Bridge functional for the molecular density functional theory with consistent pressure and surface tension and its importance for solvation in water

Cédric Gageat (1) , Luc Belloni (2) , Daniel Borgis (3, 4) , Maximilien Levesque (1)

1 PASTEUR - Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640)
2 LIONS - Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire
3 PASTEUR - Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640)
4 MDLS - Maison de la Simulation

We address the problem of predicting the solvation free energy and equilibrium solvent density profile in fews minutes from the molecular density functional theory beyond the usual hypernetted-chain approximation. We introduce a bridge functional of a coarse-grained, weighted solvent density. In few minutes at most, for solutes of sizes ranging from small compounds to large proteins, we produce (i) an estimation of the free energy of solvation within 1 kcal/mol of the experimental data for the hydrophobic solutes presented here, and (ii) the solvent distribution around the solute. Contrary to previous propositions, this bridge functional is thermodynamically consistent in that it produces the correct liquid-vapor coexistence and the experimental surface tension. We show this consistency to be of crucial importance for water at room temperature and pressure. This bridge functional is designed to be simple, local, and thus numerically efficient. Finally, we illustrate this new level of molecular theory of solutions with the study of the hydration shell of a protein.

Domaines: Chimie-Physique [physics.chem-ph]

Cédric Gageat, Luc Belloni, Daniel Borgis, Maximilien Levesque. Bridge functional for the molecular density functional theory with consistent pressure and surface tension and its importance for solvation in water. 2017. ⟨cea-01612950⟩