Assessment of approaches for dispersive forces employing graphone as a case study

TL;DR

This study compares various density functional theory methods to evaluate dispersive forces in hydrogenated graphene systems, revealing insights into hydrogenation mechanisms and surface interactions.

Contribution

It systematically assesses multiple van der Waals computational schemes on graphene and graphone, highlighting their similarities and differences in energetics and bonding.

Findings

All methods agree qualitatively on hydrogen adsorption behavior.

Discrepancies mainly appear in energetic calculations.

Hydrogen adsorption strengthens bonding with Ni(111) surface.

Abstract

We have studied two interchange layer systems, (i) free standing partly hydrogenated graphene (graphone), and (ii) graphone on the Nickel (111) surface, to assess various density functional theory based computational schemes incorporating van der Waals forces. The various van der Waals methods have been employed ranging from the semiempirical force-field-like correction of Grimme, through non-local van der Waals density functionals, up to the functionals involving exact exchange and the random phase approximation for the correlation. Generally, all computational schemes lead to a similar qualitative picture of hydrogen layer physisorption and chemisorption to graphene. The largest discrepancies between the approaches emerge for the energetics of the investigated systems. Our studies shed light on the physical mechanisms of graphene hydrogenation both in vacuum and in the proximity of metallic surface. In particular, it is revealed that the adsorption of hydrogen atoms affects the nature of the bonding between graphene and the Ni(111) surface, from the weak to strong semi-covalent bonding. On the other hand, it turns out that the adsorption of hydrogen layer to graphene is stronger in the presence of the metallic surface.