Quantum fluctuations lead to glassy electron dynamics in the good metal regime of electron doped KTaO3.

One of the central challenges in condensed matter physics is to comprehend systems that have strong disorder and strong interactions. In the strongly localized regime, their subtle competition leads to glassy electron dynamics which ceases to exist well before the insulator-to-metal transition is approached as a function of doping. Here, we report on the discovery of glassy electron dynamics deep inside the good metal regime of an electron-doped quantum paraelectric system: KTaO3. We reveal that upon excitation of electrons from defect states to the conduction band, the excess injected carriers in the conduction band relax in a stretched exponential manner with a large relaxation time, and the system evinces simple aging phenomena-a telltale sign of glassy dynamics. Most significantly, we observe a critical slowing down of carrier dynamics below 35 K, concomitant with the onset of quantum paraelectricity in the undoped KTaO3. Our combined investigation using second harmonic generation technique, density functional theory and phenomenological modeling demonstrates quantum fluctuation-stabilized soft polar modes as the impetus for the glassy behavior. This study addresses one of the most fundamental questions regarding the potential promotion of glassiness by quantum fluctuations and opens a route for exploring glassy dynamics of electrons in a well-delocalized regime.

Athermal quasistatic cavitation in amorphous solids: Effect of random pinning.

Amorphous solids are known to fail catastrophically via fracture, and cavitation at nano-metric scales is known to play a significant role in such a failure process. Micro-alloying via inclusions is often used as a means to increase the fracture toughness of amorphous solids. Modeling such inclusions as randomly pinned particles that only move affinely and do not participate in plastic relaxations, we study how the pinning influences the process of cavitation-driven fracture in an amorphous solid. Using extensive numerical simulations and probing in the athermal quasistatic limit, we show that just by pinning a very small fraction of particles, the tensile strength is increased, and also the cavitation is delayed. Furthermore, the cavitation that is expected to be spatially heterogeneous becomes spatially homogeneous by forming a large number of small cavities instead of a dominant cavity. The observed behavior is rationalized in terms of screening of plastic activity via the pinning centers, characterized by a screening length extracted from the plastic-eigenmodes.

Dependence of the Glass Transition and Jamming Densities on Spatial Dimension.

We investigate the dynamics of soft sphere liquids through computer simulations for spatial dimensions from d=3 to 8, over a wide range of temperatures and densities. Employing a scaling of density-temperature-dependent relaxation times, we precisely identify the density ϕ_{0}, which marks the ideal glass transition in the hard sphere limit, and a crossover from sub- to super-Arrhenius temperature dependence. The difference between ϕ_{0} and the athermal jamming density ϕ_{J}, small in 3 and 4 dimensions, increases with dimension, with ϕ_{0}>ϕ_{J} for d>4. We compare our results with recent theoretical calculations.

Method to probe the pronounced growth of correlation lengths in active glass-forming liquids using an elongated probe.

The growth of correlation lengths in equilibrium glass-forming liquids near the glass transition is considered a critical finding in the quest to understand the physics of glass formation. These understandings helped us understand various dynamical phenomena observed in supercooled liquids. It is known that at least two different length scales exist; one is of thermodynamic origin, while the other is dynamical in nature. Recent observations of glassy dynamics in biological and synthetic systems where the external or internal driving source controls the dynamics, apart from the usual thermal noise, lead to the emergence of the field of active glassy matter. A question of whether the physics of glass formation in these active systems is also accompanied by growing dynamic and static lengths is indeed timely. In this article, we probe the growth of dynamic and static lengths in a model active glass system using rod-like elongated probe particles, an experimentally viable method. We show that the dynamic and static lengths in these nonequilibrium systems grow much more rapidly than their passive counterparts. We then offer an understanding of the violation of the Stokes-Einstein relation and Stokes-Einstein-Debye relation using these lengths via a scaling theory.

Soft pinning: Experimental validation of static correlations in supercooled molecular glass-forming liquids.

Enormous enhancement in the viscosity of a liquid near its glass transition is a hallmark of glass transition. Within a class of theoretical frameworks, it is connected to growing many-body static correlations near the transition, often called "amorphous ordering." At the same time, some theories do not invoke the existence of such a static length scale in the problem. Thus, proving the existence and possible estimation of the static length scales of amorphous order in different glass-forming liquids is very important to validate or falsify the predictions of these theories and unravel the true physics of glass formation. Experiments on molecular glass-forming liquids become pivotal in this scenario as the viscosity grows several folds (∼1014), and simulations or colloidal glass experiments fail to access these required long-time scales. Here we design an experiment to extract the static length scales in molecular liquids using dilute amounts of another large molecule as a pinning site. Results from dielectric relaxation experiments on supercooled Glycerol with different pinning concentrations of Sorbitol and Glucose, as well as the simulations on a few model glass-forming liquids with pinning sites, indicate the versatility of the proposed method, opening possible new avenues to study the physics of glass transition in other molecular liquids.

