Kinetic and ion pairing contributions in the dielectric spectra of electrolyte aqueous solutions

Abstract

Understanding dielectric spectra can reveal important information about the dynamics of solvents and solutes from the dipolar relaxation times down to electronic ones. In the late 1970s, Hubbard and Onsager predicted that adding salt ions to a polar solution would result in a reduced dielectric permittivity that arises from the unexpected tendency of solvent dipoles to align opposite to the applied field. So far, this effect has escaped an experimental verification, mainly because of the concomitant appearance of dielectric saturation from which the Hubbard-Onsager decrement cannot be easily separated. Here we develop a novel non-equilibrium molecular dynamics simulation approach to determine this decrement accurately for the first time. Using a thermodynamic consistent all-atom force field we show that for an aqueous solution containing sodium chloride around 4.8 Mol/l, this effect accounts for 12\% of the total dielectric permittivity. The dielectric decrement can be strikingly different if a less accurate force field for the ions is used. Using the widespread GROMOS parameters, we observe in fact an {\it increment} of the dielectric permittivity rather than a decrement. We can show that this increment is caused by ion pairing, introduced by a too low dispersion force, and clarify the microscopic connection between long-living ion pairs and the appearance of specific features in the dielectric spectrum of the solution.