Abstract

Based on primitive model computer simulations with explicit microions, we calculate theeffective interactions in a binary mixture of charged colloids with species A and Bfor different size and charge ratios. An optimal pairwise interaction is obtainedby fitting the many-body effective forces. This interaction is close to a Yukawa(or Derjaguin–Landau–Verwey–Overbeek (DLVO)) pair potential but the ABcross-interaction is different from the geometric mean of the two direct AA and BBinteractions. As a function of charge asymmetry, the corresponding nonadditivityparameter is first positive, then significantly negative and is then positive again. Wefinally show that an inclusion of nonadditivity within an optimal effective Yukawamodel gives better predictions for the fluid pair structure than DLVO theory.

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