How the liquid-liquid transition affects hydrophobic hydration in deeply supercooled water.

We determine the phase diagram of liquid supercooled water by extensive computer simulations using the TIP5P-E model. We find that the transformation of water into a low density liquid in the supercooled range strongly enhances the solubility of hydrophobic particles. The transformation of water into a tetrahedrally structured liquid is accompanied by a minimum in the hydration entropy and enthalpy. The corresponding change in sign of the solvation heat capacity indicates a loss of one characteristic signature of hydrophobic hydration. The observed behavior is found to be qualitatively in accordance with the predictions of the information theory model of Garde et al.

[1]  G. Pollack,et al.  Pressure dependence of the solubility of nitrogen, argon, krypton, and xenon in water , 1990 .

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

[3]  O. Mishima The glass-to-liquid transition of the emulsified high-density amorphous ice made by pressure-induced amorphization. , 2004, The Journal of chemical physics.

[4]  Berend Smit,et al.  Understanding Molecular Simulation , 2001 .

[5]  Heat capacity effects associated with the hydrophobic hydration and interaction of simple solutes: a detailed structural and energetical analysis based on molecular dynamics simulations. , 2004, The Journal of chemical physics.

[6]  Mishima,et al.  Liquid-liquid critical point in heavy water , 2000, Physical review letters.

[7]  Alfons Geiger,et al.  Multiple liquid–liquid transitions in supercooled water , 2003 .

[8]  R. Souda Hydrophobic hydration of alkanes: its implication for the property of amorphous solid water. , 2004, The Journal of chemical physics.

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

[10]  M. Bellissent-Funel,et al.  Structure of high‐density amorphous water. II. Neutron scattering study , 1987 .

[11]  Pablo G. Debenedetti,et al.  Supercooled and glassy water , 2003 .

[12]  J L Finney,et al.  Structures of high and low density amorphous ice by neutron diffraction. , 2002, Physical review letters.

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

[14]  Erwin Mayer,et al.  A second distinct structural “state” of high-density amorphous ice at 77 K and 1 bar , 2001 .

[15]  A. Garcia,et al.  Reversible temperature and pressure denaturation of a protein fragment: a replica exchange molecular dynamics simulation study. , 2004, Physical review letters.

[16]  K. Dill,et al.  The Strength of Hydrogen Bonds in Liquid Water and Around Nonpolar Solutes , 2000 .

[17]  H Eugene Stanley,et al.  Interplay between time-temperature transformation and the liquid-liquid phase transition in water. , 2002, Physical review letters.

[18]  H. Stanley,et al.  The relationship between liquid, supercooled and glassy water , 1998, Nature.

[19]  K. Dill,et al.  A View of the Hydrophobic Effect , 2002 .

[20]  H. Eugene Stanley,et al.  Phase behaviour of metastable water , 1992, Nature.

[21]  L. Pratt Molecular theory of hydrophobic effects: "She is too mean to have her name repeated.". , 2001, Annual review of physical chemistry.

[22]  R. Crovetto,et al.  Evaluation of Data on Solubility of Simple Apolar Gases in Light and Heavy Water at High Temperature , 1989 .

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

[24]  E. Whalley,et al.  ‘Melting ice’ I at 77 K and 10 kbar: a new method of making amorphous solids , 1984, Nature.

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

[26]  Hideki Tanaka,et al.  A self-consistent phase diagram for supercooled water , 1996, Nature.

[27]  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.

[28]  T. Darden,et al.  A smooth particle mesh Ewald method , 1995 .

[29]  A. Geiger,et al.  Simulation Study on the Diffusive Motion in Deeply Supercooled Water , 1999 .