Global potentials for the interaction between rare gases and graphene-based surfaces: An atom-bond pairwise additive representation

Abstract

Global potentials for the physisorption of rare-gas atoms on graphene and graphite, amenable for a variety of dynamics simulations, are reported. An atom-bond pairwise additive form of the potential is used, where the interaction pairs, represented by proper analytical functions, are constituted by the Rg atom (Rg = He, Ne, Ar, Kr) and the C-C bonds of the graphene sheet(s). The parameters of the atom-bond pair potential, derived from the polarizability of the interacting partners, are fine-tuned, exploiting calculations of the prototypical Rg-coronene system using high-level electronic structure methods and large basis sets. The atom-graphene/graphite potential is further expanded in a Fourier series, and it is found that for an accurate representation of the interaction only a small number of corrugation terms need to be added to the laterally averaged potential. Furthermore, this corrugation part of the potential is both identical for Rg-graphene and Rg-graphite; in other words, inner layers of graphite only play a role in the laterally averaged Rg-graphite potential. For all systems, the hollow at the center of the carbon ring is the preferred adsorption site, although diffusion barriers are low. The present results compare well with previous data regarding well depths and equilibrium distances at different adsorption sites and, for graphite, the long-range dispersion coefficient C3. In addition, binding energies (eigenvalues of the laterally averaged potentials) are in a fairly good agreement with experimental determinations, providing further support for the reliability of the potentials. © 2013 American Chemical Society.