Anomalous elasticity in classical glass formers.

Amorphous solids under mechanical strains are prone to plastic responses. Recent work showed that in amorphous granular systems these plastic events, that are typically quadrupolar in nature, can screen the elastic response. When the density of the quadrupoles is high, the gradients of the quadrupole field act as emergent dipole sources, leading to qualitative changes in the mechanical response, as seen for example in the displacement field. In this paper we examine the effect of screening in classical glass formers. These are made of point particles that interact via binary forces. Both inverse power law forces and Lennard-Jones interactions are examined, and it is shown that in both cases the elastic response can be strongly screened, in agreement with the novel theory. The degree of deviation from classical elasticity theory is parametrized by a proposed measure that is shown to have a functional dependence on the amount of energy lost to plastic responses.

Robustness of mean field theory for hard sphere models.

In very recent work the mean field theory of the jamming transition in infinite-dimensional hard sphere models was presented. Surprisingly, this theory predicts quantitatively the numerically determined characteristics of jamming in two and three dimensions. This is a rare and unusual finding. Here we argue that this agreement is nongeneric: only for hard sphere models does it happen that sufficiently close to the jamming density (at any temperature) the effective interactions are binary, in agreement with mean field theory, justifying the truncation of many-body interactions (which is the exact protocol in infinite dimensions). Any softening of the bare hard sphere interactions results in many-body effective interactions that are not mean field at any density, making the d=∞ results not applicable.

Reducing anti-nutritional factor and enhancing yield with advancing time of planting and zinc application in grasspea in Ethiopia.

BACKGROUND: Grasspea (Lathyrus sativus L.) is an important pulse crop for food, feed and sustainable crop production systems in Ethiopia. Despite its advantages in nutrition and adaptability to harsh climate and low fertile soil, it contains a neurotoxin, ß-N-oxalyl-α,ß-diamiono propionic acid (ß-ODAP), which paralyses the lower limbs and is affected by genotypic and agronomic factors. To determine the effect of zinc application and planting date on yield and ß-ODAP content of two genotypes, experiments were conducted in two regions of Ethiopia. RESULTS: The main effects of variety, sowing date and zinc and their interactions were significant (P < 0.001) for ß-ODAP and seed yield, which had a linear relationship with zinc. For the improved grasspea variety, an application of 20 kg ha-1 zinc showed a reduction of ß-ODAP from 0.15% to 0.088% at Debre Zeit and 0.14% to 0.08% at Sheno and increased its yield from 841 kg ha-1 to 2260 kg ha-1 at Debre Zeit and from 715 to 1835 kg ha-1 at Sheno. Early sowing showed a reduction in ODAP content in relation to the late sowing. CONCLUSION: An application of Zn beyond even 20 kg ha-1 with an early sowing is recommended for the improved variety. © 2017 Society of Chemical Industry.

Shear bands as manifestation of a criticality in yielding amorphous solids.

Amorphous solids increase their stress as a function of an applied strain until a mechanical yield point whereupon the stress cannot increase anymore, afterward exhibiting a steady state with a constant mean stress. In stress-controlled experiments, the system simply breaks when pushed beyond this mean stress. The ubiquity of this phenomenon over a huge variety of amorphous solids calls for a generic theory that is free of microscopic details. Here, we offer such a theory: The mechanical yield is a thermodynamic phase transition, where yield occurs as a spinodal phenomenon. At the spinodal point, there exists a divergent correlation length that is associated with the system-spanning instabilities (also known as shear bands), which are typical to the mechanical yield. The theory, the order parameter used, and the correlation functions that exhibit the divergent correlation length are universal in nature and can be applied to any amorphous solids that undergo mechanical yield.

Mechanical failure in amorphous solids: Scale-free spinodal criticality.

