Dispersion Self-Free Energies and Interaction Free Energies of Finite-Sized Ions in Salt Solutions

Abstract

The role for many-body dipolar (dispersion) potentials in ion?solvent and ion?solvent?interface interactions is explored. Such many-body potentials, accessible in principle from measured dielectric data, are necessary in accounting for Hofmeister specific ion effects. Dispersion self-energy is the quantum electrodynamic analogue of the Born electrostatic self-energy of an ion. We here describe calculations of dispersion self-free energies of four different anions (OH-, Cl-, Br-, and I-) that take finite ion size into account. Three different examples of self-free energy calculations are presented. These are the self-free energy of transfer of an ion to bulk solution, which influences solubility; the dispersion potential acting between one ion and an air?water interface (important for surface tension calculations); and the dispersion potential acting between two ions (relevant to activity coefficient calculations). To illustrate the importance of dispersion self-free energies, we compare the Born and dispersion contributions to the free energy of ion transfer from water to air (oil). We have also calculated the change in interfacial tension with added salt for air (oil)?water interfaces. A new model is used that includes dispersion potentials acting on the ions near the interface, image potentials, and ions of finite size that are allowed to spill over the solution?air interface. It is shown that interfacial free energies require a knowledge of solvent profiles at the interface.