Understanding the glassy dynamics from melting temperatures in binary glass-forming liquids

Abstract

It is natural to expect that small particles in binary mixtures move faster than large ones. However, in binary glass-forming liquids with soft-core particle interactions, we observe the counterintuitive dynamic reversal between large and small particles along with the increase of pressure by performing molecular dynamics simulations. The structural relaxation (dynamic heterogeneity) of small particles is faster (weaker) than large ones at low pressures, but becomes slower (stronger) above a crossover pressure. In contrast, this dynamic reversal never happens in glass-forming liquids with hard-core interactions. We find that the difference of the effective melting temperatures felt by large and small particles can be used to understand the dynamic reversal. In binary mixtures, we derive effective melting temperatures of large and small particles simply from the conversion of units and find that particles with a higher effective melting temperature usually undergo a slower and more heterogeneous relaxation. The presence (absence) of the dynamic reversal in soft-core (hard-core) systems is simply due to the non-monotonic (monotonic) behavior of the melting temperature as a function of pressure. Interestingly, by manipulating the relative softness between large and small particles, we obtain a special case of soft-core systems, in which large particles always have higher effective melting temperatures than small ones. As a result, the dynamic reversal is totally eliminated. Our work provides another piece of evidence of the underlying connections between the properties of non-equilibrium glass-formers and equilibrium crystal-formers.