An analysis of van der Waals density functional components: Binding and corrugation of benzene and C60 on boron nitride and graphene

TL;DR

This study uses density functional theory with vdW-DF functionals to analyze how benzene and C60 molecules adsorb on graphene and boron nitride, revealing the influence of functional variants on binding and surface corrugation.

Contribution

It systematically compares vdW-DF1 and vdW-DF2 functionals, highlighting their effects on adsorption characteristics and proposing a method to assess exchange-correlation contributions.

Findings

C60 binds more strongly than benzene due to its size.

Binding separation is more sensitive to the exchange variant than the correlation.

Corrugation varies significantly with the vdW-DF version used.

Abstract

The adsorption of benzene and C60 on graphene and boron nitride (BN) is studied using density functional theory with the non-local correlation functional vdW-DF. By comparing these systems we can systematically investigate their adsorption nature and differences between the two functional versions vdW-DF1 and vdW-DF2. The bigger size of the C60 molecule makes it bind stronger to the surface than benzene, yet the interface between the molecules and the sheets are similar in nature. The binding separation is more sensitive to the exchange variant used in vdW-DF than to the correlation version. This result is related to the exchange and correlation components of the potential energy curve (PEC). We show that a moderate dipole forms for C60 on graphene, unlike for the other adsorption systems. We find that the corrugation is very sensitive to the variant or version of vdW-DF used, in particular the exchange. Further, we show that this sensitivity arise indirectly through the shift in binding separation caused by changing vdW-DF variant. Based on our results, we suggest a concerted theory-experiment approach to assess the exchange and correlation contributions to physisorption. Using DFT calculations, the corrugation can be linked to the optimal separation, allowing us to extract the exchange-correlation part of the adsorption energy. Molecules with same interfaces to the surface, but different geometries, can in turn cast light on the role of van der Waals forces.