On the performance of local density approximation in describing the adsorption of electron donating/accepting molecules on graphene

► The performance of LDA for physisorption on graphene was evaluated. ► LDA adsorption energies are lower than those from M06-2X by 0.4-3.2 kcal/mol. ► They are more significantly lower than those from PBE-D by 3-6 kcal/mol. ► Adsorption energies linearly correlate with polarizability, rather than IP. ► Molecular electronegativity shows a good linear correlation with electron transfer.