jp9b10233_si_001.pdf (5.01 MB)
Electrophilicity Indices and Halogen Bonds: Some New Alternatives to the Molecular Electrostatic Potential
journal contribution
posted on 2020-02-28, 21:31 authored by Guillaume Hoffmann, Vincent Tognetti, Laurent JoubertWe
assess the ability of various atomic and molecular electrophilicity
descriptors to predict the strength of halogen bonds. To this aim,
several physicochemical quantities rooted within the framework of
conceptual density functional theory were derived using second and
third order Taylor expansions of the electronic energy, and their
correlation to binding energies were compared with those obtained
for more usual electronic descriptors. This benchmark was performed
for a large and representative database of noncovalent complexes involving
fluorine, chlorine, and bromine atoms, and showed that some of these
new quantities, in particular the atomic cubic electrophilicity index,
exhibited more transferability and broadness of application than did
more common descriptors such as the molecular electrostatic potential.