Enhanced vibrational stability in glass droplets.

We show through simulations of amorphous solids prepared in open-boundary conditions that they possess significantly fewer low-frequency vibrational modes compared to their periodic boundary counterparts. Specifically, using measurements of the vibrational density of states, we find that the D(ω)∼ω4 law changes to D(ω)∼ωδ with δ≈5 in two dimensions and δ≈4.5 in three dimensions. Crucially, this enhanced stability is achieved when utilizing slow annealing protocols to generate solid configurations. We perform an anharmonic analysis of the minima corresponding to the lowest frequency modes in such open-boundary systems and discuss their correlation with the density of states. A study of various system sizes further reveals that small systems display a higher degree of localization in vibrations. Lastly, we confine open-boundary solids in order to introduce macroscopic stresses in the system, which are absent in the unconfined system and find that the D(ω)∼ω4 behavior is recovered.

Dynamical heterogeneity in active glasses is inherently different from its equilibrium behavior.

Activity-driven glassy dynamics, while ubiquitous in collective cell migration, intracellular transport, dynamics in bacterial and ant colonies, etc., also extends the scope and extent of the as-yet mysterious physics of glass transition. Active glasses are hitherto assumed to be qualitatively similar to their equilibrium counterparts at an effective temperature, [Formula: see text]. Here, we combine large-scale simulations and an analytical mode-coupling theory (MCT) for such systems and show that, in fact, an active glass is inherently different from an equilibrium glass. Although the relaxation dynamics can be equilibrium-like at a [Formula: see text], effects of activity on the dynamic heterogeneity (DH), which is a hallmark of glassy dynamics, are quite nontrivial and complex. With no preexisting data, we employ four distinct methods for reliable estimates of the DH length scales. Our work shows that active glasses exhibit dramatic growth of DH and systems with similar relaxation times, and thus, [Formula: see text] can have widely varying DH. To theoretically study DH, we extend active MCT and find good qualitative agreement between the theory and simulation results. Our results pave avenues for understanding the role of DH in glassy dynamics and can have fundamental significance even in equilibrium.

Relaxation time scales of interfacial water upon fluid to ripple to gel phase transitions of bilayers.

The slow relaxation of interface water (IW) across three primary phases of membranes is relevant to understand the influence of IW on membrane functions at supercooled conditions. To this objective, a total of ∼16.26µs all-atom molecular dynamics simulations of 1,2-dimyristoyl-sn-glycerol-3-phosphocholine lipid membranes are carried out. A supercooling-driven drastic slow-down in heterogeneity time scales of the IW is found at the fluid to the ripple to the gel phase transitions of the membranes. At both fluid-to-ripple-to-gel phase transitions, the IW undergoes two dynamic crossovers in Arrhenius behavior with the highest activation energy at the gel phase due to the highest number of hydrogen bonds. Interestingly, the Stokes-Einstein (SE) relation is conserved for the IW near all three phases of the membranes for the time scales derived from the diffusion exponents and the non-Gaussian parameters. However, the SE relation breaks for the time scale obtained from the self-intermediate scattering functions. The behavioral difference in different time scales is universal and found to be an intrinsic property of glass. The first dynamical transition in the α relaxation time of the IW is associated with an increase in the Gibbs energy of activation of hydrogen bond breaking with locally distorted tetrahedral structures, unlike the bulk water. Thus, our analyses unveil the nature of the relaxation time scales of the IW across membrane phase transitions in comparison with the bulk water. The results will be useful to understand the activities and survival of complex biomembranes under supercooled conditions in the future.

Quantifying dynamical heterogeneity length scales of interface water across model membrane phase transitions.

All-atom molecular dynamics simulations of 1,2-dimyristoyl-sn-glycero-3-phosphocholine lipid membranes reveal a drastic growth in the heterogeneity length scales of interface water (IW) across fluid to ripple to gel phase transitions. It acts as an alternate probe to capture the ripple size of the membrane and follows an activated dynamical scaling with the relaxation time scale solely within the gel phase. The results quantify the mostly unknown correlations between the spatiotemporal scales of the IW and membranes at various phases under physiological and supercooled conditions.

