Poisson-Boltzmann thermodynamics of counter-ions confined by curved hard walls

Ladislav Samaj 1 E. Trizac 2

Physical Review E : Statistical, Nonlinear, and Soft Matter Physics, American Physical Society, 2016, 93, pp.012601

We consider a set of identical mobile point-like charges (counter-ions) confined to a domain with curved hard walls carrying a uniform fixed surface charge density, the system as a whole being electroneutral. Three domain geometries are considered: a pair of parallel plates, the cylinder and the sphere. The particle system in thermal equilibrium is assumed to be described by the nonlinear Poisson-Boltzmann theory. While the effectively 1D plates and the 2D cylinder have already been solved, the 3D sphere problem is not integrable. It is shown that the contact density of particles at the charged surface is determined by a first-order Abel differential equation of the second kind which is a counterpart of Enig's equation in the critical theory of gravitation and combustion/explosion. This equation enables us to construct the exact series solutions of the contact density in the regions of small and large surface charge densities. The formalism provides, within the mean-field Poisson-Boltzmann framework, the complete thermodynamics of counter-ions inside a charged sphere (salt-free system).

  • 1. Institute of Physics, Slovak Academy of Sciences
  • 2. LPTMS - Laboratoire de Physique Théorique et Modèles Statistiques