Assessing the thermodynamic signatures of hydrophobic hydration for several common water models.

Following the conclusions of an information theory analysis that hydrophobic hydration is dictated by the equation of state of liquid water, we perform simulations of ten different water models to examine the correlation between the fidelity of each model to the experimental density of liquid water and the accuracy of its description of methane hydration. We find that the three- and five-point water models provide an inferior description of both the liquid density and methane solubility compared to the four-point water models. Of the four-point water models, TIP4P/2005 provides the best description of both the aqueous equation-of-state and methane hydration thermodynamics. When the optimized potentials for liquid simulation united-atom description for methane is used, we find that while the entropy and heat capacity of methane hydration are in excellent agreement with experiment, the chemical potential and enthalpy are systematically shifted upwards. We subsequently reoptimize the methane interaction to accurately reproduce the experimental solubilities as a function of temperature by accounting for missing attractive interactions.

[1]  C. Vega,et al.  A potential model for the study of ices and amorphous water: TIP4P/Ice. , 2005, The Journal of chemical physics.

[2]  P. Rossky,et al.  Water-like solvation thermodynamics in a spherically symmetric solvent model with two characteristic lengths , 2007, Proceedings of the National Academy of Sciences.

[3]  William L. Jorgensen,et al.  Optimized intermolecular potential functions for liquid hydrocarbons , 1984 .

[4]  Gerhard Hummer,et al.  New perspectives on hydrophobic effects , 2000 .

[5]  C. Vega,et al.  A general purpose model for the condensed phases of water: TIP4P/2005. , 2005, The Journal of chemical physics.

[6]  Thomas M Truskett,et al.  A simple molecular thermodynamic theory of hydrophobic hydration , 2002, The Journal of Chemical Physics.

[7]  Henry S. Frank,et al.  Free Volume and Entropy in Condensed Systems III. Entropy in Binary Liquid Mixtures; Partial Molal Entropy in Dilute Solutions; Structure and Thermodynamics in Aqueous Electrolytes , 1945 .

[8]  J. Perram,et al.  Simulation of electrostatic systems in periodic boundary conditions. I. Lattice sums and dielectric constants , 1980, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.

[9]  Molecular Realism in Default Models for Information Theories of Hydrophobic Effects , 1999, physics/9901030.

[10]  C. Sorensen,et al.  Densities of supercooled H2O and D2O in 25 μ glass capillaries , 1986 .

[11]  T. Straatsma,et al.  THE MISSING TERM IN EFFECTIVE PAIR POTENTIALS , 1987 .

[12]  A. Soper,et al.  Decreased structure on dissolving methane in water , 2005 .

[13]  J L Finney,et al.  Molecular and mesoscale structures in hydrophobically driven aqueous solutions. , 2003, Biophysical chemistry.

[14]  Themis Lazaridis,et al.  Solvent Reorganization Energy and Entropy in Hydrophobic Hydration , 2000 .

[15]  Michael W. Mahoney,et al.  A five-site model for liquid water and the reproduction of the density anomaly by rigid, nonpolarizable potential functions , 2000 .

[16]  Dietmar Paschek.  Temperature dependence of the hydrophobic hydration and interaction of simple solutes: an examination of five popular water models. , 2004, The Journal of chemical physics.

[17]  G. Hummer,et al.  Hydrophobic Effects on a Molecular Scale , 1998, physics/9807001.

[18]  L. Pratt,et al.  The Potential Distribution Theorem and Models of Molecular Solutions , 2006 .

[19]  W. Wagner,et al.  The IAPWS Formulation 1995 for the Thermodynamic Properties of Ordinary Water Substance for General and Scientific Use , 2002 .

[20]  H. Scheraga,et al.  Monte Carlo calculations in the isothermal-isobaric ensemble. 2. Dilute aqueous solution of methane , 1977 .

[21]  Hydration of krypton and consideration of clathrate models of hydrophobic effects from the perspective of quasi-chemical theory. , 2002, Biophysical chemistry.

[22]  Dietmar Paschek.  How the liquid-liquid transition affects hydrophobic hydration in deeply supercooled water. , 2005, Physical review letters.

[23]  J. Madura,et al.  Solubility of simple, nonpolar compounds in TIP4P-Ew. , 2006, The Journal of chemical physics.

[24]  H. Berendsen,et al.  Interaction Models for Water in Relation to Protein Hydration , 1981 .

[25]  G. Hummer,et al.  Temperature dependence of the solubility of non-polar gases in water. , 1999, Biophysical chemistry.

[26]  On the re-engineered TIP4P water models for the prediction of vapor–liquid equilibrium , 2006 .

[27]  Martin Karplus,et al.  SOLVATION. A MOLECULAR DYNAMICS STUDY OF A DIPEPTIDE IN WATER. , 1979 .

[28]  Holger Gohlke,et al.  The Amber biomolecular simulation programs , 2005, J. Comput. Chem..

[29]  P. Ball.  Water as an active constituent in cell biology. , 2008, Chemical reviews.

[30]  J. Banavar,et al.  Computer Simulation of Liquids , 1988 .

[31]  J. Finney,et al.  Structural determination of the hydrophobic hydration shell of Kr , 1997 .

[32]  L. Pratt,et al.  Colloquium : Scaled particle theory and the length scales of hydrophobicity , 2006 .

[33]  Walter Kauzmann,et al.  Thermodynamics of unfolding , 1987, Nature.

[34]  D. Paschek.  How Does Solute-Polarization Affect the Hydrophobic Hydration of Methane? , 2009 .

[35]  H. Berendsen,et al.  Molecular dynamics with coupling to an external bath , 1984 .

[36]  J. Ilja Siepmann,et al.  Transferable Potentials for Phase Equilibria. 1. United-Atom Description of n-Alkanes , 1998 .

[37]  J. Finney,et al.  Hydrophobic hydration and the formation of a clathrate hydrate , 1998 .

[38]  García,et al.  Origin of Entropy Convergence in Hydrophobic Hydration and Protein Folding. , 1996, Physical review letters.

[39]  Jan B. F. N. Engberts,et al.  Hydrophobic Effects. Opinions and Facts , 1993 .

[40]  R. Battino,et al.  Low-pressure solubility of gases in liquid water , 1977 .

[41]  Michael E. Paulaitis,et al.  Monomer Hydrophobicity as a Mechanism for the LCST Behavior of Poly(ethylene oxide) in Water , 2006 .

[42]  Miguel Jorge,et al.  1-Octanol/Water Partition Coefficients of n-Alkanes from Molecular Simulations of Absolute Solvation Free Energies. , 2009, Journal of chemical theory and computation.

[43]  S. Rick.  A reoptimization of the five-site water potential (TIP5P) for use with Ewald sums. , 2004, The Journal of chemical physics.

[44]  Dor Ben-Amotz,et al.  Observation of water dangling OH bonds around dissolved nonpolar groups , 2009, Proceedings of the National Academy of Sciences.

[45]  Greg L. Hura,et al.  Development of an improved four-site water model for biomolecular simulations: TIP4P-Ew. , 2004, The Journal of chemical physics.

[46]  J. Hynes,et al.  Why water reorientation slows without iceberg formation around hydrophobic solutes. , 2009, The journal of physical chemistry. B.

[47]  W. L. Jorgensen,et al.  Comparison of simple potential functions for simulating liquid water , 1983 .

[48]  Shekhar Garde,et al.  Temperature dependence of hydrophobic hydration and entropy convergence in an isotropic model of water , 2001 .

[49]  P. Rossky,et al.  Solvent molecular dynamics in regions of hydrophobic hydration , 1986 .