SEARCH

SEARCH BY CITATION

Keywords:

  • molecular dynamics;
  • interfaces;
  • alkane;
  • electrolytes;
  • ion solvation sphere

Abstract

The effect on the structural and thermodynamic properties in water/n-heptane interfaces on addition of NaCl, MgCl2, and ZnCl2 has been examined through five independent 100-ns molecular dynamics simulations. Results indicate that the interfacial thickness within the framework of the capillary-wave model decreases on addition of electrolytes in the order Na+ < Mg2+ < Zn2+, whereas the interfacial tension increases in the same order. Ionic density profiles and self-diffusion coefficients are strongly influenced by the strength of the first hydration shell, which varies in the order Na+ < Mg2+ < Zn2+. On the other hand, the Cl behavior, that is, diffusion and solvation sphere, is influenced by its counterion. Accordingly, cations are strongly expelled from the interface, which is especially remarkable for the small divalent cations. This fact alters the water geometry near the interface and in a lesser extent n-heptane order and number of hydrogen bonds per water molecule close to the interface. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011