Hydrogen bonds in aqueous electrolyte solutions: statistics and dynamics based on both geometric and energetic criteria

Abstract

We have investigated the statistics and dynamics of hydrogen bonds in a concentrated aqueous electrolyte solution and also in pure water by means of molecular dynamics simulations. Both geometric and energetic definitions are employed for the existence of a hydrogen bond. The present study extends our earlier work on the structure and dynamics of hydrogen bonds where only the geometric definition was used. In the presence of ions, like the earlier results for geometric definition, the energetic definition is also found to give a lower number of hydrogen bonds per water molecule and a wider distribution, a slightly faster rate of breaking and a slower rate of structural relaxation of hydrogen bonds. The results are explained in terms of a decrease of the potential of mean force between water molecules, an enhanced population of hydrogen bonded water pairs in the vicinity of the dividing surface that separates the hydrogen bonded and nonbonded states and an increase of the friction on translational and rotational motion of water molecules in the presence of ions.