Methane molecule over the defected and rippled graphene sheet

Adsorption of a methane molecule (CH4) onto a defected and rippled graphene sheet is studied using ab initio and molecular mechanics calculations. The optimal adsorption position and orientation of this molecule on the graphene surface (motivated by the recent realization of graphene sensors to detect individual gas molecules) is determined and the adsorption energies are calculated. In light of the density of states, we used the SIESTA code. It is found that (i) classical force field yields adsorption energy comparable with experimental result and ab initio calculation; (ii) the periodic nature of the van der Waals potential energy stored between methane and perfect sheet is altered due to the insertion vacancies and sinusoidal ripples; (iii) the van der Waals potential energy is found to be sensitive to the presence of the vacancies and the ripples so that the added molecule avoids to be around vacant cites and on top of the peaks.

► The estimated binding energy is in good agreement with ab initio and experimental. ► Both defects and ripples alter the periodicity of the vdW energy surfaces. ► CH4 avoids to be located around the defective cites and the peaks of the ripples. ► CH4 molecule prefers to be inside the valleys of the ripples.