The mechanical failure of amorphous media is a ubiquitous phenomenon from material engineering to geology. It has been noticed for a long time that the phenomenon is "scale-free," indicating some type of criticality. In spite of attempts to invoke "Self-Organized Criticality," the physical origin of this criticality, and also its universal nature, being quite insensitive to the nature of microscopic interactions, remained elusive. Recently we proposed that the precise nature of this critical behavior is manifested by a spinodal point of a thermodynamic phase transition. Demonstrating this requires the introduction of an "order parameter" that is suitable for distinguishing between disordered amorphous systems. At the spinodal point there exists a divergent correlation length which is associated with the system-spanning instabilities (known also as shear bands) which are typical to the mechanical yield. The theory, the order parameter used and the correlation functions which exhibit the divergent correlation length are universal in nature and can be applied to any amorphous solid that undergoes mechanical yield. The phenomenon is seen at its sharpest in athermal systems, as is explained below; in this paper we extend the discussion also to thermal systems, showing that at sufficiently high temperatures the spinodal phenomenon is destroyed by thermal fluctuations.

Breakdown of nonlinear elasticity in amorphous solids at finite temperatures.

It is known [H. G. E. Hentschel et al., Phys. Rev. E 83, 061101 (2011)PLEEE81539-375510.1103/PhysRevE.83.061101] that amorphous solids at zero temperature do not possess a nonlinear elasticity theory: besides the shear modulus, which exists, none of the higher order coefficients exist in the thermodynamic limit. Here we show that the same phenomenon persists up to temperatures comparable to that of the glass transition. The zero-temperature mechanism due to the prevalence of dangerous plastic modes of the Hessian matrix is replaced by anomalous stress fluctuations that lead to the divergence of the variances of the higher order elastic coefficients. The conclusion is that in amorphous solids elasticity can never be decoupled from plasticity: the nonlinear response is very substantially plastic.

Mechanical Yield in Amorphous Solids: A First-Order Phase Transition.

Amorphous solids yield at a critical value of the strain (in strain-controlled experiments); for larger strains, the average stress can no longer increase-the system displays an elastoplastic steady state. A long-standing riddle in the materials community is what the difference is between the microscopic states of the material before and after yield. Explanations in the literature are material specific, but the universality of the phenomenon begs a universal answer. We argue here that there is no fundamental difference in the states of matter before and after yield, but the yield is a bona fide first-order phase transition between a highly restricted set of possible configurations residing in a small region of phase space to a vastly rich set of configurations which include many marginally stable ones. To show this, we employ an order parameter of universal applicability, independent of the microscopic interactions, that is successful in quantifying the transition in an unambiguous manner.

Elasticity in Amorphous Solids: Nonlinear or Piecewise Linear?

Quasistatic strain-controlled measurements of stress versus strain curves in macroscopic amorphous solids result in a nonlinear-looking curve that ends up either in mechanical collapse or in a steady state with fluctuations around a mean stress that remains constant with increasing strain. It is therefore very tempting to fit a nonlinear expansion of the stress in powers of the strain. We argue here that at low temperatures the meaning of such an expansion needs to be reconsidered. We point out the enormous difference between quenched and annealed averages of the stress versus strain curves and propose that a useful description of the mechanical response is given by a stress (or strain) -dependent shear modulus for which a theoretical evaluation exists. The elastic response is piecewise linear rather than nonlinear.

Excess entropy and crystallization in Stillinger-Weber and Lennard-Jones fluids.

