Saddles in the energy landscape: extensivity and thermodynamic formalism

We formally extend the energy landscape approach for the thermodynamics of liquids to account for saddle points. By considering the extensive nature of macroscopic potential energies, we derive the scaling behavior of saddles with system size, as well as several approximations for the properties of low-order saddles (i.e., those with only a few unstable directions). We then cast the canonical partition function in a saddle-explicit form and develop, for the first time, a rigorous energy landscape approach capable of reproducing trends observed in simulations, in particular the temperature dependence of the energy and fractional order of sampled saddles.Comment: 4 pages, 1 figur

Scaled Particle Theory for Hard Sphere Pairs. I. Mathematical Structure

We develop an extension of the original Reiss-Frisch-Lebowitz scaled particle theory that can serve as a predictive method for the hard sphere pair correlation function g(r). The reversible cavity creation work is analyzed both for a single spherical cavity of arbitrary size, as well as for a pair of identical such spherical cavities with variable center-to-center separation. These quantities lead directly to prediction of g(r). Smooth connection conditions have been identified between the small-cavity situation where the work can be exactly and completely expressed in terms of g(r), and the large-cavity regime where macroscopic properties become relevant. Closure conditions emerge which produce a nonlinear integral equation that must be satisfied by the pair correlation function. This integral equation has a structure which straightforwardly generates a solution that is a power series in density. The results of this series replicate the exact second and third virial coefficients for the hard sphere system via the contact value of the pair correlation function. The predicted fourth virial coefficient is approximately 0.6 percent lower than the known exact value. Detailed numerical analysis of the nonlinear integral equation has been deferred to the sequel (following paper

Phase diagram of a polydisperse soft-spheres model for liquids and colloids

The phase diagram of soft spheres with size dispersion has been studied by means of an optimized Monte Carlo algorithm which allows to equilibrate below the kinetic glass transition for all sizes distribution. The system ubiquitously undergoes a first order freezing transition. While for small size dispersion the frozen phase has a crystalline structure, large density inhomogeneities appear in the highly disperse systems. Studying the interplay between the equilibrium phase diagram and the kinetic glass transition, we argue that the experimentally found terminal polydispersity of colloids is a purely kinetic phenomenon.Comment: Version to be published in Physical Review Letter

Mpemba effect and phase transitions in the adiabatic cooling of water before freezing

An accurate experimental investigation on the Mpemba effect (that is, the freezing of initially hot water before cold one) is carried out, showing that in the adiabatic cooling of water a relevant role is played by supercooling as well as by phase transitions taking place at 6 +/- 1 oC, 3.5 +/- 0.5 oC and 1.3 +/- 0.6 oC, respectively. The last transition, occurring with a non negligible probability of 0.21, has not been detected earlier. Supported by the experimental results achieved, a thorough theoretical analysis of supercooling and such phase transitions, which are interpreted in terms of different ordering of clusters of molecules in water, is given.Comment: revtex, 4 pages, 2 figure

Test of classical nucleation theory on deeply supercooled high-pressure simulated silica

We test classical nucleation theory (CNT) in the case of simulations of deeply supercooled, high density liquid silica, as modelled by the BKS potential. We find that at density $\rho=4.38$~g/cm$^3$, spontaneous nucleation of crystalline stishovite occurs in conventional molecular dynamics simulations at temperature T=3000 K, and we evaluate the nucleation rate J directly at this T via "brute force" sampling of nucleation events. We then use parallel, constrained Monte Carlo simulations to evaluate $\Delta G(n)$, the free energy to form a crystalline embryo containing n silicon atoms, at T=3000, 3100, 3200 and 3300 K. We find that the prediction of CNT for the n-dependence of $\Delta G(n)$ fits reasonably well to the data at all T studied, and at 3300 K yields a chemical potential difference between liquid and stishovite that matches independent calculation. We find that $n^*$, the size of the critical nucleus, is approximately 10 silicon atoms at T=3300 K. At 3000 K, $n^*$ decreases to approximately 3, and at such small sizes methodological challenges arise in the evaluation of $\Delta G(n)$ when using standard techniques; indeed even the thermodynamic stability of the supercooled liquid comes into question under these conditions. We therefore present a modified approach that permits an estimation of $\Delta G(n)$ at 3000 K. Finally, we directly evaluate at T=3000 K the kinetic prefactors in the CNT expression for J, and find physically reasonable values; e.g. the diffusion length that Si atoms must travel in order to move from the liquid to the crystal embryo is approximately 0.2 nm. We are thereby able to compare the results for J at 3000 K obtained both directly and based on CNT, and find that they agree within an order of magnitude.Comment: corrected calculation, new figure, accepted in JC

