Bond paths between distant atoms do not necessarily indicate dominant interactions

The goal of the article is to revive discussion on the interpretation of bond paths linking distant atoms, particularly tracing weak interactions in dimers. According to the Pendás' concept of privileged exchange channel, a bond path is formed between this pair of competing atoms, which is associated with larger value of the exchange energy. We point out that, due to the short‐range nature of the exchange energy, bond paths linking distant atoms clearly become doubtful indicators of dominant intermolecular interactions, particularly if some other characteristics (geometric, spectroscopic, based on electrostatic parameters, etc.) indicate other intermolecular interactions as dominant. Several such cases are thoroughly investigated. We show that electrostatic parameters are much more reliable indicators of dominant intermolecular interactions than bond paths. Then, we pay attention that the presence of (“unexpected”, i.e., not necessarily indicating dominant intermolecular interactions) bond paths between pairs of atoms featuring highly expanded charge distributions can be easily explained by visual exploration of isodensity contour plots. As always pointing in the direction of the steepest increase, the gradient vector of the electron density favors areas of its high values gaining higher exchange energy, yet being blind to highly electron deficient areas nearby, which, however, can quite often be involved in dominant intermolecular interactions as strongly suggested by many other bonding analysis. We also suggest that an interatomic component of Hellmann‐Feynman force would most likely be the most reliable indicator of attractive or repulsive character of individual interatomic interaction. © 2018 Wiley Periodicals, Inc.