Toby S. Hudson

Three-dimensional organization of rare-earth atoms at grain boundaries in silicon nitride

Used in the preparation of Si3N4 components, rare-earth elements promote the growth of needlelike grains essential to elevated toughness; evidently, La is significantly more effective than Lu. To explore this difference, we determine the three-dimensional organization of rare-earth atoms in the amorphous phase near prismatic interfaces in La- and Lu-containing Si3N4 using aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and image processing. Evidence is presented for substantial atomic structure in notionally amorphous volumes. While the atomic arrangement in the amorphous phase conforms to the periodicity of the terminating crystal plane in both cases, the attachment sites are very different.

Arrangement of rare-earth elements at prismatic grain boundaries in silicon nitride

The arrangement of rare-earth atoms at {100} prism planes of La- and Lu-containing polycrystalline Si3N4 specimens is studied using high-angle annular dark-field scanning transmission electron microscopy. For both systems, the attachment sites of rare-earth atoms are well-defined and largely conform to the periodicity of the terminating plane of the Si3N4 grain. We observe significant differences between the structural arrangement of La and Lu atoms at the interface.

The Formation of High‐Order Polybromides in a Room‐Temperature Ionic Liquid: From Monoanions ([Br5]− to [Br11]−) to the Isolation of [PC16H36]2[Br24] as Determined by van der Waals Bonding Radii

An unprecedented diversity of high-order bromine catenates (anionic polybromides) was generated in a tetraalkylphosphonium-based room temperature ionic liquid system. Raman spectroscopy was used to identify polybromide monoanions ranging from [Br5 ](-) to [Br11 ](-) in the bulk solution, while single-crystal X-ray diffraction identified extended networks of linked [Br11 ](-) units, forming a previously unknown polymeric [Br24 ](2-) dianion. This represents the largest polybromide species identified to date. In combination with recent work, this suggests that other, higher order molecular polybromide ions might be isolated.

The Densest Packing of AB Binary Hard-Sphere Homogeneous Compounds across all Size Ratios

This paper considers the homogeneous packing of binary hard spheres in an equimolar stoichiometry, and postulates the densest packing at each sphere size ratio. Monte Carlo simulated annealing optimizations are seeded with all known atomic inorganic crystal structures, and the search is performed within the degrees of freedom associated with each homogeneous AB structure type. Structures isopointal to the FeB structure type are found to have the highest packing fraction at all sphere size ratios. The optimized structures match or improve on the best previously demonstrated packings of this type, and show that compound structures can pack more densely than segregated close-packed structures at all radius ratios less than 0.62.

Communication: From rods to helices: Evidence of a screw-like nematic phase

Evidence of a special chiral nematic phase is provided using numerical simulation and Onsager theory for systems of hard helical particles. This phase appears at the high density end of the nematic phase, when helices are well aligned, and is characterized by the C2 symmetry axes of the helices spiraling around the nematic director with periodicity equal to the particle pitch. This coupling between translational and rotational degrees of freedom allows a more efficient packing and hence an increase of translational entropy. Suitable order parameters and correlation functions are introduced to identify this screw-like phase, whose main features are then studied as a function of radius and pitch of the helical particles. Our study highlights the physical mechanism underlying a similar ordering observed in colloidal helical flagella [E. Barry, Z. Hensel, Z. Dogic, M. Shribak, and R. Oldenbourg, Phys. Rev. Lett. 96, 018305 (2006)] and raises the question of whether it could be observed in other helical particle systems, such as DNA, at sufficiently high densities.

Confinement of interstitial cluster diffusion by oversized solute atoms

We study the effects of oversized solute atoms on the diffusion of clusters of self–interstitial atoms produced in metals by high–energy irradiation. We use kinetic Monte Carlo (KMC) simulations in model body–centred cubic iron, and include elastic interactions between the defects. We show that elastic repulsion between solute atoms and the clusters can confine the latter to one–dimensional segments. The easy direction of motion of each cluster is assumed to rotate infrequently, allowing it to escape to a new confined segment. The consequences of the confinement for the effective diffusivity of the cluster and its rate of reaction with other small static spherical sinks are explored both by KMC simulations and by an analytic theory. It is shown that the predictions of the theory agree very well with the computer simulations. We suggest some of the possible consequences of these findings for the design of alloys that are more resistant to the effects of high–energy radiation damage.

Self-assembly of hard helices: a rich and unconventional polymorphism

Hard helices can be regarded as a paradigmatic elementary model for a number of natural and synthetic soft matter systems, all featuring the helix as their basic structural unit, from natural polynucleotides and polypeptides to synthetic helical polymers, and from bacterial flagella to colloidal helices. Here we present an extensive investigation of the phase diagram of hard helices using a variety of methods. Isobaric Monte Carlo numerical simulations are used to trace the phase diagram; on going from the low-density isotropic to the high-density compact phases a rich polymorphism is observed, exhibiting a special chiral screw-like nematic phase and a number of chiral and/or polar smectic phases. We present full characterization of the latter, showing that they have unconventional features, ascribable to the helical shape of the constituent particles. Equal area construction is used to locate the isotropic-to-nematic phase transition, and the results are compared with those stemming from an Onsager-like theory. Density functional theory is also used to study the nematic-to-screw-nematic phase transition; within the simplifying assumption of perfectly parallel helices, we compare different levels of approximation, that is second- and third-virial expansions and a Parsons-Lee correction.

Effects of elastic interactions on post-cascade radiation damage evolution in kinetic Monte Carlo simulations

We describe a series of kinetic Monte Carlo simulations of post-cascade radiation damage evolution in α-iron that illustrates the part played by elastic interaction between defects. Elastic interactions are included as a bias to the diffusion of mobile point defects and defect clusters. The simulations show that recombination fractions are reduced, and vacancy clustering is enhanced. The sensitivity of these effects to temperature, cascade energy, and geometric description of vacancy clusters is also investigated.

Dense Packings of Hard Spheres of Different Sizes Based on Filling Interstices in Uniform Three-Dimensional Tilings

A systematic survey is presented of the maximum packing fractions obtained by decorating the 28 uniform tilings of three-dimensional space with spheres of one size and then filling the interstices of these tilings, starting with the largest, with spheres of different sizes. A number of size ratios and structures are identified that have not, to date, been considered in problems involving the packing of spheres of different sizes.

Long range stress correlations in the inherent structures of liquids at rest

Simulation studies of the atomic shear stress in the local potential energy minima (inherent structures) are reported for binary liquid mixtures in 2D and 3D. These inherent structure stresses are fundamental to slow stress relaxation and high viscosity in supercooled liquids. We find that the atomic shear stress in the inherent structures (ISs) of both liquids at rest exhibits slowly decaying anisotropic correlations. We show that the stress correlations contribute significantly to the variance of the total shear stress of the IS configurations and consider the origins of the anisotropy and spatial extent of the stress correlations.