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Range separation: The divide between local structures and field theories
This work presents parallel histories of the development of two modern
theories of condensed matter: the theory of electron structure in quantum
mechanics, and the theory of liquid structure in statistical mechanics.
Comparison shows that key revelations in both are not only remarkably similar,
but even follow along a common thread of controversy that marks progress from
antiquity through to the present. This theme appears as a creative tension
between two competing philosophies, that of short range structure (atomistic
models) on the one hand, and long range structure (continuum or density
functional models) on the other. The timeline and technical content are
designed to build up a set of key relations as guideposts for using density
functional theories together with atomistic simulation.Comment: Expanded version of a 30 minute talk delivered at the 2018 TSRC
workshop on Ions in Solution, to appear in the March, 2019 issue of
Substantia (https://riviste.fupress.net/index.php/subs/index
Quasi-Chemical and Structural Analysis of Polarizable Anion Hydration
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.Comment: slight revision, in press at J. Chem. Phy
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