Geometric interpretation of pre-vitrification in hard sphere liquids

We derive a microscopic criterion for the stability of hard sphere configurations, and we show empirically that this criterion is marginally satisfied in the glass. This observation supports a geometric interpretation for the initial rapid rise of viscosity with packing fraction, or pre-vitrification. It also implies that barely stable soft modes characterize the glass structure, whose spatial extension is estimated. We show that both the short-term dynamics and activation processes occur mostly along those soft modes, and we study some implications of these observations. This article synthesizes new and previous results [C. Brito and M. Wyart, Euro. Phys. Letters, {\bf 76}, 149-155, (2006) and C. Brito and M. Wyart, J. Stat. Mech., L08003 (2007) ] in a unified view.Comment: accepted for publication in the Journal of Chemical Physics (added discussion on RCP and ideal glass transition

Geometric and chemical non-uniformity may induce the stability of more than one wetting state in the same hydrophobic surface

It is established that roughness and chemistry play a crucial role in the wetting properties of a substrate. Yet, few studies have analyzed systematically the effect of the non-uniformity in the distribution of texture and surface tension of substrates on its wetting properties. In this work we investigate this issue theoretically and numerically. We propose a continuous model that takes into account the total energy required to create interfaces of a droplet in two possible wetting states: Cassie-Baxter(CB) with air pockets trapped underneath the droplet; and the other characterized by the homogeneous wetting of the surface, the Wenzel(W) state. To introduce geometrical non-regularity we suppose that pillar heights and pillar distances are Gaussian distributed instead of having a constant value. Similarly, we suppose a heterogeneous distribution of Young's angle on the surface to take into account the chemical non-uniformity. This allows to vary the "amount" of disorder by changing the variance of the distribution. We first solve this model analytically and then we also propose a numerical version of it, which can be applied to study any type of disorder. In both versions, we employ the same physical idea: the energies of both states are minimized to predict the thermodynamic wetting state of the droplet for a given volume and surface texture. We find that the main effect of disorder is to induce the stability of both wetting states on the same substrate. In terms of the influence of the disorder on the contact angle of the droplet, we find that it is negligible for the chemical disorder and for pillar-distance disorder. However, in the case of pillar-height disorder, it is observed that the average contact angle of the droplet increases with the amount of disorder. We end the paper investigating how the region of stability of both wetting states behaves when the droplet volume changes

Theory for Swap Acceleration near the Glass and Jamming Transitions

Swap algorithms can shift the glass transition to lower temperatures, a recent unexplained observation constraining the nature of this phenomenon. Here we show that swap dynamic is governed by an effective potential describing both particle interactions as well as their ability to change size. Requiring its stability is more demanding than for the potential energy alone. This result implies that stable configurations appear at lower energies with swap dynamics, and thus at lower temperatures when the liquid is cooled. \maa{ The magnitude of this effect is proportional to the width of the radii distribution, and decreases with compression for finite-range purely repulsive interaction potentials.} We test these predictions numerically and discuss the implications of these findings for the glass transition.We extend these results to the case of hard spheres where swap is argued to destroy meta-stable states of the free energy coarse-grained on vibrational time scales. Our analysis unravels the soft elastic modes responsible for the speed up swap induces, and allows us to predict the structure and the vibrational properties of glass configurations reachable with swap. In particular for continuously poly-disperse systems we predict the jamming transition to be dramatically altered, as we confirm numerically. A surprising practical outcome of our analysis is new algorithm that generates ultra-stable glasses by simple descent in an appropriate effective potential.Comment: 8 pages, 7 figures in the main text, 3 pages 4 figures in the supplemental material. We improved the theoretical discussion in the v3. In particular, we added a section with an extended discussion of the implications of our findings for the glass transitio

Architecture and Co-Evolution of Allosteric Materials

We introduce a numerical scheme to evolve functional materials that can accomplish a specified mechanical task. In this scheme, the number of solutions, their spatial architectures and the correlations among them can be computed. As an example, we consider an "allosteric" task, which requires the material to respond specifically to a stimulus at a distant active site. We find that functioning materials evolve a less-constrained trumpet-shaped region connecting the stimulus and active sites and that the amplitude of the elastic response varies non-monotonically along the trumpet. As previously shown for some proteins, we find that correlations appearing during evolution alone are sufficient to identify key aspects of this design. Finally, we show that the success of this architecture stems from the emergence of soft edge modes recently found to appear near the surface of marginally connected materials. Overall, our in silico evolution experiment offers a new window to study the relationship between structure, function, and correlations emerging during evolution.Comment: 6 pages, 5 figures, SI: 2 pages, 4 figure

