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Title: Molecular density functional theory for water with liquid-gas coexistence and correct pressure

The solvation of hydrophobic solutes in water is special because liquid and gas are almost at coexistence. In the common hypernetted chain approximation to integral equations, or equivalently in the homogenous reference fluid of molecular density functional theory, coexistence is not taken into account. Hydration structures and energies of nanometer-scale hydrophobic solutes are thus incorrect. In this article, we propose a bridge functional that corrects this thermodynamic inconsistency by introducing a metastable gas phase for the homogeneous solvent. We show how this can be done by a third order expansion of the functional around the bulk liquid density that imposes the right pressure and the correct second order derivatives. Although this theory is not limited to water, we apply it to study hydrophobic solvation in water at room temperature and pressure and compare the results to all-atom simulations. The solvation free energy of small molecular solutes like n-alkanes and hard sphere solutes whose radii range from angstroms to nanometers is now in quantitative agreement with reference all atom simulations. The macroscopic liquid-gas surface tension predicted by the theory is comparable to experiments. This theory gives an alternative to the empirical hard sphere bridge correction used so far by several authors.
Authors:
;  [1] ;  [2] ;  [1] ;  [3]
  1. École Normale Supérieure - PSL Research University, Département de Chimie, Sorbonne Universités - UPMC Univ. Paris 06, CNRS UMR 8640 PASTEUR, 24 rue Lhomond, 75005 Paris (France)
  2. SIS2M, LIONS, CEA, Saclay (France)
  3. (France)
Publication Date:
OSTI Identifier:
22415663
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 15; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ALKANES; APPROXIMATIONS; ATOMS; COMPARATIVE EVALUATIONS; COMPUTERIZED SIMULATION; DENSITY; DENSITY FUNCTIONAL METHOD; FREE ENERGY; HYDRATION; INTEGRAL EQUATIONS; LIQUIDS; SOLUTES; SOLVENTS; TEMPERATURE RANGE 0273-0400 K; WATER