High precision quantum-chemical treatment of adsorption: Benchmarking physisorption of molecular hydrogen on graphane

A multilevel hierarchical ab initio protocol for calculating adsorption on non-conducting surfaces is presented. It employs fully periodic treatment, which reaches local Møller-Plesset perturbation theory of second order (MP2) with correction for the basis set incompleteness via the local F12 technique. Post-MP2 corrections are calculated using finite clusters. That includes the coupled cluster treatment in the local and canonical frameworks (up to perturbative quadruples) and correlated core (with MP2). Using this protocol, the potential surface of hydrogen molecules adsorbed on graphane was computed. According to the calculations, hydrogen molecules are adsorbed on graphane in a perpendicular to the surface orientation with the minimum of the potential surface of around -3.6 kJ/mol located at the distance of 3.85 Å between the bond center of the hydrogen molecule and the mid-plane of graphane. The adsorption sites along the path from the downward-pointing carbon to the ring center of the graphane are energetically virtually equally preferable, which can enable nearly free translations of hydrogen molecules along these paths. Consequently, the hydrogen molecules on graphane most likely form a non-commensurate monolayer. The analysis of the remaining errors reveals a very high accuracy of the computed potential surface with an error bar of a few tenths of a kJ/mol. The obtained results are a high-precision benchmark for further theoretical and experimental studies of hydrogen molecules interacting with graphane.