Simple Parameter-Free Bridge Functionals for Molecular Density Functional Theory. Application to Hydrophobic Solvation

摘要

Computer simulations have been fundamental in understanding the fine details of hydrophobic solvation and hydrophobic interactions. Alternative approaches based on liquid-state theories have been proposed, but are not yet at the same degree of completeness and accuracy. In this vein, a classical, molecular density functional theory approach to hydrophobic solvation is introduced. The lowest, second-order approximation of the theory, equivalent to the hypernetted chain approximation in integral equations, fails in describing correctly cavitation free-energies. It is corrected here by two simple, angular-independent, so-called bridge functionals; they are parameter-free in the sense that all variables can be fixed unambiguously from the water bulk properties, including pressure, isothermal compressibility, and liquid-gas surface tension. A hard-sphere bridge functional, based on the known functional of a reference hard fluid system, turns out to face strong limitations for water. A simpler weighted density approximation is shown to properly reproduce the solvation free energy of hydrophobes of various sizes, from microscopic ones to the nanoscale, and predicting the solvation free energy of a data set of more than 600 model hydrophobic molecules having a variety of shapes and sizes with an accuracy of a quarter of k(B)T compared to Monte Carlo simulations values. It constitutes an excellent starting point for a general functional describing accurately both hydrophobic and hydrophilic solvation, and making it possible to study nonidealized hydrophobic interactions.