arXiv subjects

Aaron S. Keys

Publications and source records attributed to Aaron S. Keys.

15 recordsLinked to original sources

arXiv2016

Applicability of dynamic facilitation theory to binary hard disk systems

We investigate numerically the applicability of dynamic facilitation (DF) theory for glass-forming binary hard disk systems where supercompression is controlled by pressure. By using novel efficient algorithms for hard disks, we are able to generate equilibrium supercompressed states in an additive non-equimolar binary mixture, where micro-crystallization and size segregation do not emerge at high average packing fractions. Above an onset pressure where collective heterogeneous relaxation sets in, we find that relaxation times are well described by a "parabolic law" with pressure. We identify excitations, or soft-spots, that give rise to structural relaxation, and find that they are spatially localized, their average concentration decays exponentially with pressure, and their associated energy scale is logarithmic in the excitation size. These observations are consistent with the predictions of DF generalized to systems controlled by pressure rather than temperature.

cond-mat.stat-mech↗

arXiv2014

Excitations are localized and relaxation is hierarchical in glass-forming liquids

For several atomistic models of glass formers, at conditions below their glassy dynamics onset temperatures, ${T_\mathrm{o}}$, we use importance sampling of trajectory space to study the structure, statistics and dynamics of excitations responsible for structural relaxation. Excitations are detected in terms of persistent particle displacements of length $a$. At supercooled conditions, for $a$ of the order of or smaller than a particle diameter, we find that excitations are associated with correlated particle motions that are sparse and localized, occupying a volume with an average radius that is temperature independent and no larger than a few particle diameters. We show that the statistics and dynamics of these excitations are facilitated and hierarchical. Excitation energy scales grow logarithmically with $a$. Excitations at one point in space facilitate the birth and death of excitations at neighboring locations, and space-time excitation structures are microcosms of heterogeneous dynamics at larger scales. This nature of dynamics becomes increasingly dominant as temperature $T$ is lowered. We show that slowing of dynamics upon decreasing temperature below $T_\mathrm{o}$ is the result of a decreasing concentration of excitations and concomitant growing hierarchical length scales, and further that the structural relaxation time $τ$ follows the parabolic law, $\log(τ/ τ_\mathrm{o}) = J^2(1/T - 1/T_\mathrm{o})^2$, for $T<T_\mathrm{o}$, where $J$, $τ_\mathrm{o}$ and $T_\mathrm{o}$ can be predicted quantitatively from dynamics at short time scales. Particle motion is facilitated and directional, and we show this becomes more apparent with decreasing $T$. We show that stringlike motion is a natural consequence of facilitated, hierarchical dynamics.

cond-mat.stat-mech↗

arXiv2014

Using the s-Ensemble to Probe Glasses Formed by Cooling and Aging

From length scale distributions characterizing frozen amorphous domains, we relate the s-ensemble method with standard cooling and aging protocols for forming glass. We show that in a general class of models, where space-time scaling is in harmony with that of experiment, the domain size distributions obtained with the s-ensemble are identical to those obtained through cooling or aging, but the computational effort for applying the s-ensemble is generally many orders of magnitude smaller than that of straightforward numerical simulation of cooling or aging.

cond-mat.stat-mech↗

arXiv2013

Calorimetric glass transition explained by hierarchical dynamic facilitation

The glass transition refers to the non-equilibrium process by which an equilibrium liquid is transformed to a non-equilibrium disordered solid, or vice versa. Associated response functions, such as heat capacities, are markedly different on cooling than on heating, and the response to melting a glass depends markedly on the cooling protocol by which the glass was formed. This paper shows how this irreversible behavior can be interpreted quantitatively in terms of an East-model picture of localized excitations (or soft spots) in which molecules can move with a specific direction, and from which excitations with the same directionality of motion can appear or disappear in adjacent regions. As a result of this facilitated dynamics, excitations become correlated in a hierarchical fashion. These correlations are manifested in the dynamic heterogeneity of the supercooled liquid phase. While equilibrium thermodynamics is virtually featureless, a non-equilibrium glass phase emerges when the model is driven out of equilibrium with a finite cooling rate. The correlation length of this emergent phase is large and increases with decreasing cooling rate. A spatially and temporally resolved fictive temperature encodes memory of its preparation. Parameters characterizing the model can be determined from reversible transport data, and with these parameters, predictions of the model agree well with irreversible differential scanning calorimetry.

cond-mat.soft↗

arXiv2012

Manifestations of Dynamical Facilitation in Glassy Materials

By characterizing the dynamics of idealized lattice models with a tunable kinetic constraint, we explore the different ways in which dynamical facilitation manifests itself within the local dynamics of glassy materials. Dynamical facilitation is characterized both by a mobility transfer function, the propensity for highly-mobile regions to arise near regions that were previously mobile, and by a facilitation volume, the effect of an initial dynamical event on subsequent dynamics within a region surrounding it. Sustained bursts of dynamical activity -- avalanches -- are shown to occur in kinetically constrained models, but, contrary to recent claims, we find that the decreasing spatiotemporal extent of avalanches with increased supercooling previously observed in granular experiments does not imply diminishing facilitation. Viewed within the context of existing simulation and experimental evidence, our findings show that dynamical facilitation plays a significant role in the dynamics of systems investigated over the range of state points accessible to molecular simulations and granular experiments.

