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A recipe for free-energy functionals of polarizable molecular fluids

Cornell Affiliated Author(s)

Author

R. Sundararaman
K. Letchworth-Weaver
Tomas Arias

Abstract

Classical density-functional theory is the most direct approach to equilibrium structures and free energies of inhomogeneous liquids, but requires the construction of an approximate free-energy functional for each liquid of interest. We present a general recipe for constructing functionals for small-molecular liquids based only on bulk experimental properties and ab initio calculations of a single solvent molecule. This recipe combines the exact free energy of the non-interacting system with fundamental measure theory for the repulsive contribution and a weighted density functional for the short-ranged attractive interactions. We add to these ingredients a weighted polarization functional for the long-range correlations in both the rotational and molecular-polarizability contributions to the dielectric response. We also perform molecular dynamics calculations for the free energy of cavity formation and the high-field dielectric response, and show that our free-energy functional adequately describes these properties (which are key for accurate solvation calculations) for all three solvents in our study: water, chloroform, and carbon tetrachloride. © 2014 AIP Publishing LLC.

Date Published

Journal

Journal of Chemical Physics

Volume

140

Issue

14

URL

https://www.scopus.com/inward/record.uri?eid=2-s2.0-84898929896&doi=10.1063%2f1.4870653&partnerID=40&md5=14861840334c18deb7e7068f21110a88

DOI

10.1063/1.4870653

Group (Lab)

Tomas Arias Group

Funding Source

OCI-1053575
DE-SC0001086
1053575

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