Lennard-Jones Intermolecular Potentials for the Description of 6-Membered Aromatic Heterocycles Interacting with the...

We have generated Lennard-Jones potentials for the interaction between CX₂ (X = O, S) and 11 nitrogen-doped benzene derivatives in different orientations at the M06-2X/def2-tzvpp level as tools to parametrize accurate force fields and to better understand the interaction of these greenhouse gases with heterocyclic building blocks used in the design of capture and detection systems. We find that the most favorable interactions are found between the carbon in CO₂ and the main heterocycle in the ring in a parallel orientation, whereas the preferred interaction mode of CS₂ is established between sulfur and the π density of the aromatic ring. The fact that the preferences for interaction sites and orientations of CO₂ and CS₂ are most of the times opposite helps in terms of ensuring the selectivity of these systems in front of these two isoelectronic compounds. The existence of very good linear correlations ( R² values very close to one) between the number of nitrogen atoms in the heterocyclic ring and the depth of the interaction potential wells opens the door to the use of these results in generating coarse-grained potentials or models with predictive power for use in the design of larger systems.