The Formation of σ-Hole Bonds: A Physical Interpretation

Abstract

This paper discusses two quite different computational experiments relating to the formation of σ-hole bonds A···B. The first involves looking at the complex at equilibrium and finding the contour X of the electronic density which allows the iso-density envelopes of A and B to be nearly touching. This contour increases, becoming closer to the nuclei, as the strength of the interaction increases. The second experiment involves allowing A and B to approach each other, with the aim of finding the distance at which their 0.001 a.u. iso-density envelopes are nearly merging into one envelope. What is found in the second experiment may be somewhat surprising, in that the ratio of the distance between interacting atoms at this nearly merging point—divided by the sum of the van der Waals radii of these atoms—covers a narrow range, typically between 1.2 and 1.3. It is intriguing to note that for the dataset presented, approaching molecules attracted to each other appear to do so unknowing of the strength of their ultimate interaction. This second experiment also supports the notion that one should expect favorable interactions, in some instances, to have close contacts significantly greater than the sums of the van der Waals radii.