FALDI-based criterion for and the origin of an electron density bridge with an associated (3,-1) critical point on Bader's molecular graph.

Abstract

The total electron density (ED) along the λ2 -eigenvector is decomposed into contributions which either facilitate or hinder the presence of an electron density bridge (DB, often called an atomic interaction line or a bond path). Our FALDI-based approach explains a DB presence as a result of a dominating rate of change of facilitating factors relative to the rate of change of hindering factors; a novel and universal criterion for a DB presence is, thus, proposed. Importantly, facilitating factors show, in absolute terms, a concentration of ED in the internuclear region as commonly observed for most chemical bonds, whereas hindering factors show a depletion of ED in the internuclear region. We test our approach on four intramolecular interactions, namely (i) an attractive classical H-bond, (ii) a repulsive O⋅⋅⋅O interaction, (iii) an attractive Cl⋅⋅⋅Cl interaction, and (iv) an attractive CH⋅⋅⋅HC interaction. (Dis)appearance of a DB is (i) shown to be due to a "small" change in molecular environment and (ii) qualitatively and quantitatively linked with specific atoms and atom-pairs. The protocol described is equally applicable (a) to any internuclear region, (b) regardless of what kind of interaction (attractive/repulsive) atoms are involved in, (c) at any level of theory used to compute the molecular structure and corresponding wavefunction, and (d) equilibrium or nonequilibrium structures. Finally, we argue for a paradigm shift in the description of chemical interactions, from the ED perspective, in favor of a multicenter rather than diatomic approach in interpreting ED distributions in internuclear regions. © 2018 Wiley Periodicals, Inc.