Quasi-Chemical and Structural Analysis of Polarizable Anion Hydration

TL;DR

This study uses quasi-chemical theory and polarizable force fields to analyze how solute polarization and size influence the structure and thermodynamics of anion hydration, providing detailed insights into the Hofmeister series.

Contribution

It introduces a quasi-chemical approach combined with polarizable force fields to partition and analyze ion hydration free energies and structural anisotropy.

Findings

Excellent agreement with experimental hydration free energies.

Induction shows strong polarizability dependence.

Solvation anisotropy increases with ion polarizability.

Abstract

Quasi-chemical theory is utilized to analyze the roles of solute polarization and size in determining the structure and thermodynamics of bulk anion hydration for the Hofmeister series Cl$^-$, Br$^-$, and I$^-$. Excellent agreement with experiment is obtained for whole salt hydration free energies using the polarizable AMOEBA force field. The quasi-chemical approach exactly partitions the solvation free energy into inner-shell, outer-shell packing, and outer-shell long-ranged contributions by means of a hard-sphere condition. Small conditioning radii, even well inside the first maximum of the ion-water(oxygen) radial distribution function, result in Gaussian behavior for the long-ranged contribution that dominates the ion hydration free energy. The spatial partitioning allows for a mean-field treatment of the long-ranged contribution, leading to a natural division into first-order electrostatic, induction, and van der Waals terms. The induction piece exhibits the strongest ion polarizability dependence, while the larger-magnitude first-order electrostatic piece yields an opposing but weaker polarizability dependence. In addition, a structural analysis is performed to examine the solvation anisotropy around the anions. As opposed to the hydration free energies, the solvation anisotropy depends more on ion polarizability than on ion size: increased polarizability leads to increased anisotropy. The water dipole moments near the ion are similar in magnitude to bulk water, while the ion dipole moments are found to be significantly larger than those observed in quantum mechanical studies. Possible impacts of the observed over-polarization of the ions on simulated anion surface segregation are discussed.