title: A recipe for free-energy functionals of polarizable molecular fluids.
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.
authors.affiliation: Department of Physics, Cornell University, Ithaca, New York 14853, USA.
authors.forename: Ravishankar
authors.initials: R
authors.lastname: Sundararaman
authors.affiliation: Department of Physics, Cornell University, Ithaca, New York 14853, USA.
authors.forename: Kendra
authors.initials: K
authors.lastname: Letchworth-Weaver
authors.affiliation: Department of Physics, Cornell University, Ithaca, New York 14853, USA.
authors.forename: T A
authors.initials: TA
authors.lastname: Arias
mesh_terms: D002251:Carbon Tetrachloride / Q000737:chemistry*; D002725:Chloroform / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D011789:Quantum Theory; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
chemical_list: D014867:Water; D002725:Chloroform; D002251:Carbon Tetrachloride