Dynamics of Glass Forming Liquids with Randomly Pinned Particles

Abstract

It is frequently assumed that in the limit of vanishing cooling rate, the glass transition phenomenon becomes a thermodynamic transition at a temperature $T_{K}$. However, with any finite cooling rate, the system falls out of equilibrium at temperatures near $T_g(>T_{K})$, implying that the very existence of the putative thermodynamic phase transition at $T_{K}$ can be questioned. Recent studies of systems with randomly pinned particles have hinted that the thermodynamic glass transition may be observed in simulations and experiments carried out for liquids with randomly pinned particles. This expectation is based on the results of approximate calculations that suggest that the temperature of the thermodynamic glass transition increases as the concentration of pinned particles is increased and it may be possible to equilibrate the system at temperatures near the increased transition temperature. We test the validity of this prediction through extensive molecular dynamics simulations of two model glass-forming liquids in the presence of random pinning. We fit the temperature-dependence of the structural relaxation time to the Vogel-Fulcher-Tammann form that predicts a divergence of the relaxation time at a temperature $T_{VFT}$ and identify this temperature with the thermodynamic transition temperature $T_K$. We find that $T_{VFT}$ does not show any sign of increasing with increasing concentration of pinned particles. The main effect of pinning is found to be a rapid decrease in the kinetic fragility of the system with increasing pin concentration. Implications of these observations for current theories of the glass transition are discussed.