# Weak temperature dependence of ageing of structural properties in atomistic model glassformers

We have just published in the Journal of Chemical Physics the simulation work of a brilliant former master student of the School of Physics at the University of Bristol (Thomas Jenkinson) on the local structural changes occurring during ageing in two atomistic glass formers with Lennard-Jones interactions (the Kob-Andersen and Wahnström mixtures).

We find some expected results (local order steadily increases as the out-of-equilibrium liquid ages) and some more surprising ones (for example, the rate at which such increase occurs changes weakly for temperatures above the apparent dynamical divergence of viscosities, T0). We also investigate the effect of transient deep quenches, finding very moderate traces of so-called rejuvenation.

The reference to the work is J. Chem. Phys. 147, 054501, (2017).

# Nonequilibrium Phase Transition in an Atomistic Glassformer: the Connection to Thermodynamics

One central piece of the problem of dynamic arrest is whether the phenomenology of slow relaxation, increasing dynamical length scales, mild (or dramatic) structural changes are somewhat related to the existence of a zero entropy amorphous state emerging at a non-zero temperature.

A comprehensive theory would need on the one hand to take into account of the well established phenomenon of dynamical heterogeneitiesi.e. the non-homogenous patterns of diffusion that emerge together with the glassy dynamics itself; on the other hand, it should also rationalise the many findings that point (for several model systems) to a dramatic reduction of the so-called configurational entropy as one approaches a finite temperature (sometimes termed Kauzmann temperature) at which also the relaxation times appear to diverge.

In our recent work (Physical Review X 7, 031028) Thomas Speck,  C. Patrick Royall and I discuss a unified scenario that combines dynamical aspects to structural ones in order to sample very low energy and entropy states, employing dynamical large deviations.

We find that the equilibrium supercooled liquid competes with a secondary metastable  amorphous liquid rich in long-lived structural motifs, hidden in the tails of probability distributions in trajectory space. We also show that sampling the tails of such probabilities at a single moderate temperature allows us to retrieve the thermodynamic properties of the ordinary liquid in much wider range of temperatures, down to very low temperatures. We can then draw a diagram for the stable and metastable phase, pointing towards critical-like fluctuations in the region where the Kauzmann temperature is normally located, and allowing us to review currently proposed scenarios from an alternative point of view, rooted in the large deviation theory of metastability.

# Searching for a module

When installing software on an High Performance Computing unit, additional packages are often handled by the module package.

To have a list of all the modules available it is sufficient to type

 module avail 

Often one then retrieves a very long list of possible modules, in alphabetic order. This is not very convenient if one is looking for a particular feature and dos not really know how it has been categorised.

One may think that grep would suffice to filter the results. This is almost true: in order to use grep first one needs to reformat the result of module avail with the -t  option into a single column, redirect the standard error output (labelled by 2 in Bash) to the standard output (labelled by 1, so that the redirection is 2>&1) and then pipe it with grep.

For example, if we want to search for all the modules containing “python” in their name we would type:

 module avail -t 2>&1 | grep -i python 

and eventually just write a convenient script named modsearch in our ~/bin :

