Quantum theory of atoms in molecules in condensed charge density space

Abstract

By leveraging the fundamental doctrine of the quantum theory of atoms in molecules — the partitioning of the electron charge density (ρ) into regions bounded by surfaces of zero flux — we map the gradient field of ρ onto a two-dimensional space called the gradient bundle condensed charge density ([Formula: see text]). The topology of [Formula: see text] appears to correlate with regions of chemical significance in ρ. The bond wedge is defined as the image in ρ of the basin of attraction in [Formula: see text], analogous to the Bader atom, which is the basin of attraction in ρ. A bond bundle is defined as the union of bond wedges that share interatomic surfaces. We show that maxima in [Formula: see text] typically map to bond paths in ρ, though this is not necessarily always true. This observation addresses many of the concerns regarding the chemical significance of bond critical points and bond paths in the quantum theory of atoms in molecules.