Local Structural Heterogeneities in Liquid Water under Pressure

We investigate the local structural heterogeneities that may appear in liquid water by studying a model of interacting water pentamers. We find local energy minima which we identify with well-defined configurations, and advance the hypothesis that one of these configurations may be related to local ''high-density'' structural heterogeneities occurring in liquid water when subjected to high pressure. Our results are consistent with experimental data on the effect of high pressure on the radial distribution function, and are further tested by molecular dynamics simulations reported here. q 1998 Published by Elsevier Science B.V. All rights reserved. Walrafen pointed out that a wide range of experi- mental data are consistent with the possibility that each water molecule typically has four hydrogen bonds - giving rise to a pronounced peak in the oxygen-oxygen radial distribution function at about ˚

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

[2]  Statistical geometry of simple liquids in two dimensions. , 1990, Physical review. A, Atomic, molecular, and optical physics.

[3]  N. Ohtomo,et al.  The structure of liquid water by neutron scattering. II. Temperature dependence of the liquid structure. , 1981 .

[4]  N. Clark,et al.  Melting and Liquid Structure in two Dimensions , 2007 .

[5]  M. Bellissent-Funel,et al.  A structural study of deeply supercooled water , 1989 .

[6]  Yu. E. Gorbaty,et al.  X‐ray scattering in liquid water at pressures of up to 7.7 kbar: Test of a fluctuation model , 1994 .

[7]  F. Stillinger,et al.  Molecular dynamics study of liquid water under high compression , 1974 .

[8]  G. Walrafen,et al.  Raman Spectral Studies of Water Structure , 1964 .

[9]  I. R. Mcdonald,et al.  Molecular dynamics studies of the structure of water at high temperatures and density , 1981 .

[10]  Othmar Steinhauser,et al.  Reaction field simulation of water , 1982 .

[11]  M. Klein,et al.  The effects of pressure on structural and dynamical properties of associated liquids: Molecular dynamics calculations for the extended simple point charge model of water , 1997 .

[12]  J. Madura,et al.  Water under high pressure , 1988 .

[13]  F. Stillinger,et al.  Improved simulation of liquid water by molecular dynamics , 1974 .

[14]  P. Clancy,et al.  EXISTENCE OF A DENSITY MAXIMUM IN EXTENDED SIMPLE POINT CHARGE WATER , 1994 .

[15]  Masaki Sasai,et al.  Molecular scale precursor of the liquid–liquid phase transition of water , 1998 .

[16]  G. Walrafen,et al.  Temperature Dependence of the Raman OH-Stretching Overtone from Liquid Water. , 1984 .

[17]  Karmakar,et al.  Molecular clusters and correlations in water by x-ray and neutron diffraction. , 1993, Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics.

[18]  M. Bellissent-Funel,et al.  A neutron scattering study of liquid D2O under pressure and at various temperatures , 1995 .

[19]  Thomas A. Weber,et al.  Hidden structure in liquids , 1982 .

[20]  G. Walrafen,et al.  Temperature dependence of the low‐ and high‐frequency Raman scattering from liquid water , 1986 .

[21]  G. Walrafen,et al.  Raman Spectral Studies of the Effects of Temperature on Water Structure , 1967 .

[22]  Katherine J. Strandburg,et al.  Two-dimensional melting , 1988 .

[23]  Masaki Sasai,et al.  Growth and collapse of structural patterns in the hydrogen bond network in liquid water , 1996 .

[24]  W.-H. Yang,et al.  Raman isosbestic points from liquid water , 1986 .

[25]  William H. Press,et al.  Numerical recipes , 1990 .

[26]  Elmar Lang,et al.  Anomalies of Liquid Water , 1982 .