title: Solvation free-energy pressure corrections in the three dimensional reference interaction site model.
abstract: Solvation free energies are efficiently predicted by molecular density functional theory if one corrects the overpressure introduced by the usual homogeneous reference fluid approximation. Sergiievskyi et al. [J. Phys. Chem. Lett. 5, 1935-1942 (2014)] recently derived the rigorous compensation of this excess of pressure (referred as "pressure correction" or PC) and proposed an empirical "ideal gas" supplementary correction (referred as "advanced pressure correction" or PC+) that further enhances the calculated solvation free energies. In a recent paper [M. Misin, M. V. Fedorov, and D. S. Palmer, J. Chem. Phys. 142, 091105 (2015)], those corrections were applied to solvation free energy calculations using the three-dimensional reference interaction site model (3D-RISM). As for classical DFT, PC and PC+ improve greatly the predictions of 3D-RISM, but PC+ is described as decreasing the accuracy. In this article, we derive rigorously the expression of the pressure in 3D-RISM as well as the associated PC and PC+. This provides a consistent way to correct the solvation free-energies calculated by 3D-RISM method.
authors.affiliation: University Duisburg-Essen, Universitätsstraße 5, 45117 Essen, Germany.
authors.forename: Volodymyr
authors.initials: V
authors.lastname: Sergiievskyi
authors.affiliation: Max Planck Institute for Solid State Research, Heisenbergstraße 1, Stuttgart 70569, Germany.
authors.forename: Guillaume
authors.initials: G
authors.lastname: Jeanmairet
authors.affiliation: École Normale Supérieure, PSL Research University, Département de Chimie, Sorbonne Universités - UPMC Université Paris 06, CNRS UMR 8640 PASTEUR, 24 rue Lhomond, 75005 Paris, France.
authors.forename: Maximilien
authors.initials: M
authors.lastname: Levesque
authors.affiliation: École Normale Supérieure, PSL Research University, Département de Chimie, Sorbonne Universités - UPMC Université Paris 06, CNRS UMR 8640 PASTEUR, 24 rue Lhomond, 75005 Paris, France.
authors.forename: Daniel
authors.initials: D
authors.lastname: Borgis