Bond Paths as Privileged Exchange Channels

Abstract

AbstractEvidence that the bond paths of the quantum theory of atoms‐in‐molecules (QTAIM) signal preferred quantum‐mechanical exchange channels is presented. We show how bond paths between an atom A and the atoms B in its environment appear to be determined by competition among the A–B exchange‐correlation energies that always contribute to stabilize the A–B interactions. These pairwise additive stabilizations depend neither on the attractive or repulsive nature of the classical electrostatic interaction between the atoms’ charge densities, nor on the change in the self energies of the atoms involved. These other terms may well cause an overall molecular‐energy increase in spite of a possibly large A–B exchange‐correlation stabilization. After our proposal, bond paths, both at and out of equilibrium geometries, are endowed with a specific energetic meaning that should contribute to reconcile the orthodox QTAIM interpretation with other widely accepted views, and to settle recent controv

Evelio Francisco Miguélez

Associate Professor

Associate Professor of Physical Chemistry at the University of Oviedo. Expert in the development and application of quantum chemical topology methods, IQA analysis, and electron correlation descriptors.