Liquid Limits: The Glass Transition and Liquid-Gas Spinodal Boundaries of Metastable Liquids

The liquid-gas spinodal and the glass transition define ultimate boundaries beyond which substances cannot exist as (stable or metastable) liquids. The relation between these limits is analyzed {\it via} computer simulations of a model liquid. The results obtained indicate that the liquid - gas spinodal and the glass transition lines intersect at a finite temperature, implying a glass - gas mechanical instability locus at low temperatures. The glass transition lines obtained by thermodynamic and dynamic criteria agree very well with each other.Comment: 5 pages, 4 figures, to appear in Phys. Rev. Let

Stacking Entropy of Hard Sphere Crystals

Classical hard spheres crystallize at equilibrium at high enough density. Crystals made up of stackings of 2-dimensional hexagonal close-packed layers (e.g. fcc, hcp, etc.) differ in entropy by only about $10^{-3}k_B$ per sphere (all configurations are degenerate in energy). To readily resolve and study these small entropy differences, we have implemented two different multicanonical Monte Carlo algorithms that allow direct equilibration between crystals with different stacking sequences. Recent work had demonstrated that the fcc stacking has higher entropy than the hcp stacking. We have studied other stackings to demonstrate that the fcc stacking does indeed have the highest entropy of ALL possible stackings. The entropic interactions we could detect involve three, four and (although with less statistical certainty) five consecutive layers of spheres. These interlayer entropic interactions fall off in strength with increasing distance, as expected; this fall-off appears to be much slower near the melting density than at the maximum (close-packing) density. At maximum density the entropy difference between fcc and hcp stackings is $0.00115 +/- 0.00004 k_B$ per sphere, which is roughly 30% higher than the same quantity measured near the melting transition.Comment: 15 page

Freezing by Monte Carlo Phase-Switch

We describe a Monte Carlo procedure which allows sampling of the disjoint configuration spaces associated with crystalline and fluid phases, within a single simulation. The method utilises biased sampling techniques to enhance the probabilities of gateway states (in each phase) which are such that a global switch (to the other phase) can be implemented. Equilibrium freezing-point parameters can be determined directly; statistical uncertainties prescribed transparently; and finite-size effects quantified systematically. The method is potentially quite general; we apply it to the freezing of hard spheres.Comment: 5 pages, 2 figure

Potential Energy Landscape Equation of State

Depth, number, and shape of the basins of the potential energy landscape are the key ingredients of the inherent structure thermodynamic formalism introduced by Stillinger and Weber [F. H. Stillinger and T. A. Weber, Phys. Rev. A 25, 978 (1982)]. Within this formalism, an equation of state based only on the volume dependence of these landscape properties is derived. Vibrational and configurational contributions to pressure are sorted out in a transparent way. Predictions are successfully compared with data from extensive molecular dynamics simulations of a simple model for the fragile liquid orthoterphenyl.Comment: RevTeX4, 4 pages, 5 figure

Properties of a continuous-random-network model for amorphous systems

We use a Monte Carlo bond-switching method to study systematically the thermodynamic properties of a "continuous random network" model, the canonical model for such amorphous systems as a-Si and a-SiO$_2$. Simulations show first-order "melting" into an amorphous state, and clear evidence for a glass transition in the supercooled liquid. The random-network model is also extended to study heterogeneous structures, such as the interface between amorphous and crystalline Si.Comment: Revtex file with 4 figure

Lattice-switch Monte Carlo

We present a Monte Carlo method for the direct evaluation of the difference between the free energies of two crystal structures. The method is built on a lattice-switch transformation that maps a configuration of one structure onto a candidate configuration of the other by `switching' one set of lattice vectors for the other, while keeping the displacements with respect to the lattice sites constant. The sampling of the displacement configurations is biased, multicanonically, to favor paths leading to `gateway' arrangements for which the Monte Carlo switch to the candidate configuration will be accepted. The configurations of both structures can then be efficiently sampled in a single process, and the difference between their free energies evaluated from their measured probabilities. We explore and exploit the method in the context of extensive studies of systems of hard spheres. We show that the efficiency of the method is controlled by the extent to which the switch conserves correlated microstructure. We also show how, microscopically, the procedure works: the system finds gateway arrangements which fulfill the sampling bias intelligently. We establish, with high precision, the differences between the free energies of the two close packed structures (fcc and hcp) in both the constant density and the constant pressure ensembles.Comment: 34 pages, 9 figures, RevTeX. To appear in Phys. Rev.

