Halogen and Chalcogen Binding Dominated by Density-Driven Errors.

Abstract

Dispersion corrections of various kinds usually improve DFT energetics of weak noncovalent interactions. However, in some cases involving molecules or halides, especially those with σ-hole interactions, the density-driven errors of uncorrected DFT are larger than the dispersion corrections. In these abnormal situations, HF-DFT (using Hartree-Fock densities instead of self-consistent densities) greatly improves bond energies, while dispersion corrections can even worsen the results. On the other hand, pnictogen bonds and the S22 data set are normal and are not improved by this procedure. Such effects should be accounted for when parametrizing dispersion interactions.