Reproducibility of potential energy surfaces of organic/metal interfaces on the example of PTCDA on Ag(111)

Molecular adsorption at organic/metal interfaces depends on a range of mechanisms: covalent bonds, charge transfer, Pauli repulsion, and van der Waals (vdW) interactions shape the potential energy surface (PES), making it key to understanding organic/metal interfaces. Describing such interfaces with density functional theory requires carefully selecting the exchange correlation (XC) functional and vdW correction scheme. To explore the reproducibility of the PES with respect to the choice of method, we present a benchmark of common local, semi-local, and non-local XC functionals in combination with various vdW corrections. We benchmark these methods using perylene-tetracarboxylic dianhydride on Ag(111), one of the most frequently studied organic/metal interfaces. For each method, we determine the PES using a Gaussian process regression algorithm, which requires only about 50 density functional theory calculations as input. This allows a detailed analysis of the PESs’ features, such as the positions and energies of minima and saddle points. Comparing the results from different combinations of XC functionals and vdW corrections enables us to identify trends and differences between the approaches. PESs for different computation methods are in qualitative agreement but also display significant quantitative differences. In particular, the lateral positions of adsorption geometries agree well with experiment, while adsorption heights, energies, and barriers show larger discrepancies