  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.