Liquid-Solid Phase Transition of the System with Two particles in a Rectangular Box

We study the statistical properties of two hard spheres in a two dimensional rectangular box. In this system, the relation like Van der Waals equation loop is obtained between the width of the box and the pressure working on side walls. The auto-correlation function of each particle's position is calculated numerically. By this calculation near the critical width, the time at which the correlation become zero gets longer according to the increase of the height of the box. Moreover, fast and slow relaxation processes like $\alpha$ and $\beta$ relaxations observed in supper cooled liquid are observed when the height of the box is sufficiently large. These relaxation processes are discussed with the probability distribution of relative position of two particles.Comment: 6 figure

Potential energy landscape-based extended van der Waals equation

The inherent structures ({\it IS}) are the local minima of the potential energy surface or landscape, $U({\bf r})$, of an {\it N} atom system. Stillinger has given an exact {\it IS} formulation of thermodynamics. Here the implications for the equation of state are investigated. It is shown that the van der Waals ({\it vdW}) equation, with density-dependent $a$ and $b$ coefficients, holds on the high-temperature plateau of the averaged {\it IS} energy. However, an additional ``landscape'' contribution to the pressure is found at lower $T$. The resulting extended {\it vdW} equation, unlike the original, is capable of yielding a water-like density anomaly, flat isotherms in the coexistence region {\it vs} {\it vdW} loops, and several other desirable features. The plateau energy, the width of the distribution of {\it IS}, and the ``top of the landscape'' temperature are simulated over a broad reduced density range, $2.0 \ge \rho \ge 0.20$, in the Lennard-Jones fluid. Fits to the data yield an explicit equation of state, which is argued to be useful at high density; it nevertheless reproduces the known values of $a$ and $b$ at the critical point

Anomaly in the stability limit of liquid helium 3

We propose that the liquid-gas spinodal line of helium 3 reaches a minimum at 0.4 K. This feature is supported by our cavitation measurements. We also show that it is consistent with extrapolations of sound velocity measurements. Speedy [J. Phys. Chem. 86, 3002 (1982)] previously proposed this peculiar behavior for the spinodal of water and related it to a change in sign of the expansion coefficient alpha, i. e. a line of density maxima. Helium 3 exhibits such a line at positive pressure. We consider its extrapolation to negative pressure. Our discussion raises fundamental questions about the sign of alpha in a Fermi liquid along its spinodal.Comment: 5 pages, 3 figure

A case study evaluation of competitors undertaking an antarctic ultra-endurance event: nutrition, hydration and body composition variables

Background: The nutritional demands of ultra-endurance racing are well documented. However, the relationship between nutritional consumption and performance measures are less obvious for athletes competing in Polar conditions. Therefore, the aim of this study was to evaluate dietary intake, hydration status, body composition and performance times throughout an 800-km Antarctic race. Methods: The event organisers declared that 17 competitors would participate in the South Pole race. Of the 17 competitors, pre-race data were collected from 13 participants (12 males and 1 female (M±SD): age: 40.1±8.9 years; weight 83.9±10.3kg; and body fat percentage: 21.9±3.8%). Dietary recall, body composition and urinary osmolarity were assessed pre-race, midway checkpoint and end race. Data were compared on the basis of fast finishers (the Norwegian team (n=3) who won in a record of 14 day) and slower finishers (the remaining teams (n=10) reaching the South Pole between 22 and 28 days). Results: The percentage contribution of macronutrients to daily energy intake for all participants was as follows: carbohydrate (CHO) - 23.7% (221±82 g.day-1), fat = 60.6% (251±127g.day-1) and protein = 15.7% (117±52g.day-1). Energy demands were closer met by faster finishers compared to slower finishers (5,332±469 vs. 3,048±1,140kcal.day-1, p=0.02). Average reduction in body mass throughout the race was 8.3±5.5kg, with an average loss of lean mass of 2.0±4.1kg. There as a significant negative correlation between changes in lean mass and protein intake (p=0.03), and lean mass and energy intake (p=0.03). End-race urinary osmolarity was significantly elevated for faster finishers compared to slower finishers and control volunteers (faster finishers: 933±157mOsmol.L-1; slower finishers: 543±92mOsmol.L-1; control: 515±165mOsmol.L-1, p+0.04). Conclusions: Throughout the race, both groups were subjected to a negative change in energy balance which partly explained reduced body mass. Carbohydrate availability was limited inferring a greater reliance on fat and protein metabolism. Consequently, loss in fat-free mass was more prevalent with insufficient protein and caloric intake, which may relate to performance