Structural and dynamical properties of hydrogen fluoride in aqueous solution: An ab initio quantum mechanical charge field molecular dynamics simulation

Abstract

The novel ab initio quantum mechanical charge field (QMCF) molecular dynamics simulation at the Hartree - Fock level has been employed to investigate hydration structure and dynamics of hydrogen fluoride in aqueous solution. The average H-F bond length of 0.93 Åobtained from the QMCF MD simulation is in good agreement with the experimental data. The HHF⋯O W distance of 1.62 Åwas evaluated for the first hydration shell, and 2.00 Å was observed for the FHF⋯HW distance. The stability of hydrogen bonding is more pronounced in the hydrogen site of hydrogen fluoride, with a single water molecule in this part of the first hydration shell. A wide range of coordination numbers between 3 and 9 with an average value of 5.6 was obtained for the fluorine site. The force constants of 819.1 and 5.9 N/m were obtained for the HHF_FHF and HHF⋯OW interactions, respectively, proving the stability of the nondissociated form of hydrogen fluoride in aqueous solution. The mean residence times of 2.1 and 2.5 ps were determined for ligand exchange processes in the neighborhood of fluorine and hydrogen atoms of hydrogen fluoride, respectively, indicating a weak structure-making effect of hydrogen fluoride in water. The corresponding H-bond lifetimes attribute this effect to the H atom site of HF. © 2008 American Chemical Society.