Noncovalent Interactions between Molecular Hydrogen and the Alkali Fluorides: H–H···F–M (M = Li, Na, K, Rb, Cs). High Level Theoretical Predictions and SAPT Analysis

Various types of hydrogen bonds have been recognized during the past century. In this research, a new type of noncovalent interaction, the dipole-induced hydrogen bond formed between a hydrogen molecule and an alkali halide, H–H···F–M, is studied. Proposed by Zhang and co-workers (Phys. Chem. Chem. Phys. 2015, 17, 20361), these systems are extensively investigated initially using the “gold standard” CCSD­(T) method in conjunction with augmented correlation-consistent polarized core–valence basis sets up to quadruple-ζ. The full triple excitations CCSDT method has been used to further refine the energies. Several properties including geometries, bond energies, vibrarional frequencies, charge distributions, and dipole moments have been reported. The earlier Zhang research considered only the linear H–H···F–M structures. However, we find these linear stationary points to be separated by very small barriers from the much lower lying bent Cs structures. The CCSDT/aug-cc-pCVQZ­(‑PP) method predicts the dissociation energies for bent H–H···F–M (M = Li, Na, K, Rb, Cs) are 2.76, 2.96, 3.00, 2.89, and 2.49 kcal mol–1, respectively, suggesting that the H···F hydrogen bond becomes gradually stronger when alkali metal M goes down the periodic table from Li to K but becomes slightly weaker for Rb and even more for Cs. This Li Rb > Cs order is consistent with that for the dipole moments for the isolated MF (M = Li, Na, K, Rb, Cs) diatomics. Symmetry adapted perturbation theory (SAPT) is used to understand these unusual noncovalent interactions