Supercooled liquids become more and more viscous as their temperature is reduced. The increased viscosity corresponds to an enormous increase in the characteristic time for the relaxation of density fluctuations. What is often puzzling is that, differently from many other physical phenomena, this dramatic change in the correlations in time appears to be weakly reflected in conventional measures of spatial correlations. These are typically so-called pair or two-body correlations, measuring how likely it is to find randomly chosen pairs of particles at particular characteristic distances.
The lack of strong correlations between two-body spatial correlation and the emergent, enormous relaxation times of supercooled liquids suggests that more complex, eventually multi-body correlations may be at play.
Thanks to the work of a very gifted PhD student in Paddy Royall‘s group, Joshua F. Robinson, we have obtained a first theoretical insight on the origin of such emergent correlations in a reference model for supercooled liquids, i.e. hard spheres, which are often employed to understand the behaviour of colloidal particles and as a basis to develop approximate theories of liquids.
We rooted our work in a geometric approach to treat the free energy of thermal hard spheres developed by Roland Roth (a co-author of our work) termed morphometric theory and this has allowed us to study the free energy of a certain number of thermal structural motifs of hard spheres immersed in an effective medium and predict with a high degree of precision their respective populations. Furthermore, the approach that we have used has revealed that it is possible to follow local deformations of the motifs and compute the free energy barriers between them.
The work appeared as an Editor’s Suggestion in Physical Review Letters: