Aleksandar Donev
Program in Applied and Computational Mathematics, Princeton University, Princeton, New Jersey 08544, USA and Princeton Institute for the Science and Technology of Materials, Princeton University, Princeton, New Jersey 08544, USA

Frank H. Stillinger
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA

Salvatore Torquato
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA, Program in Applied and Computational Mathematics, Princeton University, Princeton, New Jersey 08544, USA, Princeton Institute for the Science and Technology of Materials, Princeton University, Princeton, New Jersey 08544, USA and Princeton Center for Theoretical Physics, Princeton University, Princeton, New Jersey 08544, USA

J. Chem. Phys. 127, 124509 (2007).

Received: 5 April 2007; accepted: 2 August 2007; published: 28 September 2007.

Abstract

We study the thermodynamics of a binary hard-disk mixture in which the ratio of disk diameters is k =1.4. We use a recently developed molecular dynamics algorithm to calculate the free-volume entropy of glassy configurations and obtain the configurational entropy (degeneracy) of the supercompressed liquid as a function of density. We find that the configurational entropy of the glasses near the kinetic glass transition is very close to the mixing entropy, suggesting that the degeneracy is zero only for the phase-separated crystal. We explicitly construct an exponential number of jammed packings with densities spanning the spectrum from the accepted "amorphous" glassy state to the phase-separated crystal, thus showing that there is no ideal glass transition in binary hard-disk mixtures. This construction also demonstrates that the ideal glass, defined as having zero configurational entropy, is not amorphous, but instead is nothing more than a phase-separated crystal. This critique of the presumed existence of an ideal glass parallels our previous critique of the idea that there is a most-dense random (close) packing for hard spheres [Torquato et al., Phys. Rev. Lett. 84, 2064 (2000)]. We also perform free-energy calculations to determine the equilibrium phase behavior of the system. The calculations predict a first-order freezing transition at a density below the kinetic glass transition. However, this transition appears to be strongly kinetically suppressed and is not observed directly. New simulation techniques are needed in order to gain a more complete understanding of the thermodynamic and kinetic behavior of the binary disk mixture and, in particular, of the demixing process during crystallization.