Solvation of complex surfaces via molecular density functional theory

Abstract

We show that classical molecular density functional theory (MDFT), here in the homogeneous reference fluid approximation in which the functional is inferred from the properties of the bulk solvent, is a powerful new tool to study, at a fully molecular level, the solvation of complex surfaces and interfaces by polar solvents. This implicit solvent method allows for the determination of structural, orientational and energetic solvation properties that are on a par with all-atom molecular simulations performed for the same system, while reducing the computer time by two orders of magnitude. This is illustrated by the study of an atomistically-resolved clay surface composed of over a thousand atoms wetted by a molecular dipolar solvent. The high numerical efficiency of the method is exploited to carry a systematic analysis of the electrostatic and non-electrostatic components of the surface-solvent interaction within the popular CLAYFF force field. Solvent energetics and structure are found to depend weakly upon the atomic charges distribution of the clay surface, even for a rather polar solvent. We conclude on the consequences of such findings for force-field development.

accepted by J. Chem. Phys., nov. 2012

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• Improved association in a classical density functional theory for water
• Pressure Correction for Solvation Theories
• Solvation in atomic liquids: connection between Gaussian field theory and density functional theory
• Molecular integral equations theory in the near critical region of CO2
• Continuum model of the simple dielectric fluid: Consistency between density based and continuum mechanics methods