cond-mat.stat-mech↗

arXiv2012

Self-Assembly of Patchy Particles into Diamond Structures through Molecular Mimicry

Fabrication of diamond structures by self-assembly is a fundamental challenge in making three-dimensional photonic crystals. We simulate a system of model hard particles with attractive patches and show that they can self-assemble into a diamond structure from an initially disordered state. We quantify the extent to which the formation of the diamond structure can be facilitated by "seeding" the system with small diamond crystallites or by introducing a rotation interaction to mimic a carbon-carbon antibonding interaction. Our results suggest patchy particles may serve as colloidal "atoms" and "molecules" for the bottom-up self-assembly of three-dimensional crystals.

cond-mat.stat-mech↗

arXiv2011

Self Assembly of Soft Matter Quasicrystals and Their Approximants

The surprising recent discoveries of quasicrystals and their approximants in soft matter systems poses the intriguing possibility that these structures can be realized in a broad range of nano- and micro-scale assemblies. It has been theorized that soft matter quasicrystals and approximants are largely entropically stabilized, but the thermodynamic mechanism underlying their formation remains elusive. Here, we use computer simulation and free energy calculations to demonstrate a simple design heuristic for assembling quasicrystals and approximants in soft matter systems. Our study builds on previous simulation studies of the self-assembly of dodecagonal quasicrystals and approximants in minimal systems of spherical particles with complex, highly-specific interaction potentials. We demonstrate an alternative entropy-based approach for assembling dodecagonal quasicrystals and approximants based solely on particle functionalization and shape, thereby recasting the interaction-potential-based assembly strategy in terms of simpler-to-achieve bonded and excluded-volume interactions. Here, spherical building blocks are functionalized with mobile surface entities to encourage the formation of structures with low surface contact area, including non-close-packed and polytetrahedral structures. The building blocks also possess shape polydispersity, where a subset of the building blocks deviate from the ideal spherical shape, discouraging the formation of close-packed crystals. We show that three different model systems with both of these features -- mobile surface entities and shape polydispersity -- consistently assemble quasicrystals and/or approximants. We argue that this design strategy can be widely exploited to assemble quasicrystals and approximants on the nano- and micro- scales. In addition, our results further elucidate the formation of soft matter quasicrystals in experiment.

cond-mat.soft↗

arXiv2010

Disordered, Quasicrystalline and Crystalline Phases of Densely Packed Tetrahedra

All hard, convex shapes are conjectured by Ulam to pack more densely than spheres, which have a maximum packing fraction of ϕ = π/\sqrt18 ~ 0.7405. For many shapes, simple lattice packings easily surpass this packing fraction. For regular tetrahedra, this conjecture was shown to be true only very recently; an ordered arrangement was obtained via geometric construction with ϕ = 0.7786, which was subsequently compressed numerically to ϕ = 0.7820. Here we show that tetrahedra pack much better than this, and in a completely unexpected way. Following a conceptually different approach, using thermodynamic computer simulations that allow the system to evolve naturally towards high-density states, we observe that a fluid of hard tetrahedra undergoes a first-order phase transition to a dodecagonal quasicrystal, which can be compressed to a packing fraction of ϕ = 0.8324. By compressing a crystalline approximant of the quasicrystal, the highest packing fraction we obtain is ϕ = 0.8503. If quasicrystal formation is suppressed, the system remains disordered, jams, and compresses to ϕ = 0.7858. Jamming and crystallization are both preceded by an entropy-driven transition from a simple fluid of independent tetrahedra to a complex fluid characterized by tetrahedra arranged in densely packed local motifs that form a percolating network at the transition. The quasicrystal that we report represents the first example of a quasicrystal formed from hard or non-spherical particles. Our results demonstrate that particle shape and entropy can produce highly complex, ordered structures.

cond-mat.soft↗

arXiv2010

A Tale of Two Tilings

What do you get when you cross a crystal with a quasicrystal? The surprising answer stretches from Fibonacci to Kepler, who nearly 400 years ago showed how the ancient tiles of Archimedes form periodic patterns.

cond-mat.mtrl-sci↗

arXiv2010

Harmonic Order Parameters for Characterizing Complex Particle Morphologies

Order parameters based on spherical harmonics and Fourier coefficients already play a significant role in condensed matter research in the context of systems of spherical or point particles. Here, we extend these types of order parameter to more complex shapes, such as those encountered in nanoscale self-assembly applications. To do so, we build on a powerful set of techniques that originate in the computer science field of "shape matching." We demonstrate how shape matching techniques can be applied to identify unknown structures and create highly-specialized \textit{ad hoc} order parameters. Additionally, we investigate the special symmetry properties of harmonic descriptors, and demonstrate how they can be exploited to provide optimal solutions to certain classes of problems. Our techniques can be applied to particle systems in general, both simulated and experimental, provided the particle positions are known.

