Paper detail

Coarse-Grained Modeling of Charged Colloidal Suspensions: From Poisson-Boltzmann Theory to Effective Interactions

Electrostatic interactions between macroions largely govern the equilibrium thermodynamic and dynamical properties of charge-stabilized colloidal suspensions and polyelectrolyte solutions. Predicting the properties of such complex, multicomponent systems with accuracy sufficient to guide and interpret experiments requires realistic modeling of the interparticle interactions and collective behavior of many-particle systems. While the fundamental interactions may be simple, the sheer number of particles and the broad ranges of length and time scales confront the modeler with significant computational challenges. A general strategy for mitigating such challenges is to "coarse grain" or "integrate out" the degrees of freedom of some components, reducing the original multicomponent model to a simpler model of fewer components. The trade-off for so reducing complexity is that the simpler model is governed by modified (effective) interparticle interactions. This chapter is a "how-to" manual for implementing coarse-graining methods to derive effective electrostatic interactions in systems of charged macroions. After reviewing the cell model implementation of the Poisson-Boltzmann theory of charged colloids and polyelectrolytes, we describe an alternative implementation, based on perturbation theory. From a linear response approximation, we derive effective electrostatic interactions for charge-stabilized suspensions of spherical colloids.