The Calculus of Boundary Variations and the Dielectric Boundary Force in the Poisson-Boltzmann Theory for Molecular Solvation

In a continuum model of the solvation of charged molecules in an aqueous solvent, the classical Poisson-Boltzmann (PB) theory for the electrostatics of an ionic solution is generalized to include the solute point charges and the dielectric boundary that separates the high-dielectric solvent from the low-dielectric solutes. With such a setting, we construct an effective electrostatic free-energy functional of ionic concentrations. The functional admits a unique minimizer whose corresponding electrostatic potential is the unique solution to the boundary-value problem of the nonlinear dielectric boundary PB equation. The negative first variation of this minimum free energy with respect to variations of the dielectric boundary defines the normal component of the dielectric boundary force. Together with the solute-solvent interfacial tension and van der Waals interaction forces, such boundary force drives an underlying charged molecular system to a stable equilibrium, as described by a variational implicit-solvent model. We develop an L-2-theory for boundary variations and derive an explicit formula of the dielectric boundary force. Our results agree with a molecular-level prediction that the electrostatic force points from the high-dielectric aqueous solvent to the low-dielectric charged molecules. Our method of analysis is general as it does not rely on any variational principles.

Automated summary

In this paper, the classical Poisson-Boltzmann theory is generalized to include solute point charges and dielectric boundary in the solvation of charged molecules in aqueous solvent. By analyzing boundary variations, an explicit formula of dielectric boundary force is derived, describing the stable equilibrium state of the charged molecular system. The results align with molecular-level predictions, showing that the electrostatic force points from the high-dielectric solvent to the low-dielectric charged molecules.