Interaction Energy Landscapes of Aromatic Heterocycles through a Reliable yet Affordable Computational Approach.

Abstract

Noncovalent interactions between homodimers of several aromatic heterocycles (pyrrole, furan, thiophene, pyridine, pyridazine, pyrimidine, and pyrazine) are investigated at the ab initio level, employing the Möller-Plesset second-order perturbation theory, coupled with small Gaussian basis sets (6-31G* and 6-31G**) with specifically tuned polarization exponents. The latter are modified using a systematic and automated procedure, the MP2mod approach, based on a comparison with high level CCSD(T) calculations extrapolated to a complete basis set. The MP2mod results achieved with the modified 6-31G** basis set show an excellent agreement with CCSD(T)/CBS reference energies, with a standard deviation less than 0.3 kcal/mol. Exploiting its low computational cost, the MP2mod approach is then used to explore sections of the intermolecular energy of the considered homodimers, with the aim of rationalizing the results. It is found that the direct electrostatic interaction between the monomers electron clouds is at the origin of some observed features, and in many cases multipoles higher than dipole play a relevant role, although often the interplay with other contributions to the noncovalent forces (as for instance induction, π-π or XH-π interactions) makes a simple rationalization rather difficult.