The Myth of “Anti‐Electrostatic” Bonds
Year: 2026
Type: article
Abstract: ABSTRACT Some specific halogen‐ or hydrogen‐bonded complexes between ions of like charge have been described as “anti‐electrostatic.” However, the analyses of the bonding in these complexes have not used a valid electrostatic model because, for instance, the effect of counterions has been neglected. Complete and appropriate ab initio and DFT studies are now reported that confirm that the observed complexes do not contradict an electrostatic model of their bonding, as must be the case. Indeed, a simple point‐charge emulates the gas‐phase behavior of the chloride ion interacting with an iodine‐substituted anion to give a metastable minimum because of charge‐dipole interactions. Inclusion of counterions in the calculations gives positive V S(max) values at the iodine σ ‐hole. The effects of an empirical dispersion correction and solvation were investigated.
DOI: 10.1002/jcc.70410
Author: Timothy Clark
Institution: Friedrich-Alexander-Universität Erlangen-Nürnberg
Language: English
Subfield: Physical and Theoretical Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,520
OpenAlex ID: W7162784486