Molecular dynamics simulations are used to contrast the supercooling and crystallization behaviour of monatomic liquids that exemplify the transition from simple to anomalous, tetrahedral liquids. As examples of simple fluids, we use the Lennard-Jones (LJ) liquid and a pair-dominated Stillinger-Weber liquid (SW16). As examples of tetrahedral, water-like fluids, we use the Stillinger-Weber model with variable tetrahedrality parameterized for germanium (SW20), silicon (SW21), and water (SW(23.15) or mW model). The thermodynamic response functions show clear qualitative differences between simple and water-like liquids. For simple liquids, the compressibility and the heat capacity remain small on isobaric cooling. The tetrahedral liquids in contrast show a very sharp rise in these two response functions as the lower limit of liquid-phase stability is reached. While the thermal expansivity decreases with temperature but never crosses zero in simple liquids, in all three tetrahedral liquids at the studied pressure, there is a temperature of maximum density below which thermal expansivity is negative. In contrast to the thermodynamic response functions, the excess entropy on isobaric cooling does not show qualitatively different features for simple and water-like liquids; however, the slope and curvature of the entropy-temperature plots reflect the heat capacity trends. Two trajectory-based computational estimation methods for the entropy and the heat capacity are compared for possible structural insights into supercooling, with the entropy obtained from thermodynamic integration. The two-phase thermodynamic estimator for the excess entropy proves to be fairly accurate in comparison to the excess entropy values obtained by thermodynamic integration, for all five Lennard-Jones and Stillinger-Weber liquids. The entropy estimator based on the multiparticle correlation expansion that accounts for both pair and triplet correlations, denoted by S(trip), is also studied. S(trip) is a good entropy estimator for liquids where pair and triplet correlations are important such as Ge and Si, but loses accuracy for purely pair-dominated liquids, like LJ fluid, or near the crystallization temperature (T(thr)). Since local tetrahedral order is compatible with both liquid and crystalline states, the reorganisation of tetrahedral liquids is accompanied by a clear rise in the pair, triplet, and thermodynamic contributions to the heat capacity, resulting in the heat capacity anomaly. In contrast, the pair-dominated liquids show increasing dominance of triplet correlations on approaching crystallization but no sharp rise in either the pair or thermodynamic heat capacities.

Triplet correlation functions in liquid water.

Triplet correlations have been shown to play a crucial role in the transformation of simple liquids to anomalous tetrahedral fluids [M. Singh, D. Dhabal, A. H. Nguyen, V. Molinero, and C. Chakravarty, Phys. Rev. Lett. 112, 147801 (2014)]. Here we examine triplet correlation functions for water, arguably the most important tetrahedral liquid, under ambient conditions, using configurational ensembles derived from molecular dynamics (MD) simulations and reverse Monte Carlo (RMC) datasets fitted to experimental scattering data. Four different RMC data sets with widely varying hydrogen-bond topologies fitted to neutron and x-ray scattering data are considered [K. T. Wikfeldt, M. Leetmaa, M. P. Ljungberg, A. Nilsson, and L. G. M. Pettersson, J. Phys. Chem. B 113, 6246 (2009)]. Molecular dynamics simulations are performed for two rigid-body effective pair potentials (SPC/E and TIP4P/2005) and the monatomic water (mW) model. Triplet correlation functions are compared with other structural measures for tetrahedrality, such as the O-O-O angular distribution function and the local tetrahedral order distributions. In contrast to the pair correlation functions, which are identical for all the RMC ensembles, the O-O-O triplet correlation function can discriminate between ensembles with different degrees of tetrahedral network formation with the maximally symmetric, tetrahedral SYM dataset displaying distinct signatures of tetrahedrality similar to those obtained from atomistic simulations of the SPC/E model. Triplet correlations from the RMC datasets conform closely to the Kirkwood superposition approximation, while those from MD simulations show deviations within the first two neighbour shells. The possibilities for experimental estimation of triplet correlations of water and other tetrahedral liquids are discussed.

Triplet correlations dominate the transition from simple to tetrahedral liquids.

The total, triplet, and pair contributions to the entropy with increasing tetrahedrality are mapped out for the Stillinger-Weber liquids to demonstrate the qualitative and quantitative differences between triplet-dominated, tetrahedral liquids and pair-dominated, simple liquids with regard to supercooling and crystallization. The heat capacity anomaly of tetrahedral liquids originates in local ordering due to both pair and triplet correlations. The results suggest that structural correlations can be directly related to thermodynamic anomalies, phase changes, and self-assembly in other atomic and colloidal fluids.

Structural correlations and cooperative dynamics in supercooled liquids.

