On the Uselessness of Bond Paths Linking Distant Atoms and on the Violation of the Concept of Privileged Exchange Channels

We refer to frequently used determinants suggesting dominant interactions between distant atoms in various dimers. First of all, we show, against the still‐prevailling opinion, that, in general, bond paths have nothing in common with dominant intermolecular interactions and therefore they are useless in such cases. Quite the contrary, reliable information about dominant intermolecular interactions can be obtained by means of electrostatic potential maps, which very convincingly explain mutual orientation of molecules in a dimer. For the first time, numerous examples of interactions that violate both the concept of privileged exchange channels proposed by Pendás and his collaborators as well as inequalities obtained by Tognetti and Joubert for the β parameter related to secondary interactions are presented. The possible cause of this violation is suggested. We also show that the so‐called counterintuitive bond paths result from quite natural behavior of the electron density gradient vector, i. e. searching for those areas of space that are characterized by large values of electron density or the most expanded its distributions.