Liquid-Liquid Phase Transitions for Soft-Core Attractive Potentials

Using event driven molecular dynamics simulations, we study a three dimensional one-component system of spherical particles interacting via a discontinuous potential combining a repulsive square soft core and an attractive square well. In the case of a narrow attractive well, it has been shown that this potential has two metastable gas-liquid critical points. Here we systematically investigate how the changes of the parameters of this potential affect the phase diagram of the system. We find a broad range of potential parameters for which the system has both a gas-liquid critical point and a liquid-liquid critical point. For the liquid-gas critical point we find that the derivatives of the critical temperature and pressure, with respect to the parameters of the potential, have the same signs: they are positive for increasing width of the attractive well and negative for increasing width and repulsive energy of the soft core. This result resembles the behavior of the liquid-gas critical point for standard liquids. In contrast, for the liquid-liquid critical point the critical pressure decreases as the critical temperature increases. As a consequence, the liquid-liquid critical point exists at positive pressures only in a finite range of parameters. We present a modified van der Waals equation which qualitatively reproduces the behavior of both critical points within some range of parameters, and give us insight on the mechanisms ruling the dependence of the two critical points on the potential's parameters. The soft core potential studied here resembles model potentials used for colloids, proteins, and potentials that have been related to liquid metals, raising an interesting possibility that a liquid-liquid phase transition may be present in some systems where it has not yet been observed.Comment: 29 pages, 15 figure

Heterogeneous nucleation near a metastable vapour-liquid transition: the effect of wetting transitions

Phase transformations such as freezing typically start with heterogeneous nucleation. Heterogeneous nucleation near a wetting transition, of a crystalline phase is studied. The wetting transition occurs at or near a vapour-liquid transition which occurs in a metastable fluid. The fluid is metastable with respect to crystallisation, and it is the crystallisation of this fluid phase that we are interested in. At a wetting transition a thick layer of a liquid phase forms at a surface in contact with the vapour phase. The crystalline nucleus is then immersed in this liquid layer, which reduces the free energy barrier to nucleation and so dramatically increases the nucleation rate. The variation in the rate of heterogeneous nucleation close to wetting transitions is calculated for systems in which the longest-range forces are dispersion forces.Comment: 11 pages including 3 figure

Mode Coupling relaxation scenario in a confined glass former

Molecular dynamics simulations of a Lennard-Jones binary mixture confined in a disordered array of soft spheres are presented. The single particle dynamical behavior of the glass former is examined upon supercooling. Predictions of mode coupling theory are satisfied by the confined liquid. Estimates of the crossover temperature are obtained by power law fit to the diffusion coefficients and relaxation times of the late $\alpha$ region. The $b$ exponent of the von Schweidler law is also evaluated. Similarly to the bulk, different values of the exponent $\gamma$ are extracted from the power law fit to the diffusion coefficients and relaxation times.Comment: 5 pages, 4 figures, changes in the text, accepted for publication on Europhysics Letter

Gaussian excitations model for glass-former dynamics and thermodynamics

We describe a model for the thermodynamics and dynamics of glass-forming liquids in terms of excitations from an ideal glass state to a Gaussian manifold of configurationally excited states. The quantitative fit of this three parameter model to the experimental data on excess entropy and heat capacity shows that ``fragile'' behavior, indicated by a sharply rising excess heat capacity as the glass transition is approached from above, occurs in anticipation of a first-order transition -- usually hidden below the glass transition -- to a ``strong'' liquid state of low excess entropy. The dynamic model relates relaxation to a hierarchical sequence of excitation events each involving the probability of accumulating sufficient kinetic energy on a separate excitable unit. Super-Arrhenius behavior of the relaxation rates, and the known correlation of kinetic with thermodynamic fragility, both follow from the way the rugged landscape induces fluctuations in the partitioning of energy between vibrational and configurational manifolds. A relation is derived in which the configurational heat capacity, rather than the configurational entropy of the Adam Gibbs equation, controls the temperature dependence of the relaxation times, and this gives a comparable account of the experimental observations.Comment: 21 pp., 17 fig