Activity coefficients of aqueous electrolytes from implicit-water molecular dynamics simulations

We obtain activity coefficients in NaCl and KCl solutions from implicit-water molecular dynamics simulations, at 298.15 K and 1 bar, using two distinct approaches. In the first approach, we consider ions in a continuum with constant relative permittivity (ɛ_r) equal to that of pure water; in the other approach, we take into account the concentration-dependence of ɛ_r, as obtained from explicit-water simulations. Individual ion activity coefficients (IIACs) are calculated using gradual insertion of single ions with uniform neutralizing backgrounds to ensure electroneutrality. Mean ionic activity coefficients (MIACs) obtained from the corresponding IIACs in simulations with constant ɛ_r show reasonable agreement with experimental data for both salts. Surprisingly, large systematic negative deviations are observed for both IIACs and MIACs in simulations with concentration-dependent ɛ_r. Our results suggest that the absence of hydration structure in implicit-water simulations cannot be compensated by correcting for the concentration-dependence of the relative permittivity ɛ_r. Moreover, even in simulations with constant ɛ_r for which the calculated MIACs are reasonable, the relative positioning of IIACs of anions and cations is incorrect for NaCl. We conclude that there are severe inherent limitations associated with implicit-water simulations in providing accurate activities of aqueous electrolytes, a finding with direct relevance to the development of electrolyte theories and to the use and interpretation of implicit-solvent simulations.