A New Phase-Field Approach to Variational Implicit Solvation of Charged Molecules with the Coulomb-Field Approximation

TL;DR

This paper introduces a novel phase-field model for charged molecule solvation that improves accuracy and stability by self-consistently coupling surface, van der Waals, and electrostatic energies, with proven convergence and efficient numerical solutions.

Contribution

A new phase-field approach incorporating a coupled variational free-energy functional for charged molecules with Coulomb-field approximation, ensuring better accuracy and stability.

Findings

Enhanced localization of system forces near the solute-solvent interface.

Maintains hyperbolic tangent profile at larger interfacial widths.

Improves physical realism by avoiding negative phase-field values.

Abstract

We construct a new phase-field model for the solvation of charged molecules with a variational implicit solvent. Our phase-field free-energy functional includes the surface energy, solute-solvent van der Waals dispersion energy, and electrostatic interaction energy that is described by the Coulomb-field approximation, all coupled together self-consistently through a phase field. By introducing a new phase-field term in the description of the solute-solvent van der Waals and electrostatic interactions, we can keep the phase-field values closer to those describing the solute and solvent regions, respectively, making it more accurate in the free-energy estimate. We first prove that our phase-field functionals $\Gamma$-converge to the corresponding sharp-interface limit. We then develop and implement an efficient and stable numerical method to solve the resulting gradient-flow equation to obtain equilibrium conformations and their associated free energies of the underlying charged molecular system. Our numerical method combines a linear splitting scheme, spectral discretization, and exponential time differencing Runge-Kutta approximations. Applications to the solvation of single ions and a two-plate system demonstrate that our new phase-field implementation improves the previous ones by achieving the localization of the system forces near the solute-solvent interface and maintaining more robustly the desirable hyperbolic tangent profile for even larger interfacial width. This work provides a scheme to resolve the possible unphysical feature of negative values in the phase-field function found in the previous phase-field modeling (cf. H. Sun, et al. J. Chem. Phys., 2015) of charged molecules with the Poisson--Boltzmann equation for the electrostatic interaction.