Charged colloidal system: Small ion distribution and effective interaction

We applied a molecular dynamics simulation technique to charged colloidal systems in order to investigate small ion distribution in thermal equilibrium and to evaluate the effective interaction among macroions. For a system containing a single macroion, screening by counterions was evaluated. The screening becomes more complete for larger macroion charge. In spite of the large inhomogeneity, the chemical potential of small ions is constant for the entire system. Using a thermodynamic integral method, the effective potential (Helmholtz free energy) for two-macroion systems was evaluated as a function of macroion separation distance, and found to be repulsive under normal conditions. Many-body effect is also discussed by comparing the effective potentials for two- and three-macroion systems.

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► Screening by counterion becomes more complete for larger macroion charge.
► Chemical potential of small ions is constant throughout the system.
► Effective interaction between two macroions of same charge is normally repulsive.
► Effective interaction is similar to the usual models with renormalized charge.
► Many-body effect is attractive for short distance.