Coupled Cluster Investigation of the interaction of Beryllium, Magnesium, and Calcium with Pyridine: Implications for the Adsorption on Nitrogen-Doped Graphene

Publication date: Available online 22 January 2019Source: Computational and Theoretical ChemistryAuthor(s): Saif Ullah, Pablo A. Denis, Fernando SatoAbstractWe performed benchmark calculations to study the complexes of pyridine with beryllium, magnesium, and calcium. In all cases, the σ structures, in which the alkaline-earth element interacts with nitrogen, were found to be more stable than the ones featuring interactions with the π cloud. At the CCSD(T)/CBS level of theory, the dissociation energies (De) are 6.5, 3.7 and 7.2 kcal/mol, for beryllium, magnesium, and calcium, respectively. Our estimation of the D0 of the calcium-pyridine complex is in excellent agreement with the experimental value. For comparative purposes, we studied the performance of the M06-2X, PBE-D3BJ, vdW-DF, and B2PLYP-D2BJ density functionals. All of the DFT methods employed significantly overestimated the dissociation energies. Finally, in light of the results obtained, pyridinic nitrogen is the doping configuration to be chosen in nitrogen-doped graphene to improve the adsorption of alkaline-earth elements on this material.Graphical abstract

Source: Computational and Theoretical Chemistry - January 22, 2019 Category: Chemistry Source Type: research