Molecular Density Functional Theory of Water.
Three-dimensional implementations of liquid-state theories offer an efficient alternative to computer simulations for the atomic-level description of aqueous solutions in complex environments. In this context, we present a (classical) molecular density functional theory (MDFT) of water that is derived from first principles and is based on two classical density fields, a scalar one, the particle density, and a vectorial one, the multipolar polarization density. Its implementation requires as input the partial charge distribution of a water molecule and three measurable bulk properties, namely, the structure factor and the k-dependent longitudinal and transverse dielectric constants. It has to be complemented by a solute-solvent three-body term that reinforces tetrahedral order at short-range. The approach is shown to provide the correct 3-D microscopic solvation profile around various molecular solutes, possibly possessing H-bonding sites, at a computer cost two to three orders of magnitude lower than with explicit simulations.
†Pôle de Physico-Chimie Théorique, École Normale Supérieure, UMR 8640 CNRS-ENS-UPMC, 24, rue Lhomond, 75005 Paris, France.
Guillaume
G
Jeanmairet
†Pôle de Physico-Chimie Théorique, École Normale Supérieure, UMR 8640 CNRS-ENS-UPMC, 24, rue Lhomond, 75005 Paris, France.|‡Université Pierre et Marie Curie, UMR 7195 PECSA, CNRS-UPMC-ESPCI, 75005 Paris, France.
Maximilien
M
Levesque
†Pôle de Physico-Chimie Théorique, École Normale Supérieure, UMR 8640 CNRS-ENS-UPMC, 24, rue Lhomond, 75005 Paris, France.
Rodolphe
R
Vuilleumier
†Pôle de Physico-Chimie Théorique, École Normale Supérieure, UMR 8640 CNRS-ENS-UPMC, 24, rue Lhomond, 75005 Paris, France.
Daniel
D
Borgis
classical density functional theory; free-energy; implicit solvent method; molecular structure; solvation; water