Adsorption energies of benzene on close packed transition metal surfaces using the random phase approximation

TL;DR

This paper demonstrates that the random phase approximation (RPA) provides highly accurate predictions of benzene adsorption energies on transition metal surfaces, outperforming other density functional methods, especially on reactive metals.

Contribution

The study systematically applies RPA to predict benzene adsorption energies on various metals, showing improved accuracy over existing methods and highlighting the need for advanced many-body approaches.

Findings

RPA achieves better than 10% agreement with experimental data.

Dispersion corrected DFT overestimates energies on reactive metals.

Coverage-dependent energies are well captured by RPA.

Abstract

The adsorption energy of benzene on various metal substrates is predicted using the random phase approximation (RPA) for the correlation energy. Agreement with available experimental data is systematically better than 10% for both coinage and reactive metals. The results are also compared with more approximate methods, including vdW-density functional theory (DFT), as well as dispersion corrected DFT functionals. Although dispersion corrected DFT can yield accurate results, for instance, on coinage metals, the adsorption energies are clearly overestimated on more reactive transition metals. Furthermore, coverage dependent adsorption energies are well described by the RPA. This shows that for the description of aromatic molecules on metal surfaces further improvements in density functionals are necessary, or more involved many body methods such as the RPA are required.