Stretching force constants as descriptors of energy and geometry of F···HF hydrogen bonds

In this work applicability of proton donor group stretching vibration force constants k_s and intermolecular stretching force constants k_σ for evaluations of hydrogen bond strength and geometry are discussed. For a set of 30 complexes with F···HF hydrogen bonds in a wide range 0.5-48 kcal/mol by means of quantum chemical calculations equilibrium geometries, complexation energies, vibrational frequencies and corresponding force constants were calculated (MP2/aug-cc-pVTZ). It is shown, that properties of a hydrogen bond are more strictly correlated with the values of force constants than with vibrational frequencies. Easy-to-use equations for estimations of hydrogen bond energy ∆E and geometry (r_FH, r_FF) based on k_s and k_σ values are proposed.