Theoretical investigation on the interaction between beryllium, magnesium and calcium with benzene, coronene, cirumcoronene and graphene

• Published in: Chemical physics 2014-02, Vol.430, p.1-6
• Main Authors: Denis, Pablo A., Iribarne, Federico
• Format: Article
• Language: English
• Subjects: Adsorption; Carbon nanomaterials; Density functional calculations; Doping; Graphene
• ISSN: 0301-0104
• DOI: 10.1016/j.chemphys.2013.11.013

•The binding energies between benzene and Be, Mg and Ca are 1.8, 2.3 and 3.2kcal/mol.•The alkaline earth complexes with benzene favor the non ionic configuration.•For these complexes charge transfer does not take place.•The performance of the DFT functionals assayed was poor. The interaction energies (IE) between benzene and beryllium, magnesium and calcium were calculated at the CCSD(T)/CBS level and including corrections for core-valence and relativistic effects. The IE are 1.8, 2.3 and 3.2kcal/mol for Be, Mg and Ca, respectively, In contrast with our previous findings for the benzene–Li complex, we found that the non-ionic structure is more stable than the ionic configuration. Thus, charge-transfer from alkaline earths to benzene would not take place. The performance of MP2 and DFT functionals is poor. At the complete basis set limit, M06-2X, M06-L, B97D and MP2 exhibited similar MAD (∼ 0.7–0.8kcal/mol). When larger aromatic models were considered, the IE were similar to those computed for benzene. Finally, taking into account the drawbacks of the DFT functionals, the computed IE for the non-ionic adsorption of Be, Mg and Ca onto graphene, are tentatively estimated as 2.1, 2.7 and 2.9kcal/mol, respectively.