Minimization of Electrostatic Free Energy and the Poisson–Boltzmann Equation for Molecular Solvation with Implicit Solvent

Source abstract

In an implicit-solvent description of the solvation of charged molecules (solutes), the electrostatic free energy is a functional of concentrations of ions in the solvent. The charge density is determined by such concentrations together with the point charges of the solute atoms, and the electrostatic potential is determined by the Poisson equation with a variable dielectric coefficient. Such a free-energy functional is considered in this work for both the case of point ions and that of ions with a uniform finite size. It is proved for each case that there exists a unique set of equilibrium concentrations that minimize the free energy and that are given by the corresponding Boltzmann distributions through the equilibrium electrostatic potential. Such distributions are found to depend on the boundary data for the Poisson equation. Pointwise upper and lower bounds are obtained for the free-energy minimizing concentrations. Proofs are also given for the existence and uniqueness of the boundary-value problem of the resulting Poisson–Boltzmann equation that determines the equilibrium electrostatic potential. Finally, the equivalence of two different forms of such a boundary-value problem is proved.