We study crystallization in a model system for eicosane (C20) by means of molecular dynamics simulation and identify the microscopic mechanisms of homogeneous crystal nucleation and growth. For the nucleation process, we observe that chains first align and then straighten. Then the local density increases and finally the monomer units become ordered positionally. The subsequent crystal growth process is characterized by a sliding-in motion of the chains. Chains preferably attach to the crystalline cluster with one end and then move along the stems of already crystallized chains towards their final position. This process is cooperative, i.e., neighboring chains tend to get attached in clusters rather than independently. © 2013 AIP Publishing LLC. [http://dx

Glasses are among the most widely used of everyday materials, yet the process by which a liquid’s viscosity increases by 14 decades to become a glass remains unclear, as often contradictory theories provide equally good descriptions of the available data. Knowledge of emergent lengthscales and higher-order structure could help resolve this, but this requires time-resolved measurements of dense particle coordinates—previously only obtained over a limited time interval. Here we present an experimental study of a model colloidal system over a dynamic window significantly larger than previous measurements, revealing structural ordering more strongly linked to dynamics than previously found. Furthermore we find that immobile regions and domains of local structure grow concurrently with density, and that these regions have low configurational entropy. We thus show that local structure plays an important role at deep supercooling, consistent with a thermodynamic interpretation of the glass transition rather than a principally dynamic description.

Tackling the low-temperature fate of supercooled liquids is challenging due to the immense timescales involved, which prevent equilibration and lead to the operational glass transition. Relating glassy behaviour to an underlying, thermodynamic phase transition is a long-standing open question in condensed matter physics. Like experiments, computer simulations are limited by the small time window over which a liquid can be equilibrated. Here we address the challenge of low temperature equilibration using trajectory sampling in a system undergoing a nonequilibrium phase transition. This transition occurs in trajectory space between the normal supercooled liquid and a glassy state rich in low-energy geometric motifs. Our results indicate that this transition might become accessible in equilibrium configurational space at a temperature close to the so-called Kauzmann temperature, and provide a possible route to unify dynamical and thermodynamical theories of the glass transition.

Key to resolving the scientific challenge of the glass transition is to understand the origin of the massive increase in viscosity of liquids cooled below their melting temperature (avoiding crystallisation). A number of competing and often mutually exclusive theoretical approaches have been advanced to describe this phenomenon. Some posit a bona fide thermodynamic phase to an 'ideal glass', an amorphous state with exceptionally low entropy. Other approaches are built around the concept of the glass transition as a primarily dynamic phenomenon. These fundamentally different interpretations give equally good descriptions of the data available, so it is hard to determine which-if any-is correct. Recently however this situation has begun to change. A consensus has emerged that one powerful means to resolve this longstanding question is to approach the putative thermodynamic transition sufficiently closely, and a number of techniques have emerged to meet this challenge. Here we review the results of some of these new techniques and discuss the implications for the existence-or otherwise-of the thermodynamic transition to an ideal glass.