Room temperature compressibility and diffusivity of liquid water from first principles.

The isothermal compressibility of water is essential to understand its anomalous properties. We compute it by ab initio molecular dynamics simulations of 200 molecules at five densities, using two different van der Waals density functionals. While both functionals predict compressibilities within ~30% of experiment, only one of them accurately reproduces, within the uncertainty of the simulation, the density dependence of the self-diffusion coefficient in the anomalous region. The discrepancies between the two functionals are explained in terms of the low- and high-density structures of the liquid.

[1]  D. Bowler,et al.  Chemical accuracy for the van der Waals density functional , 2009, Journal of physics. Condensed matter : an Institute of Physics journal.

[2]  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.

[3]  Stefan Goedecker,et al.  ABINIT: First-principles approach to material and nanosystem properties , 2009, Comput. Phys. Commun..

[4]  H. Eugene Stanley,et al.  Configurational entropy and diffusivity of supercooled water , 1999, Nature.

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

[6]  D. Sánchez-Portal,et al.  Numerical atomic orbitals for linear-scaling calculations , 2001, cond-mat/0104170.

[7]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[8]  Fabiano Corsetti,et al.  Optimal finite-range atomic basis sets for liquid water and ice , 2013, Journal of physics. Condensed matter : an Institute of Physics journal.

[9]  H. Stanley,et al.  Thermal conductivity minimum: a new water anomaly. , 2007, The journal of physical chemistry. B.

[10]  F. Gygi,et al.  A simplified implementation of van der Waals density functionals for first-principles molecular dynamics applications. , 2012, The Journal of chemical physics.

[11]  Bin Chen,et al.  Liquid Water from First Principles: Investigation of Different Sampling Approaches , 2004 .

[12]  J. Junquera,et al.  Systematic generation of finite-range atomic basis sets for linear-scaling calculations , 2002 .

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

[14]  C. Vega,et al.  Anomalies in water as obtained from computer simulations of the TIP4P/2005 model: density maxima, and density, isothermal compressibility and heat capacity minima , 2009, 0905.4009.

[15]  Troy Van Voorhis,et al.  Nonlocal van der Waals density functional: the simpler the better. , 2010, The Journal of chemical physics.

[16]  P. Gallo,et al.  A route to explain water anomalies from results on an aqueous solution of salt. , 2010, The Journal of chemical physics.

[17]  R. Mills,et al.  Self-diffusion in normal and heavy water in the range 1-45.deg. , 1973 .

[18]  A. Zunger,et al.  Self-interaction correction to density-functional approximations for many-electron systems , 1981 .

[19]  J. Skinner,et al.  Hydrogen bonding definitions and dynamics in liquid water. , 2007, The Journal of chemical physics.

[20]  Francesco Sciortino,et al.  Study of the ST2 model of water close to the liquid-liquid critical point. , 2011, Physical chemistry chemical physics : PCCP.

[21]  D. J. Wilbur,et al.  Self‐diffusion in compressed liquid heavy water , 1976 .

[22]  J. Soler,et al.  Efficient implementation of a van der Waals density functional: application to double-wall carbon nanotubes. , 2008, Physical review letters.

[23]  Peter H. Poole,et al.  Line of compressibility maxima in the phase diagram of supercooled water , 1997 .

[24]  Valeria Molinero,et al.  Structural transformation in supercooled water controls the crystallization rate of ice , 2011, Nature.

[25]  Bertrand Guillot,et al.  A reappraisal of what we have learnt during three decades of computer simulations on water , 2002 .

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

[27]  Network equilibration and first-principles liquid water. , 2004, The Journal of chemical physics.

[28]  Nicola Marzari,et al.  Static and dynamical properties of heavy water at ambient conditions from first-principles molecular dynamics. , 2005, The Journal of chemical physics.

[29]  C P Herrero,et al.  Anomalous nuclear quantum effects in ice. , 2011, Physical review letters.

[30]  Carlos Vega,et al.  Widom line and the liquid-liquid critical point for the TIP4P/2005 water model. , 2010, The Journal of chemical physics.

[31]  H. Ogasawara,et al.  Highly Compressed Two-Dimensional Form of Water at Ambient Conditions , 2013, Scientific Reports.

