Methylbenzenes on graphene

We present a theory study of the physisorption of the series of methylbenzenes (toluene, xylene and mesitylene), as well as benzene, on graphene. The aim is two fold: we provide data that will be used as input to larger-scale methods like molecular-dynamics simulations, and at the same time we enhance the basic understanding of graphene used as a material for sensors and as an idealized model for the carbon in active carbon filters. The molecules are studied in a number of positions and orientations relative to graphene, using density functional theory with the van der Waals functional vdW-DF. The molecules are adsorbed fractional coverage. We focus on the vdW-DF1 and vdW-DF-cx functionals, and find that the binding energy of the molecules on graphene grows linearly with the number of methyl groups, at the rate of 0.09 eV (vdW-DF1) to 0.11 eV (vdW-DF-cx) per added methyl group. We further find that the orientation of the methyl groups of the molecules relative to graphene is at least as important as the lateral position of the whole molecule on graphene. © 2017 Elsevier B.V