Percolation and cooperation with mobile agents: Geometric and strategy clusters

We study the conditions for persistent cooperation in an off-lattice model of mobile agents playing the Prisoner's Dilemma game with pure, unconditional strategies. Each agent has an exclusion radius rP, which accounts for the population viscosity, and an interaction radius rint, which defines the instantaneous contact network for the game dynamics. We show that, differently from the rP=0 case, the model with finite-sized agents presents a coexistence phase with both cooperators and defectors, besides the two absorbing phases, in which either cooperators or defectors dominate. We provide, in addition, a geometric interpretation of the transitions between phases. In analogy with lattice models, the geometric percolation of the contact network (i.e., irrespective of the strategy) enhances cooperation. More importantly, we show that the percolation of defectors is an essential condition for their survival. Differently from compact clusters of cooperators, isolated groups of defectors will eventually become extinct if not percolating, independently of their size

Principles for optimal cooperativity in allosteric materials

Allosteric proteins transmit a mechanical signal induced by binding a ligand. However, understanding the nature of the information transmitted and the architectures optimizing such transmission remains a challenge. Here we show using an {\it in-silico} evolution scheme and theoretical arguments that architectures optimized to be cooperative, which propagate efficiently energy, {qualitatively} differ from previously investigated materials optimized to propagate strain. Although we observe a large diversity of functioning cooperative architectures (including shear, hinge and twist designs), they all obey the same principle {of displaying a {\it mechanism}, i.e. an extended {soft} mode}. We show that its optimal frequency decreases with the spatial extension $L$ of the system as $L^{-d/2}$, where $d$ is the spatial dimension. For these optimal designs, cooperativity decays logarithmically with $L$ for $d=2$ and does not decay for $d=3$. Overall our approach leads to a natural explanation for several observations in allosteric proteins, and { indicates an experimental path to test if allosteric proteins lie close to optimality}.Comment: 11 pages, 9 figures in the main text, 9 pages 9 figures in the supplemental materia

On the Modeling of Droplet Evaporation on Superhydrophobic Surfaces

When a drop of water is placed on a rough surface, there are two possible extreme regimes of wetting: the one called Cassie-Baxter (CB) with air pockets trapped underneath the droplet and the one characterized by the homogeneous wetting of the surface, called the Wenzel (W) state. A way to investigate the transition between these two states is by means of evaporation experiments, in which the droplet starts in a CB state and, as its volume decreases, penetrates the surface's grooves, reaching a W state. Here we present a theoretical model based on the global interfacial energies for CB and W states that allows us to predict the thermodynamic wetting state of the droplet for a given volume and surface texture. We first analyze the influence of the surface geometric parameters on the droplet's final wetting state with constant volume, and show that it depends strongly on the surface texture. We then vary the volume of the droplet keeping fixed the geometric surface parameters to mimic evaporation and show that the drop experiences a transition from the CB to the W state when its volume reduces, as observed in experiments. To investigate the dependency of the wetting state on the initial state of the droplet, we implement a cellular Potts model in three dimensions. Simulations show a very good agreement with theory when the initial state is W, but it disagrees when the droplet is initialized in a CB state, in accordance with previous observations which show that the CB state is metastable in many cases. Both simulations and theoretical model can be modified to study other types of surface.Comment: 23 pages, 7 figure

Fast generation of ultrastable computer glasses by minimization of an augmented potential energy

We present a model and protocol that enable the generation of extremely stable computer glasses at minimal computational cost. The protocol consists of an instantaneous quench in an augmented potential energy landscape, with particle radii as additional degrees of freedom. We demonstrate how our glasses' mechanical stability, which is readily tunable in our approach, is reflected both in microscopic and macroscopic observables. Our observations indicate that the stability of our computer glasses is at least comparable to that of computer glasses generated by the celebrated Swap Monte Carlo algorithm. Strikingly, some key properties support even qualitatively enhanced stability in our scheme: the density of quasilocalized excitations displays a gap in our most stable computer glasses, whose magnitude scales with the polydispersity of the particles. We explain this observation, which is consistent with the lack of plasticity we observe at small stress. It also suggests that these glasses are depleted from two-level systems, similarly to experimental vapor-deposited ultrastable glasses.Comment: 11 pages, 10 figure