The effect of surfaces and interfaces on the molecular properties and structure is of a great interest in the applied sciences and technology. In the following thesis, a theoretical framework for the calculations of the free energy and properties, including the effect of interfaces and surfaces, in quantum-mechanical formalism is presented. The model of choice is Polarizable Continuum Method (PCM), ...

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 ...

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- ...