The relationships between diffusivity and the excess, pair and residual multiparticle contributions to the entropy are examined for Lennard-Jones liquids and binary glassformers, in the context of approximate inverse power law mappings of simple liquids. In the dense liquid where diffusivities are controlled by collisions and cage relaxations, Rosenfeld-type excess entropy scaling of diffusivities is found to hold for both crystallizing as well as vitrifying liquids. The crucial differences between the two categories of liquids emerge only when local cooperative effects in the dynamics result in significant caging effects in the time-dependent behaviour of the single-particle mean square displacement. In the case of glassformers, onset of such local cooperativity coincides with onset of deviations from Rosenfeld-type excess entropy scaling of diffusivities and increasing spatiotemporal heterogeneity. In contrast, for two- and three-dimensional liquids with a propensity to crystallise, the onset of local cooperative dynamics is sufficient to trigger crystallization provided that the liquid is sufficiently supercooled that the free energy barrier to nucleation of the solid phase is negligible. The state points corresponding to onset of transient caging effects can be associated with typical values, within reasonable bounds, of the excess, pair, and residual multiparticle entropy as a consequence of the isomorph-invariant character of the excess entropy, diffusivity and related static and dynamic correlation functions.

Excess entropy scaling of transport properties in network-forming ionic melts (SiO(2) and BeF(2)).

The regime of validity of Rosenfeld excess entropy scaling of diffusivity and viscosity is examined for two tetrahedral, network-forming ionic melts (BeF(2) and SiO(2)) using molecular dynamics simulations. With decrease in temperature, onset of local caging behavior in the diffusional dynamics is shown to be accompanied by a significant increase in the effect of three-body and higher-order particle correlations on the excess entropy, diffusivity, ionic conductivity, and entropy-transport relationships. The signature of caging effects on the Rosenfeld entropy scaling of transport properties is a distinctly steeper dependence of the logarithm of the diffusivity on the excess entropy in ionic melts. This is shown to be true also for a binary Lennard-Jones glassformer, based on available results in the literature. Our results suggest that the onset of a landscape-influenced regime in the dynamics is correlated with this characteristic departure from Rosenfeld scaling. The breakdown of the Nernst-Einstein relation in the ionic melts can also be correlated with the emerging cooperative dynamics.

Relationship between structure, entropy, and diffusivity in water and water-like liquids.

Anomalous behavior of the excess entropy (S(e)) and the associated scaling relationship with diffusivity are compared in liquids with very different underlying interactions but similar water-like anomalies: water (SPC/E and TIP3P models), tetrahedral ionic melts (SiO(2) and BeF(2)), and a fluid with core-softened, two-scale ramp (2SRP) interactions. We demonstrate the presence of an excess entropy anomaly in the two water models. Using length and energy scales appropriate for onset of anomalous behavior, we show the density range of the excess entropy anomaly to be much narrower in water than in ionic melts or the 2SRP fluid. While the reduced diffusivities (D*) conform to the excess-entropy-scaling relation, D* = A exp(alphaS(e)) for all the systems (Rosenfeld, Y. Phys. Rev. A 1977, 15, 2545), the exponential scaling parameter, alpha, shows a small isochore dependence in the case of water. Replacing S(e) by pair correlation-based approximants accentuates the isochore dependence of the diffusivity scaling. Isochores with similar diffusivity-scaling parameters are shown to have the temperature dependence of the corresponding entropic contribution. The relationship between diffusivity, excess entropy, and pair correlation approximants to the excess entropy are very similar in all the tetrahedral liquids.

Excess entropy and structural transitions in a two-dimensional square-shoulder fluid.

Metropolis Monte Carlo simulations on the square-shoulder fluid of Malescio and Pellicane are used to trace the temperature dependent excess entropy, the heat capacity, and configurational energy along several isochores, including those for which mechanically stable zero-temperature structures have been predicted. Thermodynamic signatures of structural phase transitions are identified along several isochores, in addition to the low-density triangular solid and stripe phase transitions identified earlier. The finite temperature phases illustrate the competition between cluster formation and stripe formation as competing mechanisms for generating minimum free energy configurations as a function of density, consistent with earlier results at zero temperature. We also critically examine the usefulness of a phase-ordering rule based on the residual multiparticle entropy (RMPE) in predicting the formation of this diverse set of ordered structures from a disordered fluid phase. For the majority of the isochores studied, the RMPE prediction and the thermodynamic evidence for a phase transition were consistent. However, this criterion fails along isochores that are in regions of coexistence. Thus, the zero-RMPE rule is only likely to be approximately predictive in systems with small phase coexistence regimes, e.g., in the case of liquid crystal forming systems.