Communication: Kinetic and pairing contributions in the dielectric spectra of electrolyte solutions

J Chem Phys. 2014 Jun 7;140(21):211101. doi: 10.1063/1.4880237.

Abstract

In the late 1970s, Hubbard and Onsager predicted that adding salt 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. Here we develop a novel non-equilibrium molecular dynamics simulation approach to determine this decrement accurately. 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 increment of the dielectric permittivity rather than a decrement, caused by ion pairing and introduced by a too low dispersion force.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Chlorine Compounds / chemistry
  • Electrolytes / chemistry*
  • Kinetics
  • Molecular Dynamics Simulation
  • Potassium / chemistry
  • Salts / chemistry
  • Sodium / chemistry*
  • Solutions / chemistry*
  • Solvents / chemistry
  • Thermodynamics*
  • Water / chemistry

Substances

  • Chlorine Compounds
  • Electrolytes
  • Salts
  • Solutions
  • Solvents
  • Water
  • Sodium
  • Potassium