Colm Kelleher

Long-wavelength fluctuations and the glass transition in two dimensions and three dimensions

Significance For phase transitions and fluid dynamics, there are significant qualitative differences between two dimensions and three dimensions. However, it has been long assumed that the glass transition is similar in two and three dimensions. Here, we present experimental data on 2D and 3D colloidal systems near their glass transitions. We demonstrate that the differences between two dimensions and three dimensions are due to long-wavelength fluctuations, precisely those that distinguish 2D and 3D phase transitions. We show that the influence of these fluctuations can be disentangled from the underlying dynamics, and that 2D and 3D glass transitions are otherwise similar. Phase transitions significantly differ between 2D and 3D systems, but the influence of dimensionality on the glass transition is unresolved. We use microscopy to study colloidal systems as they approach their glass transitions at high concentrations and find differences between two dimensions and three dimensions. We find that, in two dimensions, particles can undergo large displacements without changing their position relative to their neighbors, in contrast with three dimensions. This is related to Mermin–Wagner long-wavelength fluctuations that influence phase transitions in two dimensions. However, when measuring particle motion only relative to their neighbors, two dimensions and three dimensions have similar behavior as the glass transition is approached, showing that the long-wavelength fluctuations do not cause a fundamental distinction between 2D and 3D glass transitions.Phase transitions significantly differ between two-dimensional and three-dimensional systems, but the influence of dimensionality on the glass transition is unresolved. We use microscopy to study colloidal systems as they approach their glass transitions at high concentrations, and find differences between 2D and 3D. We find that in 2D particles can undergo large displacements without changing their position relative to their neighbors, in contrast with 3D. This is related to Mermin-Wagner longwavelength fluctuations that influence phase transitions in 2D. However, when measuring particle motion only relative to their neighbors, 2D and 3D have similar behavior as the glass transition is approached, showing that the long wavelength fluctuations do not cause a fundamental distinction between 2D and 3D glass transitions.

Charged hydrophobic colloids at an oil–aqueous phase interface

Hydrophobic poly(methyl methacrylate) (PMMA) colloidal particles, when dispersed in oil with a relatively high dielectric constant, can become highly charged. In the presence of an interface with a conducting aqueous phase, image-charge effects lead to strong binding of colloidal particles to the interface, even though the particles are wetted very little by the aqueous phase. We study both the behavior of individual colloidal particles as they approach the interface and the interactions between particles that are already interfacially bound. We demonstrate that using particles which are minimally wetted by the aqueous phase allows us to isolate and study those interactions which are due solely to charging of the particle surface in oil. Finally, we show that these interactions can be understood by a simple image-charge model in which the particle charge q is the sole fitting parameter.

Freezing on a Sphere

The best understood crystal ordering transition is that of two-dimensional freezing, which proceeds by the rapid eradication of lattice defects as the temperature is lowered below a critical threshold. But crystals that assemble on closed surfaces are required by topology to have a minimum number of lattice defects, called disclinations, that act as conserved topological charges—consider the 12 pentagons on a football or the 12 pentamers on a viral capsid. Moreover, crystals assembled on curved surfaces can spontaneously develop additional lattice defects to alleviate the stress imposed by the curvature. It is therefore unclear how crystallization can proceed on a sphere, the simplest curved surface on which it is impossible to eliminate such defects. Here we show that freezing on the surface of a sphere proceeds by the formation of a single, encompassing crystalline ‘continent’, which forces defects into 12 isolated ‘seas’ with the same icosahedral symmetry as footballs and viruses. We use this broken symmetry—aligning the vertices of an icosahedron with the defect seas and unfolding the faces onto a plane—to construct a new order parameter that reveals the underlying long-range orientational order of the lattice. The effects of geometry on crystallization could be taken into account in the design of nanometre- and micrometre-scale structures in which mobile defects are sequestered into self-ordered arrays. Our results may also be relevant in understanding the properties and occurrence of natural icosahedral structures such as viruses.

Addendum: Freezing on a sphere

After the publication of our Letter, we were made aware of some pioneering simulations by Prestipino Giarrita et al. that investigated the icosahedral ordering of defects in assemblies of hard particles packed on the surfaces of spheres1,2. This work anticipated the notion that lattice defects were an inevitable part of ordered structures assembled on spherical shells, and they defined a pair defect-density correlation2, gdef, similar to the g55 function that we plot in Fig. 2a of our Letter. This work1,2 represents a solid contribution to the field and merits wider recognition.