Stability of supercooled binary liquid mixtures

Recently the supercooled Wahnstrom binary Lennard-Jones mixture was partially crystallized into ${\rm MgZn_2}$ phase crystals in lengthy Molecular Dynamics simulations. We present Molecular Dynamics simulations of a modified Kob-Andersen binary Lennard-Jones mixture that also crystallizes in lengthy simulations, here however by forming pure fcc crystals of the majority component. The two findings motivate this paper that gives a general thermodynamic and kinetic treatment of the stability of supercooled binary mixtures, emphasizing the importance of negative mixing enthalpy whenever present. The theory is used to estimate the crystallization time in a Kob-Andersen mixture from the crystallization time in a series of relared systems. At T=0.40 we estimate this time to be 5$\times 10^{7}$ time units ($\approx 1. ms$). A new binary Lennard-Jones mixture is proposed that is not prone to crystallization and faster to simulate than the two standard binary Lennard-Jones mixtures; this is obtained by removing the like-particle attractions by switching to Weeks-Chandler-Andersen type potentials, while maintaining the unlike-particle attraction

Crystallization of the Wahnstr\"om Binary Lennard-Jones Liquid

We report observation of crystallization of the glass-forming binary Lennard-Jones liquid first used by Wahnstr\"om [G. Wahnstr\"om, Phys. Rev. A 44, 3752 (1991)]. Molecular dynamics simulations of the metastable liquid on a timescale of microseconds were performed. The liquid crystallized spontaneously. The crystal structure was identified as MgZn_2. Formation of transient crystallites is observed in the liquid. The crystallization is investigate at different temperatures and compositions. At high temperature the rate of crystallite formation is the limiting factor, while at low temperature the limiting factor is growth rate. The melting temperature of the crystal is estimated to be T_m=0.93 at rho=0.82. The maximum crystallization rate of the A_2B composition is T=0.60+/-0.02.Comment: 4 pages, 4 figures; corrected typo

The Geometry of Slow Structural Fluctuations in a Supercooled Binary Alloy

The liquid structure of a glass-forming binary alloy is studied using molecular dynamics simulations. The analysis combines common neighbour analysis with the geometrical approach of Frank and Kasper to establish that the supercooled liquid contains extended clusters characterised by the same short range order as the crystal. Fluctuations in these clusters exhibit strong correlations with fluctuations in the inherent structure energy. The steep increase in the heat capacity on cooling is, thus, directly coupled to the growing fluctuations of the Frank-Kasper clusters. The relaxation of particles in the clusters dominates the slow tail of the self-intermediate scattering function

Strong pressure-energy correlations in liquids as a configuration space property: Simulations of temperature down jumps and crystallization

Computer simulations recently revealed that several liquids exhibit strong correlations between virial and potential energy equilibrium fluctuations in the NVT ensemble [U. R. Pedersen {\it et al.}, Phys. Rev. Lett. {\bf 100}, 015701 (2008)]. In order to investigate whether these correlations are present also far from equilibrium constant-volume aging following a temperature down jump from equilibrium was simulated for two strongly correlating liquids, an asymmetric dumbbell model and Lewis-Wahnstr{\"o}m OTP, as well as for SPC water that is not strongly correlating. For the two strongly correlating liquids virial and potential energy follow each other closely during the aging towards equilibrium. For SPC water, on the other hand, virial and potential energy vary with little correlation as the system ages towards equilibrium. Further proof that strong pressure-energy correlations express a configuration space property comes from monitoring pressure and energy during the crystallization (reported here for the first time) of supercooled Lewis-Wahnstr{\"o}m OTP at constant temperature

Extreme case of density scaling:The Weeks-Chandler-Andersen system at low temperatures

This paper studies numerically the Weeks-Chandler-Andersen (WCA) system, which is shown to obey hidden scale invariance with a density-scaling exponent that varies from below 5 to above 500. This unprecedented variation makes it advantageous to use the fourth-order Runge-Kutta algorithm for tracing out isomorphs. Good isomorph invariance of the structure and dynamics is observed over more than three orders of magnitude temperature variation. For all state points studied, the virial potential-energy correlation coefficient and the density-scaling exponent are controlled mainly by the temperature. A mean-field theory is presented based on the assumption of statistically independent pair interactions, which rationalizes this finding

Estimating the density scaling exponent of viscous liquids from specific heat and bulk modulus data

It was recently shown by computer simulations that a large class of liquids exhibits strong correlations in their thermal fluctuations of virial and potential energy [Pedersen et al., Phys. Rev. Lett. 100, 015701 (2008)]. Among organic liquids the class of strongly correlating liquids includes van der Waals liquids, but excludes ionic and hydrogen-bonding liquids. The present note focuses on the density scaling of strongly correlating liquids, i.e., the fact their relaxation time tau at different densities rho and temperatures T collapses to a master curve according to the expression tau propto F(rho^gamma/T) [Schroder et al., arXiv:0803.2199]. We here show how to calculate the exponent gamma from bulk modulus and specific heat data, either measured as functions of frequency in the metastable liquid or extrapolated from the glass and liquid phases to a common temperature (close to the glass transition temperature). Thus an exponent defined from the response to highly nonlinear parameter changes may be determined from linear response measurements

A repulsive reference potential reproducing the dynamics of a liquid with attractions

A well-known result of liquid state theory is that the structure of dense fluids is mainly determined by repulsive forces. The WCA potential, which cuts intermolecular potentials at their minima, is therefore often used as a reference. However, this reference gives quite wrong results for the viscous dynamics of the Kob-Andersen binary Lennard-Jones liquid [Berthier and Tarjus, Phys. Rev. Lett. 103, 170601 (2009)]. We show that repulsive inverse-power law potentials provide a useful reference for this liquid by reproducing its structure, dynamics, and isochoric heat capacity