Je. Roberts et J. Schnitker, BOUNDARY-CONDITIONS IN SIMULATIONS OF AQUEOUS IONIC-SOLUTIONS - A SYSTEMATIC STUDY, Journal of physical chemistry, 99(4), 1995, pp. 1322-1331
The room temperature properties of aqueous solutions of SPC, TIP4P, an
d MCY water are examined using either a potential cutoff or Ewald summ
ation. The effects of interaction truncation are compared to the impor
tance of the medium (vacuum or metal) that the entire system is immers
ed in; for this purpose simulations an also carried out in which the u
nit cell surface polarization term of De Leeuw, Perram, and Smith (Pro
c. R. Soc. London 1980, A373, 27) is explicitly accounted for. Both pu
re water and dilute solutions of Cl- and Fe2+ are investigated. It is
found that not only solvent-solvent orientational correlations but als
o ion-solvent energies, ion-induced solvent reorganization energies, a
nd ionic diffusion coefficients can be exceedingly sensitive to the na
ture of the surroundings. It is asserted that reaction field methods a
nd Ewald summation are the preferred types of boundary conditions, but
that the method of parametrization of the potential functions has to
be consistent with the eventual simulation conditions.