Dielectric Constant of Ionic Solutions: Combined Effects of Correlations and Excluded Volume


  Ram Adar [1]  ,  Tomer Markovich [2]  ,  Amir Levy [3]  ,  Henri Orland [4]  ,  David Andelman [1]  
[1] Raymond and Beverly Sackler School of Physics and Astronomy, Tel Aviv University
[2] Center for Theoretical Biological Physics, Rice University
[3] Department of Physics, Massachusetts Institute of Technology
[4] Institut de Physique Theorique, CE-Saclay CEA

The dielectric constant of ionic solutions is known to reduce with increasing ionic concentrations. However, the origin of this effect has not been thoroughly explored. We derive a compact anlytical expression for the dielectric constant and show that both long-range Coulombic correlations and solvent excluded-volume are required in order to capture the important features of the dielectric behavior. For highly polar solvents, such as water, the dielectric constant is given by the product of the solvent volume fraction and a concentration-dependent susceptibility per volume fraction. The available solvent volume decreases as a function of ionic strength due the increasing volume fraction of ions. A similar decrease occurs for the susceptibility due to the correlations between the ions and solvent, reducing the dielectric response even further. Our predictions for the dielectric constant fit well with experiments for a wide range of concentrations for different salts in different temperatures, using a single fit parameter related to the ion size.