 #!/bin/bash module avail -t 2>&1 | grep -i $1 so that in the future we will just have to type  modsearch python  # 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). # Binary Crystals and Kinetic Traps During an invited talk at the University of Bath on May 3rd 2017, I have had the chance to discuss the work that we have done in Bristol on binary crystals and binary mixtures. The story, that you can find in the following slides, discusses experimental and numerical aspects in the formation and dissolution of binary crystals: • The routes to the formation interstitial solid solution (work with I. Rios de Anda). • The role of compositional frustration (work with P. Crowther), published here. • The emergence of dynamical transition under mechanical deformation of the crystals (work with E. Brillaux). # 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 # Box Counting in Numpy The fractal dimension of an object is a single scalar number that allows us to quantify how compact an object is , i.e. how wiggly a curve is, how wrinkled a surface is, how porous a complex volume is. However, estimating the fractal dimension of an object is not an easy task, and many methods exist. The simplest method is box counting: the idea is to fully cover the object with many boxes of a given size, count how many boxes are needed to cover the object and repeat the process for many box sizes. The scaling of the number of boxes covering the object with the size of the boxes gives an estimate for the fractal dimension of the object. The algorithm has many limitations, but in its simplest form it can be easily implemented in Python. The idea is to simply bin the object in a histogram of variable bin sizes. This can be easily generalised to any dimensions, thanks to Numpy’s histrogramdd function. In the following code, I test the idea with a known fractal, Sierpinski’s triangle, which has an exact (Hausdorff) fractal dimension of log(3)/log(2). import numpy as np import pylab as pl def rgb2gray(rgb): r, g, b = rgb[:,:,0], rgb[:,:,1], rgb[:,:,2] gray = 0.2989 * r + 0.5870 * g + 0.1140 * b return gray image=rgb2gray(pl.imread("Sierpinski.png")) # finding all the non-zero pixels pixels=[] for i in range(image.shape[0]): for j in range(image.shape[1]): if image[i,j]>0: pixels.append((i,j)) Lx=image.shape[1] Ly=image.shape[0] print Lx, Ly pixels=pl.array(pixels) # pl.plot(pixels[:,1], pixels[:,0], '.', ms=0.01) # pl.show() print pixels.shape # computing the fractal dimension #considering only scales in a logarithmic list scales=np.logspace(0.01, 10, num=10, endpoint=False, base=2) Ns=[] # looping over several scales for scale in scales: print "======= Scale :",scale # computing the histogram H, edges=np.histogramdd(pixels, bins=(np.arange(0,Lx,scale),np.arange(0,Ly,scale))) Ns.append(np.sum(H>0)) # linear fit, polynomial of degree 1 coeffs=np.polyfit(np.log(scales), np.log(Ns), 1) pl.plot(np.log(scales),np.log(Ns), 'o', mfc='none') pl.plot(np.log(scales), np.polyval(coeffs,np.log(scales))) pl.xlabel('log$\epsilon\$')
pl.ylabel('log N')
pl.savefig('sierpinski_dimension.pdf')

print "The Hausdorff dimension is", -coeffs[0] #the fractal dimension is the OPPOSITE of the fitting coefficient
np.savetxt("scaling.txt", zip(scales,Ns))


# Clustering and periodic boundaries

Clustering in Python can be nicely done using the statistical tools provided by the sklearn library.

For example, the DBSCAN method easily implements a clustering algorithm that detects connected regions, given a maximum distance between two elements of a cluster.

However, natively the library does not support periodic boundaries, which can be sometimes annoying. But an easy workaround can be found precisely exploiting the power of the library: methods like DBSCAN can be given in input distance matrices directly, and then the clustering is computed on these.

The workaround is to compute the distance matrix with the periodic boundaries in it. The easiest way that I have found is to use the scipy function pdist on each coordinate, correct for the periodic boundaries, then combine the result in order to obtain a distance matrix (in square form) that can be digested by DBSCAN.

The following example may give you a better feeling of how it works.

import pylab as pl
from sklearn.cluster import DBSCAN
from scipy.spatial.distance import pdist,squareform

# box size
L=5.
threshold=0.3
# create data
X=pl.uniform(-1,1, size=(500,2))
# create for corners
X[XL*0.5]-=L

# finding clusters, no periodic boundaries
db=DBSCAN(eps=threshold).fit(X)

pl.scatter(X[:,0], X[:,1],c=db.labels_, s=3,edgecolors='None')
pl.figure()

# 1) find the correct distance matrix
for d in xrange(X.shape[1]):
# find all 1-d distances
pd=pdist(X[:,d].reshape(X.shape[0],1))
# apply boundary conditions
pd[pd>L*0.5]-=L

try:
# sum
total+=pd**2
except Exception, e:
# or define the sum if not previously defined
total=pd**2
# transform the condensed distance matrix...
total=pl.sqrt(total)
# ...into a square distance matrix
square=squareform(total)
db=DBSCAN(eps=threshold, metric='precomputed').fit(square)
pl.scatter(X[:,0], X[:,1],c=db.labels_,s=3, edgecolors='None')
pl.show()


Before the periodic boundaries (Lx=Ly=5):

… and after (Lx=Ly=5):