A classical density-functional theory for describing water interfaces.

We develop a classical density functional for water which combines the White Bear fundamental-measure theory (FMT) functional for the hard sphere fluid with attractive interactions based on the statistical associating fluid theory variable range (SAFT-VR). This functional reproduces the properties of water at both long and short length scales over a wide range of temperatures and is computationally efficient, comparable to the cost of FMT itself. We demonstrate our functional by applying it to systems composed of two hard rods, four hard rods arranged in a square, and hard spheres in water.

[1]  Douglas J. Tobias,et al.  Does Nitric Acid Dissociate at the Aqueous Solution Surface , 2011 .

[2]  S. B. Kiselev,et al.  A new analytical formulation for the generalized corresponding states model for thermodynamic and surface properties in pure fluids , 2006 .

[3]  S. Yoo,et al.  On the phase diagram of water with density functional theory potentials: The melting temperature of ice I(h) with the Perdew-Burke-Ernzerhof and Becke-Lee-Yang-Parr functionals. , 2009, The Journal of chemical physics.

[4]  N. Mermin.  Thermal Properties of the Inhomogeneous Electron Gas , 1965 .

[5]  Erich A. Müller,et al.  Molecular-Based Equations of State for Associating Fluids: A Review of SAFT and Related Approaches , 2001 .

[6]  N. Ashcroft,et al.  Weighted-density-functional theory of inhomogeneous liquids and the freezing transition. , 1985, Physical review. A, General physics.

[7]  Francois Gygi,et al.  Towards an assessment of the accuracy of density functional theory for first principles simulations of water. II. , 2004, The Journal of chemical physics.

[8]  M. Wertheim,et al.  Fluids with highly directional attractive forces. III. Multiple attraction sites , 1986 .

[9]  G. Jackson,et al.  A SAFT-DFT approach for the vapour-liquid interface of associating fluids , 2002 .

[10]  Petros Koumoutsakos,et al.  Hydrophobic hydration of C60 and carbon nanotubes in water , 2004 .

[11]  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.

[12]  Hartmut Löwen,et al.  Fundamental-measure free-energy density functional for hard spheres: Dimensional crossover and freezing , 1997 .

[13]  Barry Honig,et al.  Reevaluation of the Born model of ion hydration , 1985 .

[14]  C. Gray,et al.  Density-functional theory of the water liquid-vapour interface , 1992 .

[15]  C. Vega,et al.  Surface tension of the most popular models of water by using the test-area simulation method. , 2007, The Journal of chemical physics.

[16]  Tarazona.  Density functional for hard sphere crystals: A fundamental measure approach , 2000, Physical review letters.

[17]  S. Yoo,et al.  Communication: The effect of dispersion corrections on the melting temperature of liquid water. , 2011, The Journal of chemical physics.

[18]  G. Jackson,et al.  An accurate density functional theory for the vapor-liquid interface of associating chain molecules based on the statistical associating fluid theory for potentials of variable range. , 2004, The Journal of chemical physics.

[19]  Walter G Chapman,et al.  A comparison of density functional and integral equation theories vs Monte Carlo simulations for hard sphere associating fluids near a hard wall , 1998 .

[20]  J. Barker,et al.  What is "liquid"? Understanding the states of matter , 1976 .

[21]  K. Jaqaman,et al.  Classical density functional theory of orientational order at interfaces: application to water. , 2004, The Journal of chemical physics.

[22]  Walter G Chapman,et al.  Associating fluids with four bonding sites against a hard wall: density functional theory , 1997 .

[23]  Y. Rosenfeld,et al.  Free energy model for inhomogeneous fluid mixtures: Yukawa‐charged hard spheres, general interactions, and plasmas , 1993 .

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

[25]  A. Seitsonen,et al.  Importance of van der Waals interactions in liquid water. , 2009, The journal of physical chemistry. B.

[26]  Hans-Peter Lenhof,et al.  Electrostatic potentials of proteins in water: a structured continuum approach , 2007, Bioinform..

[27]  Andrew J. Haslam,et al.  Developing optimal Wertheim-like models of water for use in Statistical Associating Fluid Theory (SAFT) and related approaches , 2006 .

[28]  M. Head‐Gordon,et al.  Reaction field cavity optimization: A born-again Born model for ionic hydration , 1999 .

[29]  Gerhard Kahl,et al.  Fundamental measure theory for hard-sphere mixtures revisited: the White Bear version , 2002 .