[32]  D. van der Spoel,et al.  GROMACS: A message-passing parallel molecular dynamics implementation , 1995 .

[33]  Kyuho Lee,et al.  Investigation of Exchange Energy Density Functional Accuracy for Interacting Molecules. , 2009, Journal of chemical theory and computation.

[34]  H. Stanley,et al.  Possible relation of water structural relaxation to water anomalies , 2013, Proceedings of the National Academy of Sciences.

[35]  Anders Nilsson,et al.  Benchmark oxygen-oxygen pair-distribution function of ambient water from x-ray diffraction measurements with a wide Q-range. , 2013, The Journal of chemical physics.

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

[37]  Stefano de Gironcoli,et al.  Nonlocal van der Waals density functional made simple and efficient , 2013 .

[38]  Kyuho Lee,et al.  Higher-accuracy van der Waals density functional , 2010, 1003.5255.

[39]  Yingkai Zhang,et al.  Comment on “Generalized Gradient Approximation Made Simple” , 1998 .

[40]  Martins,et al.  Efficient pseudopotentials for plane-wave calculations. , 1991, Physical review. B, Condensed matter.

[41]  H. Stanley,et al.  Translational and rotational diffusion in stretched water , 2002, cond-mat/0201138.

[42]  R. Car,et al.  Intermolecular dynamical charge fluctuations in water: a signature of the H-bond network. , 2005, Physical review letters.

[43]  G. Galli,et al.  Dispersion interactions and vibrational effects in ice as a function of pressure: a first principles study. , 2012, Physical review letters.

[44]  Emilio Artacho,et al.  Density, structure, and dynamics of water: the effect of van der Waals interactions. , 2010, The Journal of chemical physics.

[45]  M. Dion,et al.  van der Waals density functional for general geometries. , 2004, Physical review letters.

[46]  A. Seitsonen,et al.  Importance of van der Waals interactions in liquid water. , 2009, Journal of Physical Chemistry B.

[47]  Ricci,et al.  Structures of high-density and low-density water , 2000, Physical review letters.

[48]  A. Nilsson,et al.  The inhomogeneous structure of water at ambient conditions , 2009, Proceedings of the National Academy of Sciences.

[49]  J. Nørskov,et al.  Ab initio van der waals interactions in simulations of water alter structure from mainly tetrahedral to high-density-like. , 2011, The journal of physical chemistry. B.

[50]  F. Gygi,et al.  Structural and Vibrational Properties of Liquid Water from van der Waals Density Functionals. , 2011, Journal of chemical theory and computation.

[51]  Emilio Artacho,et al.  Electrons and hydrogen-bond connectivity in liquid water. , 2005, Physical review letters.

[52]  Pablo G. Debenedetti,et al.  Relationship between structural order and the anomalies of liquid water , 2001, Nature.

[53]  David T. Limmer,et al.  Phase diagram of supercooled water confined to hydrophilic nanopores. , 2012, The Journal of chemical physics.

[54]  Leonard Kleinman,et al.  Efficacious Form for Model Pseudopotentials , 1982 .

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

[56]  C. Vega,et al.  Note: Equation of state and compressibility of supercooled water: simulations and experiment. , 2011, The Journal of chemical physics.

[57]  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 .

[58]  Kurt Kremer,et al.  Molecular dynamics simulation of a polymer chain in solution , 1993 .

[59]  Matthias Krack,et al.  Static and Dynamical Properties of Liquid Water from First Principles by a Novel Car-Parrinello-like Approach. , 2009, Journal of chemical theory and computation.

[60]  Joost VandeVondele,et al.  Isobaric-isothermal molecular dynamics simulations utilizing density functional theory: an assessment of the structure and density of water at near-ambient conditions. , 2009, The journal of physical chemistry. B.

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

[62]  Spatially inhomogeneous bimodal inherent structure of simulated liquid water. , 2011, Physical chemistry chemical physics : PCCP.

[63]  D. Vanderbilt,et al.  First Principles Calculations of Surface Stress , 1988 .

[64]  D. Sánchez-Portal,et al.  The SIESTA method for ab initio order-N materials simulation , 2001, cond-mat/0111138.

[65]  Kazimierz Krynicki,et al.  Pressure and temperature dependence of self-diffusion in water , 1978 .