http://static.sif.it/SIF/resources/public/files/va2012/likos_0710.pdf

Effective interactions in soft condensed matter physics

The anomalous properties of cold and supercooled water, such as the fact that at sufficiently low temperatures it becomes more compressible and less dense when cooled, and more fluid when compressed, have attracted the attention of physical scientists for a long time. The discovery in the 1970s that several thermodynamic and transport properties of supercooled water exhibit a pronounced temperature dependence and appear to diverge slightly below the homogeneous nucleation temperature inspired a large number of experimental and theoretical studies. Likewise, an important body of work on glassy water has been stimulated by experiments, starting in the mid-1980s and continuing to this date, which suggest that vitreous water can exist in at least two apparently distinct forms. A coherent theory of the thermodynamic and transport properties of supercooled and glassy water does not yet exist. Nevertheless, significant progress towards this goal has been made during the past 20 years. This article summarizes the known experimental facts and reviews critically theoretical and computational work aimed at interpreting the observations and providing a unified viewpoint on cold, non-crystalline, metastable states of water.

https://iopscience.iop.org/article/10.1088/0953-8984/15/45/R01/pdf

Supercooled and glassy water

Density functional theory methods for characterization of porous materials

Quenched solid density functional theory and pore size analysis of micro-mesoporous carbons

Water is the most abundant liquid on earth and also the substance with the largest number of anomalies in its properties. It is a prerequisite for life and as such a most important subject of current research in chemical physics and physical chemistry. In spite of its simplicity as a liquid, it has an enormously rich phase diagram where different types of ices, amorphous phases, and anomalies disclose a path that points to unique thermodynamics of its supercooled liquid state that still hides many unraveled secrets. In this review we describe the behavior of water in the regime from ambient conditions to the deeply supercooled region. The review describes simulations and experiments on this anomalous liquid. Several scenarios have been proposed to explain the anomalous properties that become strongly enhanced in the supercooled region. Among those, the second critical-point scenario has been investigated extensively, and at present most experimental evidence point to this scenario. Starting from very low ...

/pdf/water-a-tale-of-two-liquids-hxorql1ud9.pdf

Water: A Tale of Two Liquids

A semi-empirical `universal' corresponding-states relationship, for the dimensionless transport coefficients of dense fluids as functions of the reduced configurational entropy, was proposed more than twenty years ago and established by many simulations. Here it is shown analytically, by appealing to Enskog's original results for the inverse-power potentials, that the quasi-universal entropy scaling can be extended also to dilute gases. The analytic form and the possible origin for the entropy scaling for dense fluids are discussed in view of this unexpected result. On the basis of the entropy scaling we predict a minimum in the shear viscosity as a function of temperature for all soft inverse-power potentials, in quantitative agreement with the available simulations.

https://iopscience.iop.org/article/10.1088/0953-8984/11/28/303/pdf

A quasi-universal scaling law for atomic transport in simple fluids

A geometrically based fundamental-measure free-energy density functional unified the scaled-particle and Percus-Yevick theories for the hard-sphere fluid mixture. It has been successfully applied to the description of simple ~‘‘atomic’’ ! three-dimensional ~3D! fluids in the bulk and in slitlike pores, and has been extended to molecular fluids. However, this functional was unsuitable for fluids in narrow cylindrical pores, and was inadequate for describing the solid. In this work we analyze the reason for these deficiencies, and show that, in fact, the fundamental-measure geometrically based theory provides a free-energy functional for 3D hard spheres with the correct properties of dimensional crossover and freezing. After a simple modification of the functional, as we propose, it retains all the favorable D53 properties of the original functional, yet gives reliable results even for situations of extreme confinements that reduce the effective dimensionality D drastically. The modified functional is accurate for hard spheres between narrow plates (D52), and inside narrow cylindrical pores ( D51), and it gives the exact excess free energy in the D50 limit ~a cavity that cannot hold more than one particle!. It predicts the ~vanishingly small! vacancy concentration of the solid, provides the fcc hard-sphere solid equation of state from closest packing to melting, and predicts the hard-sphere fluid-solid transition, all in excellent agreement with the simulations. @S1063-651X~97!07404-7#

/pdf/fundamental-measure-free-energy-density-functional-for-hard-1k84xsulto.pdf

Fundamental-measure free-energy density functional for hard spheres: Dimensional crossover and freezing

On the basis of the fundamental-measure free energy functional for hard spheres and thermodynamic perturbation theory, a unified analytical description of classical bulk solids and fluids is obtained, predicting correctly the major features of their equations of state and freezing parameters as obtained by simulations. The fundamentally different fluid and solid asymptotic high density expansions for the potential energy, featuring a static-lattice Madelung term and the harmonic 3/2k B T correction, on one hand, and a fluid Madelung energy with a ˜T 3/5 thermal energy correction, on the other, both originate from the same singularity in the hard sphere free energy functional.

Density functional theory and the asymptotic high density expansion of the free energy of classical solids and fluids

By capturing the correct geometrical features, the fundamental-measure free-energy density functional [Y. Rosenfeld, Phys. Rev. Lett. 63, 980 (1989); J. Chem. Phys. 98, 8126 (1993)] leads to an accurate description of the general inhomogeneous simple (``atomic'') fluid. It is based on the convolution decomposition of the excluded volume for a pair of spheres in terms of characteristic functions for the geometry of the individual spheres. By relating that convolution decomposition for spheres with the Gauss-Bonnet theorem for general convex bodies, the fundamental-measure functional is made applicable to fluids of asymmetric molecules.

Density functional theory of molecular fluids: Free-energy model for the inhomogeneous hard-body fluid.

A modified geometrically based free-energy functional for hard spheres is proposed which gives reliable results even for situations of extreme confinements that reduce the effective dimensionality D. It is accurate for hard spheres between narrow plates .D D 2/, inside narrow cylindrical pores .D D 1/, and is exact in the 0D limit (a cavity that cannot hold more than one particle). This functional also predicts the hard-sphere fluid-solid transition in excellent agreement with the simulations.

/pdf/dimensional-crossover-and-the-freezing-transition-in-density-35f2n1eid2.pdf

Yaakov Rosenfeld

Papers

A quasi-universal scaling law for atomic transport in simple fluids

Fundamental-measure free-energy density functional for hard spheres: Dimensional crossover and freezing

Density functional theory and the asymptotic high density expansion of the free energy of classical solids and fluids

Density functional theory of molecular fluids: Free-energy model for the inhomogeneous hard-body fluid.

Dimensional crossover and the freezing transition in density functional theory