[30]  Roberto Car,et al.  Nuclear quantum effects in water. , 2008, Physical review letters.

[31]  M. Wertheim,et al.  Fluids with highly directional attractive forces. IV. Equilibrium polymerization , 1986 .

[32]  Y. Rosenfeld,et al.  From zero-dimension cavities to free-energy functionals for hard disks and hard spheres , 1997 .

[33]  H. Kahl,et al.  Modified PT-LJ-SAFT Density Functional Theory I. Prediction of surface properties and phase equilibria of non-associating fluids , 2008 .

[34]  A. Seitsonen,et al.  Van der Waals effects in ab initio water at ambient and supercritical conditions. , 2011, The Journal of chemical physics.

[35]  Kendra Letchworth-Weaver,et al.  A computationally efficacious free-energy functional for studies of inhomogeneous liquid water. , 2011, The Journal of chemical physics.

[36]  John Bentley,et al.  VOLUME POLARIZATION IN REACTION FIELD THEORY , 1998 .

[37]  Kenneth S. Pitzer,et al.  The Free Energy of Hydration of Gaseous Ions, and the Absolute Potential of the Normal Calomel Electrode , 1939 .

[38]  M. Wertheim,et al.  Fluids with highly directional attractive forces. II. Thermodynamic perturbation theory and integral equations , 1984 .

[39]  김삼묘,et al.  “Bioinformatics” 특집을 내면서 , 2000 .

[40]  Car,et al.  Unified approach for molecular dynamics and density-functional theory. , 1985, Physical review letters.

[41]  Eric W. Lemmon,et al.  Thermophysical Properties of Fluid Systems , 1998 .

[42]  C. Gray,et al.  Density-functional theory of the water liquid-vapour interface: II , 1994 .

[43]  G. Jackson,et al.  An examination of the vapour-liquid interface of associating fluids using a SAFT-DFT approach , 2001 .

[44]  D. Chandler,et al.  Scaling of Hydrophobic Solvation Free Energies , 2001 .

[45]  Jianzhong Wu,et al.  Structures of hard-sphere fluids from a modified fundamental-measure theory , 2002 .

[46]  P. Hohenberg,et al.  Inhomogeneous Electron Gas , 1964 .

[47]  Density-functional theory for the freezing of water. , 1987, Physical review letters.

[48]  George Jackson,et al.  Statistical associating fluid theory for chain molecules with attractive potentials of variable range , 1997 .

[49]  Journal of Chemical Physics , 1932, Nature.

[50]  T. Arias,et al.  Classical density-functional theory of inhomogeneous water including explicit molecular structure and nonlinear dielectric response. , 2009, The journal of physical chemistry. B.

[51]  M. Wertheim,et al.  Fluids with highly directional attractive forces. I. Statistical thermodynamics , 1984 .

[52]  D. Chandler,et al.  Hydrophobicity at Small and Large Length Scales , 1999 .

[53]  Jianzhong Wu,et al.  A fundamental-measure theory for inhomogeneous associating fluids , 2002 .

[54]  Jianzhong Wu,et al.  Vapor−Liquid Equilibria and Interfacial Tensions of Associating Fluids within a Density Functional Theory , 2005 .

[55]  G. N. Chuev,et al.  Hydration of hydrophobic solutes treated by the fundamental measure approach. , 2006, The journal of physical chemistry. B.

[56]  George Jackson,et al.  SAFT: Equation-of-state solution model for associating fluids , 1989 .

[57]  E. Ungureanu,et al.  Molecular Physics , 2008, Nature.

[58]  Rosenfeld,et al.  Free-energy model for the inhomogeneous hard-sphere fluid mixture and density-functional theory of freezing. , 1989, Physical review letters.

[59]  G. Jackson,et al.  Prediction of the Vapor−Liquid Interfacial Tension of Nonassociating and Associating Fluids with the SAFT-VR Density Functional Theory† , 2007 .

[60]  D. Stroud,et al.  Density-functional theory of simple classical fluids. I. Surfaces , 1976 .

[61]  R. Netz,et al.  Entropy and enthalpy convergence of hydrophobic solvation beyond the hard-sphere limit. , 2011, The Journal of chemical physics.

[62]  Joachim Gross,et al.  A density functional theory for vapor-liquid interfaces using the PCP-SAFT equation of state. , 2009, The Journal of chemical physics.

[63]  R Blossey,et al.  Novel formulation of nonlocal electrostatics. , 2004, Physical review letters.