Smarajit Karmakar

Growing length and time scales in glass-forming liquids

The glass transition, whereby liquids transform into amorphous solids at low temperatures, is a subject of intense research despite decades of investigation. Explaining the enormous increase in relaxation times of a liquid upon supercooling is essential for understanding the glass transition. Although many theories, such as the Adam–Gibbs theory, have sought to relate growing relaxation times to length scales associated with spatial correlations in liquid structure or motion of molecules, the role of length scales in glassy dynamics is not well established. Recent studies of spatially correlated rearrangements of molecules leading to structural relaxation, termed “spatially heterogeneous dynamics,” provide fresh impetus in this direction. A powerful approach to extract length scales in critical phenomena is finite-size scaling, wherein a system is studied for sizes traversing the length scales of interest. We perform finite-size scaling for a realistic glass-former, using computer simulations, to evaluate the length scale associated with spatially heterogeneous dynamics, which grows as temperature decreases. However, relaxation times that also grow with decreasing temperature do not exhibit standard finite-size scaling with this length. We show that relaxation times are instead determined, for all studied system sizes and temperatures, by configurational entropy, in accordance with the Adam–Gibbs relation, but in disagreement with theoretical expectations based on spin-glass models that configurational entropy is not relevant at temperatures substantially above the critical temperature of mode-coupling theory. Our results provide new insights into the dynamics of glass-forming liquids and pose serious challenges to existing theoretical descriptions.

Breakdown of the Stokes-Einstein relation in two, three, and four dimensions

The breakdown of the Stokes-Einstein (SE) relation between diffusivity and viscosity at low temperatures is considered to be one of the hallmarks of glassy dynamics in liquids. Theoretical analyses relate this breakdown with the presence of heterogeneous dynamics, and by extension, with the fragility of glass formers. We perform an investigation of the breakdown of the SE relation in 2, 3, and 4 dimensions in order to understand these interrelations. Results from simulations of model glass formers show that the degree of the breakdown of the SE relation decreases with increasing spatial dimensionality. The breakdown itself can be rationalized via the difference between the activation free energies for diffusivity and viscosity (or relaxation times) in the Adam-Gibbs relation in three and four dimensions. The behavior in two dimensions also can be understood in terms of a generalized Adam-Gibbs relation that is observed in previous work. We calculate various measures of heterogeneity of dynamics and find that the degree of the SE breakdown and measures of heterogeneity of dynamics are generally well correlated but with some exceptions. The two-dimensional systems we study show deviations from the pattern of behavior of the three- and four-dimensional systems both at high and low temperatures. The fragility of the studied liquids is found to increase with spatial dimensionality, contrary to the expectation based on the association of fragility with heterogeneous dynamics.

Comparison of static length scales characterizing the glass transition.

The dramatic dynamic slowing down associated with the glass transition is considered by many to be related to the existence of a static length scale that grows when temperature decreases. Defining, identifying, and measuring such a length is a subtle problem. Recently, two proposals, based on very different insights regarding the relevant physics, were put forward. One approach is based on the point-to-set correlation technique and the other on the scale where the lowest eigenvalue of the Hessian matrix becomes sensitive to disorder. Here we present numerical evidence that the two approaches might result in the same identical length scale. This provides mutual support for their relevance and, at the same time, raises interesting theoretical questions, discussed in the conclusion.

Statistical Physics of the Yielding Transition in Amorphous Solids

The art of making structural, polymeric, and metallic glasses is rapidly developing with many applications. A limitation is that under increasing external strain all amorphous solids (like their crystalline counterparts) have a finite yield stress which cannot be exceeded without effecting a plastic response which typically leads to mechanical failure. Understanding this is crucial for assessing the risk of failure of glassy materials under mechanical loads. Here we show that the statistics of the energy barriers ΔE that need to be surmounted changes from a probability distribution function that goes smoothly to zero as ΔE=0 to a pdf which is finite at ΔE=0 . This fundamental change implies a dramatic transition in the mechanical stability properties with respect to external strain. We derive exact results for the scaling exponents that characterize the magnitudes of average energy and stress drops in plastic events as a function of system size.

