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 NH(3)BH(3) (dative bond). Through the study of molecular complexes it turns out that dispersion energy is either important to a system’s stabilization (for the C(2)H(4) dimer) or not important (for Gly…H(2)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. [Figure: see text] ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (10.1007/s00894-018-3717-5) contains supplementary material, which is available to authorized users.