A new dynamical definition of the effective colloidal charge, especially suitable for the Monte Carlo and Molecular-dynamics simulations, is proposed. It is shown that for aqueous colloidal suspensions containing monovalent counterions the "dynamical" effective charge agrees perfectly with the "statistical" effective charge calculated using the Alexander prescription. In the case of multivalent ions, the effective charge behaves in a qualitatively different way from the predictions of the Poisson-Boltzmann theory.
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Diehl et al. (2004) studied this question.
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