Direct estimate of the static length-scale accompanying the glass transition

Glasses are liquids whose viscosity has increased so much that they cannot flow. Accordingly, there have been many attempts to define a static length-scale associated with the dramatic slowing down of supercooled liquid with decreasing temperature. Here we present a simple method to extract the desired length-scale which is highly accessible both for experiments and for numerical simulations. The fundamental new idea is that low lying vibrational frequencies come in two types, those related to elastic response and those determined by plastic instabilities. The minimal observed frequency is determined by one or the other, crossing at a typical length-scale which is growing with the approach of the glass transition. This length-scale characterizes the correlated disorder in the system: on longer length-scales the details of the disorder become irrelevant, dominated by the Debye model of elastic modes. To connect the newly defined length-scale to relaxation dynamics near the glass transition, we show that supercooled liquids in which there exist random pinning sites of density ρim∼1/ξsd exhibit complete jamming of all dynamics. This is a direct demonstration that the proposed length scale is indeed the static length that was long sought-after.

Adam-Gibbs relation for glass-forming liquids in two, three, and four dimensions.

The Adam-Gibbs relation between relaxation times and the configurational entropy has been tested extensively for glass formers using experimental data and computer simulation results. Although the form of the relation contains no dependence on the spatial dimensionality in the original formulation, subsequent derivations of the Adam-Gibbs relation allow for such a possibility. We test the Adam-Gibbs relation in two, three, and four spatial dimensions using computer simulations of model glass formers. We find that the relation is valid in three and four dimensions. But in two dimensions, the relation does not hold, and interestingly, no single alternate relation describes the results for the different model systems we study.

Do athermal amorphous solids exist

We study the elastic theory of amorphous solids made of particles with finite range interactions in the thermodynamic limit. For the elastic theory to exist, one requires all the elastic coefficients, linear and nonlinear, to attain a finite thermodynamic limit. We show that for such systems the existence of nonaffine mechanical responses results in anomalous fluctuations of all the nonlinear coefficients of the elastic theory. While the shear modulus exists, the first nonlinear coefficient B(2) has anomalous fluctuations and the second nonlinear coefficient B(3) and all the higher order coefficients (which are nonzero by symmetry) diverge in the thermodynamic limit. These results call into question the existence of elasticity (or solidity) of amorphous solids at finite strains, even at zero temperature. We discuss the physical meaning of these results and propose that in these systems elasticity can never be decoupled from plasticity: the nonlinear response must be very substantially plastic.

Predicting Plastic Flow Events in Athermal Shear-Strained Amorphous Solids

We propose a method to predict the value of the external strain where a generic amorphous solid will fail by a plastic response (i.e., an irreversible deformation), solely on the basis of measurements of the nonlinear elastic moduli. While usually considered fundamentally different, with the elastic properties describing reversible phenomena and plastic failure epitomizing irreversible behavior, we show that the knowledge of some nonlinear elastic moduli is enough to predict where plasticity sets in.

Finite Size Scaling for the Glass Transition: the Role of a Static Length Scale

Over the past decade, computer simulations have had an increasing role in shedding light on difficult statistical physical phenomena, and in particular on the ubiquitous problem of the glass transition. Here in a wide variety of materials the viscosity of a supercooled liquid increases by many orders of magnitude upon decreasing the temperature over a modest range. A natural concern in these computer simulations is the very small size of the simulated systems compared to experimental ones, raising the issue of how to assess the thermodynamic limit. Here we turn this limitation to our advantage by performing finite size scaling on the system size dependence of the relaxation time for supercooled liquids to emphasize the importance of a growing static length scale in the theory of glass transition. We demonstrate that the static length scale that was discovered by us in Physica A 391, 1001 (2012) fits the bill extremely well, allowing us to provide a finite-size scaling theory for the α-relaxation time of the glass transition, including predictions for the thermodynamic limit based on simulations in small systems.

Size of plastic events in strained amorphous solids at finite temperatures.

We address the system-size dependence of plastic flow events when an amorphous solid is put under a fixed external strain rate at a finite temperature. For small system sizes at low strain rates and low temperatures the magnitude of plastic events grows with the system size. We explain, however, that this must be a finite-size effect; for larger systems there exist two crossover length scales xi{1} and xi{2}, the first determined by the elastic time scale and the second by the thermal energy scale. For systems of size L>>xi there must exist (L/xi){d} uncorrelated plastic events which occur simultaneously. We present a scaling theory that culminates with the dependence of the crossover scales on temperature and strain rate. Finally, we relate these findings to the temperature and size dependence of the stress fluctuations. We comment on the importance of these considerations for theories of elastoplasticity.