cond-mat.soft↗

arXiv2010

Measurement of Growing Dynamical Lengthscales and Prediction of the Jamming Transition in a Granular Material

Supercooled liquids and dense colloids exhibit anomalous behaviour known as "spatially heterogeneous dynamics" (SHD), which becomes increasingly pronounced with approach to the glass transition. Recently, SHD has been observed in confined granular packings under slow shear near the onset of jamming, bolstering speculation that the two transitions are related. Here, we report measurements of SHD in a system of air-driven granular beads, as a function of both density and effective temperature. On approach to jamming, the dynamics become progressively slower and more spatially heterogeneous. The rapid growth of dynamical time and length scales characterizing the heterogeneities can be described both by mode-coupling theory and the Vogel-Tammann-Fulcher (VTF) equation, in analogy with glass-forming liquids. The value of the control variable at the VTF transition coincides with point-J, the random close-packed jamming density at which all motion ceases, indicating analogy with a zero temperature ideal glass transition. Our findings demonstrate further universality of the jamming concept and provide a significant step forward in the quest for a unified theory of jamming in disparate systems.

cond-mat.soft↗

arXiv2010

Characterizing Complex Particle Morphologies Through Shape Matching: Descriptors, Applications, and Algorithms

Many standard structural quantities, such as order parameters and correlation functions, exist for common condensed matter systems, such as spherical and rod-like particles. However, these structural quantities are often insufficient for characterizing the unique and highly complex structures often encountered in the emerging field of nano and microscale self-assembly, or other disciplines involving complex structures such as computational biology. Computer science algorithms known as "shape matching" methods pose a unique solution to this problem by providing robust metrics for quantifying the similarity between pairs of arbitrarily complex structures. This pairwise matching operation, either implicitly or explicitly, lies at the heart of most standard structural characterization schemes for particle systems. By substituting more robust "shape descriptors" into these schemes we extend their applicability to structures formed from more complex building blocks. Here, we describe several structural characterization schemes and shape descriptors that can be used to obtain various types of structural information about particle systems. We demonstrate the application of shape matching algorithms to a variety of example problems, for topics including local and global structure identification and classification, automated phase diagram mapping, and the construction of spatial and temporal correlation functions. The methods are applicable to a wide range of systems, both simulated and experimental, provided particle positions are known or can be accurately imaged.

cond-mat.soft↗

arXiv2010

How Do Quasicrystals Grow?

Using molecular simulations, we show that the aperiodic growth of quasicrystals is controlled by the ability of the growing quasicrystal `nucleus' to incorporate kinetically trapped atoms into the solid phase with minimal rearrangement. In the system under investigation, which forms a dodecagonal quasicrystal, we show that this process occurs through the assimilation of stable icosahedral clusters by the growing quasicrystal. Our results demonstrate how local atomic interactions give rise to the long-range aperiodicity of quasicrystals.

cond-mat.other↗

arXiv2010

Characterizing Structure Through Shape Matching and Applications to Self Assembly

Structural quantities such as order parameters and correlation functions are often employed to gain insight into the physical behavior and properties of condensed matter systems. While standard quantities for characterizing structure exist, often they are insufficient for treating problems in the emerging field of nano and microscale self-assembly, where the structures encountered may be complex and unusual. The computer science field of "shape matching" offers a robust solution to this problem by defining diverse methods for quantifying the similarity between arbitrarily complex shapes. Most order parameters and correlation functions used in condensed matter apply a specific measure of structural similarity within the context of a broader scheme. By substituting shape matching quantities for traditional quantities, we retain the essence of the broader scheme, but extend its applicability to more complex structures. Here we review some standard shape matching techniques and discuss how they might be used to create highly flexible structural metrics for diverse systems such as self-assembled matter. We provide three proof-of-concept example problems applying shape matching methods to identifying local and global structures, and tracking structural transitions in complex assembled systems. The shape matching methods reviewed here are applicable to a wide range of condensed matter systems, both simulated and experimental, provided particle positions are known or can be accurately imaged.

cond-mat.soft↗

arXiv2007

Icosahedral packing of polymer-tethered nanospheres and stabilization of the gyroid phase

We present results of molecular simulations that predict the phases formed by the self-assembly of model nanospheres functionalized with a single polymer "tether", including double gyroid, perforated lamella and crystalline bilayer phases. We show that microphase separation of the immiscible tethers and nanospheres causes confinement of the nanoparticles, which promotes local icosahedral packing that stabilizes the gyroid and perforated lamella phases. We present a new metric for determining the local arrangement of particles based on spherical harmonic "fingerprints", which we use to quantify the extent of icosahedral ordering.

cond-mat.soft↗