A polarizable continuum model for molecules at spherical diffuse interfaces.

We present an extension of the Polarizable Continuum Model (PCM) to simulate solvent effects at diffuse interfaces with spherical symmetry, such as nanodroplets and micelles. We derive the form of the Green's function for a spatially varying dielectric permittivity with spherical symmetry and exploit the integral equation formalism of the PCM for general dielectric environments to recast the solvation problem into a continuum solvation framework. This allows the investigation of the solvation of ions and molecules in nonuniform dielectric environments, such as liquid droplets, micelles or membranes, while maintaining the computationally appealing characteristics of continuum solvation models.

Wavelet formulation of the polarizable continuum model. II. Use of piecewise bilinear boundary elements.

The simplicity of dielectric continuum models has made them a standard tool in almost any Quantum Chemistry (QC) package. Despite being intuitive from a physical point of view, the actual electrostatic problem at the cavity boundary is challenging: the underlying boundary integral equations depend on singular, long-range operators. The parametrization of the cavity boundary should be molecular-shaped, smooth and differentiable.