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Bond Paths as Privileged Exchange Channels
Author(s) -
Pendás A. Martín,
Francisco Evelio,
Blanco Miguel A.,
Gatti Carlo
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200700408
Subject(s) - atoms in molecules , steric effects , chemistry , molecule , hydrogen bond , quantum , interpretation (philosophy) , atom (system on chip) , chemical physics , meaning (existential) , quantum mechanics , physics , epistemology , stereochemistry , computer science , embedded system , programming language , philosophy , organic chemistry
Evidence 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 controversies questioning the meaning of hydrogen–hydrogen bonding and the nature of the so‐called “steric interactions”, the role of bond paths in endohedral complexes, and the generality of the results provided by the QTAIM. Implications for the nature of more general closed‐shell interactions are also briefly discussed.