Experimental Evidence for a Structural-Dynamical Transition in Trajectory Space

Rattachai Pinchaipat is a crafty experimentalist (PhD student in Bristol) that I have had the pleasure to work with within a Bristol-Mainz collaboration aimed at demonstrating in experiments the existence of phase transitions in trajectory space for supercooled liquids. Our work is going to appear in Physical Review Letters. Here is the preprint.

In Mainz, preliminary simulations on hard spheres in trajectory space (by Matteo Campo) have sampled the tails of the probability distribution of time-integrated structural observables and predicted long non-gaussian tails (signature of a phase transition). In experiments, Rattachai managed to find an analogous signature via subsampling the trajectories of a rather large system.

The result demonstrates that the dynamical heterogeneities that characterise fragile glass forming liquids can be read as the coexistence, in trajectory space, of different long-lived (metastable) stationary states: some are structure-less, while others show the presence of extraordinary extended and long-lived motifs. Crucially, the phase transition between the two states is not accessible in current experiments, and could eventually never be accessible, if it is always buried in the tails of the probability distribution.

But this is another story… (actually, this story).

From Glass Formation to Icosahedral Ordering by Curving Three-Dimensional Space

Our work on curved space and frustration with Gilles Tarjus at the Université Pierre et Marie Curie in Paris is going to appear published in Physical Review Letters, 118, 215501.

In it, we provide a test of one of the competing theories for the origins of the glass transition: this is geometric frustration, i.e. the idea that the slowing down observed in glass forming liquids goes hand in hand with the formation of particular non-cristalline geometric motifs, that increase in size as the liquids are cooled.

We test this on the most favourable ground for the theory, which is a curved manifold. We do this for the first time in three dimensions, observing the structural evolution of a glass former on the surface of a sphere embedded in four dimensions (This is a funny space to work in. A beautiful way to visualise such a hypersurface is to use the so-called two-ball construction, see image above, which nicely matches with the vision of the universe that Dante and his teacher Brunetto Latini had).

What we find is that geometrical motifs become gradually unfrustrated as the curvature increases (which is compatible with the basic assumptions of geometric frustration) and ordered phases (with some tricky defects, that we discuss in the Supplemental Material) spontaneously form for low enough temperatures. However, the size of the domains in such motifs is tightly coupled with the slowing down only for very strong curvatures, making geometric frustration just one of the mechanisms that eventually play a role in realistic glass-forming fluids (that exist in our ordinary Euclidean space).

Effects of vertical confinement on gelation and sedimentation of colloids

Disordered systems under confinement may show very specific properties, such as enhanced density fluctuations or flow instabilities.

Azaima Razali (Bristol) and Christopher Fullerton (Bath, now in Montpellier) have performed experiments and simulations on the effect of extreme confinement in colloidal gels and their work (to which I have the pleasure to add my contribution) has just been published in Soft Matter.

The notable result is that while gelation is often employed in bulk systems in order to slow down sedimentation, in strongly confined systems the opposite appears to be true, with sedimentation facilitated by the formation of a percolating network.

The full article can be found here:

A. Razali, C. J. Fullerton, F. Turci,  J. E. Hallett, R. L Jack and C. P. Royall, Effects of vertical confinement on gelation and sedimentation of colloids, Soft Matter, (2017), doi:10.1039/C6SM02221A

Local structure of percolating gels at very low volume fractions

We have recently published on the Journal of Chemical Physics the study resulting from the work of a Master Student in Bristol Chemistry: via numerical simulations, we explore the very low volume fraction regime of a colloidal gel and find striking structural signatures related to the compactness of the gel arms. Moreover, we find that the only limit for gel formation truly is the accessible observation time.

Full reference: S. Griffiths, F. Turci and C. P. Royall,   The Journal of Chemical Physics 146, 014905 (2017); doi: http://dx.doi.org/10.1063/1.4973351