Correlations between Computation and Experimental Thermodynamics of Halogen Bonding

Correlations between experimental, solution-phase thermodynamic data and calculated gas-phase energies of interaction are investigated for noncovalent halogen bonding interactions between electron-deficient iodo compounds and Lewis bases. The experimental data consist of free energies of interaction spanning roughly 7 kcal/mol; they encompass halogen bonds involving both organic (iodoperfluoroarene or iodoperfluoroalkane) and inorganic (I₂, IBr, ICN) donors with nitrogen- and oxygen-based acceptors and are divided into two sets according to the identity of the solvent in which they were determined (alkanes or CCl₄). Adiabatic energies of halogen bonding were calculated using a variety of methods, including 22 DFT exchange-correlation functionals, using geometries optimized at the MP2/6-31+G­(d,p) level of theory. Certain DFT functionals, particularly the B97-1, B97-2, and B98 family, provide outstanding linear correlations with the experimental thermodynamic data, as assessed by a variety of statistical methods