Refined SMD Parameters for Bromine and Iodine Accurately Model Halogen-bonding Interactions in Solution

Engelage, E.; Schulz, N.; Heinen, F.; Huber, S. M.; Truhlar, D. G.; Cramer, C. J.
Chem. Eur. J. 2018, 24, 15983 (doi:10.1002/chem.201803652).

Motivated by the need to calculate liquid-phase free energies of species and equilibria involving halogen bonding, we used recent experimental data to optimize new Coulomb radii for Br and I for use in the SMD universal solvation model for calculating free energies of solvation. The use of the SMD model with these parameters for Br and I and the SMD values of all other parameters is called SMD18. After parametrization, the SMD18 model was tested for data not used in the parametrization. These data are standard-state free energies (equivalent to equilibrium constants) for 18 ionic equilibria involve Cl, Br, and I halogen bonding in acetonitile, and the agreement of theory and experiment is satisfactory. The SMD18 model is then used to compare hydrogen bonding to halogen bonding and to reassess the interpretation of recent experiments.