title: Octanol-Water Partition Coefficient from 3D-RISM-KH Molecular Theory of Solvation with Partial Molar Volume Correction.
abstract: The octanol-water partition coefficient is an important physical-chemical characteristic widely used to describe hydrophobic/hydrophilic properties of chemical compounds. The partition coefficient is related to the transfer free energy of a compound from water to octanol. Here, we introduce a new protocol for prediction of the partition coefficient based on the statistical-mechanical, 3D-RISM-KH molecular theory of solvation. It was shown recently that with the compound-solvent correlation functions obtained from the 3D-RISM-KH molecular theory of solvation, the free energy functional supplemented with the correction linearly related to the partial molar volume obtained from the Kirkwood-Buff/3D-RISM theory, also called the "universal correction" (UC), provides accurate prediction of the hydration free energy of small compounds, compared to explicit solvent molecular dynamics [ Palmer , D. S. ; J. Phys.: Condens. Matter 2010 , 22 , 492101 ]. Here we report that with the UC reparametrized accordingly this theory also provides an excellent agreement with the experimental data for the solvation free energy in nonpolar solvent (1-octanol) and so accurately predicts the octanol-water partition coefficient. The performance of the Kovalenko-Hirata (KH) and Gaussian fluctuation (GF) functionals of the solvation free energy, with and without UC, is tested on a large library of small compounds with diverse functional groups. The best agreement with the experimental data for octanol-water partition coefficients is obtained with the KH-UC solvation free energy functional.
authors.affiliation: †Department of Mechanical Engineering, University of Alberta, Edmonton, Alberta Canada.|‡National Institute for Nanotechnology, National Research Council of Canada, Edmonton, Alberta Canada.
authors.forename: WenJuan
authors.initials: W
authors.lastname: Huang
authors.affiliation: †Department of Mechanical Engineering, University of Alberta, Edmonton, Alberta Canada.|‡National Institute for Nanotechnology, National Research Council of Canada, Edmonton, Alberta Canada.
authors.forename: Nikolay
authors.initials: N
authors.lastname: Blinov
authors.affiliation: †Department of Mechanical Engineering, University of Alberta, Edmonton, Alberta Canada.|‡National Institute for Nanotechnology, National Research Council of Canada, Edmonton, Alberta Canada.
authors.forename: Andriy
authors.initials: A
authors.lastname: Kovalenko