On the directionality and non-linearity of halogen and hydrogen bonds

Abstract

Benchmark quality structures and interaction energies have been produced using explicitly correlated coupled cluster methods for a systematic series of hydrogen and halogen bonded complexes: B⋯HCCH, B⋯HCl and B⋯ClF, with six different Lewis bases B. Excellent agreement with experimental structures is observed, verifying the method used to deduce the equilibrium deviation from collinearity of the intermolecular bond via rotational spectroscopy. This level of agreement also suggests that the chosen theoretical method can be employed when experimental equilibrium data are not available. The application of symmetry adapted perturbation theory reveals differences in the underlying mechanisms of interaction for hydrogen and halogen bonding, providing insights into the differences in non-linearity. In the halogen bonding case it is shown that the dispersion term is approximately equal to the overall interaction energy, highlighting the importance of choosing the correct theoretical method for this type of interaction.