MP2-IQA: upscaling the analysis of topologically partitioned electron correlation.

When electronic correlation energy is partitioned topologically, a detailed picture of its distribution emerges, both within atoms and between any two atoms. This methodology allows one to study dispersion beyond its more narrow definition in long-range Rayleigh-Schrödinger perturbation theory. The interacting quantum atoms (IQA) method was applied to MP2/6-31G(d,p) (uncontracted) wave functions of a wide variety of systems: glycine…water (hydration), the ethene dimer (π-π interactions), benzene (aromaticity), cyclobutadiene (antiaromaticity), and NH3 BH3 (dative bond). Through the study of molecular complexes it turns out that dispersion energy is either important to a system's stabilization (for the C2 H4 dimer) or not important (for Gly…H2 O). We have also discovered that the delocalization in benzene lowers the strength of Coulomb repulsion in the bonds, which has been quantified for the first time through IQA. Finally, we showed that the nature of the dative bond is much different from that of a regular covalent bond as it is not destabilized by electronic correlation. Finally, the conclusions obtained for these archetypical systems have implications for the future of the quantum topological force field FFLUX in the simulation of larger systems. Graphical abstract Atomic and bond dynamic correlation energies are now available thanks to IQA. Larger molecules can now be accessed to include resonance and solvation of FFLUX force field.