Mean-field theory and computation of electrostatics with ionic concentration dependent dielectrics (Q900240)

In this article, a mean-field variational model for electrostatics of an ionic solution is developed. Specifically, this model takes into account that the dielectric coefficient \(\varepsilon(\bar{c})\) (and therefore also the process of electrostatic interaction) depends itself on the local concentration of ions, as observed in physical experiments: mainly, \(\varepsilon(\cdot)\) is assumed to decrease monotonically and to be convex in the total concentration of ions \(\bar{c}\). The total free energy functional then reads as \[ F[c]=\int_\Omega \frac12 \rho(c)\psi(c)dV+\int_{\Gamma_N}\frac12 \sigma\psi(c)dS+\beta^{-1}\sum_{i=1}^M\int_\Omega c_i[\log(\Lambda^3c_i)+1]dV-\sum_{i=1}^M\mu_i\int_\Omega c_idV. \] There, \(c=(c_1,\ldots,c_M)\) denotes the vector of concentrations of the \(M\) ionic species, \(\rho(c)\) is the total charge density and \(\psi(c)\) is the electrostatic potential (related to \(c\) via Poisson's equation) on the spatial domain \(\Omega\subset\mathbb{R}^3\). The article deals with a close investigation of the above functional. First and second variations are derived and critical points -- called generalized Boltzmann distributions -- are found, providing a extension of the classical theory (for constant \(\varepsilon\)) to the framework of state-dependent dielectric coefficients. One important difference to the case of constant \(\varepsilon\) is the possible non-convexity of the energy functional \(F\). Numerical studies of a sample system are also made in the paper.