$-conjugated organic molecule on different noble metal surfaces, which is based on x-ray standing wave (XSW) measurements and density functional theory calculations with van der Waals (vdW) interactions. The bonding distances of diindenoperylene on Cu(111), Ag(111), and Au(111) surfaces (2.51, 3.01, and 3.10 \AA{}, respectively) determined with the normal-incidence XSW technique are compared with calculations. Excellent agreement with the experimental data, i.e., deviations less than 0.1 \AA{}, is achieved using the Perdew-Burke-Ernzerhof (PBE) functional with vdW interactions that include the collective response of substrate electrons (the $\mathrm{PBE}+{\mathrm{vdW}}^{\mathrm{surf}}$ method). It is noteworthy that the calculations show that the vdW contribution to the adsorption energy increases in the order $\text{Au}(111)<\text{Ag}(111)<\text{Cu}(111)$.