Universal mechanical instabilities in the energy landscape of amorphous solids: Evidence from athermal quasistatic expansion.

Using numerical simulations, we study the failure of an amorphous solid under athermal quasistatic expansion starting from a homogeneous high-density state. During the expansion process, plastic instabilities occur, manifested via sudden jumps in pressure and energy, with the largest event happening via cavitation leading to the material's yielding. We demonstrate that all these plastic events are characterized by saddle-node bifurcation, during which the smallest nonzero eigenvalue of the Hessian matrix vanishes via a square-root singularity. We find that after yielding and prior to complete fracture, the statistics of pressure or energy jumps corresponding to the plastic events show subextensive system-size scaling, similar to the case of simple shear but with different exponents. Thus, overall, our paper reveals universal features in the fundamental characteristics during mechanical failure in amorphous solids under any quasistatic deformation protocol.

Enhanced short time peak in four-point dynamic susceptibility in dense active glass-forming liquids.

Active glassy systems are simple model systems that imitate complex biological processes. Sometimes, it becomes crucial to estimate the amount of activity present in such biological systems, such as predicting the progression rate of the cancer cells or the healing time of the wound, etc. In this work, we study a model active glassy system to quantify the degree of activity from the collective, long-wavelength fluctuations in the system. These long-wavelength fluctuations present themselves as an additional peak in the four-point dynamic susceptibility (χ4(t)) apart from the usual peak at structural relaxation time. We then show how the degree of the activity at such a small timescale can be obtained by measuring the variation in χ4(t) due to changing activity. A Detailed finite size analysis of the peak height of χ4(t) suggests the existence of an intrinsic dynamic length scale that grows with increasing activity. Finally, we show that this peak height is a unique function of effective activity across all system sizes, serving as a possible parameter for characterizing the degree of activity in a system.

Universal non-Debye low-frequency vibrations in sheared amorphous solids.

We study energy minimised configurations of amorphous solids with a simple shear degree of freedom. We show that the low-frequency regime of the vibrational density of states of structural glass formers is crucially sensitive to the macroscopic stress of the sampled configurations. In both two and three dimensions, shear-stabilised configurations display a D(ωmin) ∼ ω5min regime, as opposed to the ω4min regime observed under unstrained conditions. In order to isolate the source of these deviations from crystalline behaviour, we also study configurations of two dimensional, strained amorphous solids close to a plastic event. We show that the minimum eigenvalue distribution at a strain 'γ' near the plastic event occurring at 'γP' assumes a universal form that displays a collapse when scaled by , and with the number of particles as N-0.22. Notably, at low frequencies, this scaled distribution displays a robust D(ωmin) ∼ ω6min power-law regime, which survives in the large N limit. Finally, we probe the properties of these configurations through a characterisation of the second and third eigenvalues of the Hessian matrix near a plastic event.

Thermodynamics and its correlation with dynamics in a mean-field model and pinned systems: A comparative study using two different methods of entropy calculation.

A recent study introduced a novel mean-field model system where each particle over and above the interaction with its regular neighbors interacts with k extra pseudo-neighbors. Here, we present an extensive study of thermodynamics and its correlation with the dynamics of this system. We surprisingly find that the well-known thermodynamic integration (TI) method of calculating the entropy provides unphysical results. It predicts vanishing of the configurational entropy at temperatures close to the onset temperature of the system and negative values of the configurational entropy at lower temperatures. Interestingly, well below the temperature at which the configurational entropy vanishes, both the collective and the single-particle dynamics of the system show complete relaxation. Negative values of the configurational entropy are unphysical, and complete relaxation when the configurational entropy is zero violates the prediction of the random first-order transition theory (RFOT). However, the entropy calculated using the two-phase thermodynamics (2PT) method remains positive at all temperatures for which we can equilibrate the system, and its values are consistent with RFOT predictions. We find that with an increase in k, the difference in the entropy computed using the two methods increases. A similar effect is also observed for a system where a randomly selected fraction of the particles are pinned in their positions in the equilibrated liquid. We show that the difference in entropy calculated via the 2PT and TI methods increases with pinning density.

Spatial Dimensionality Dependence of Heterogeneity, Breakdown of the Stokes-Einstein Relation, and Fragility of a Model Glass-Forming Liquid.

We investigate the heterogeneity of dynamics, the breakdown of the Stokes-Einstein relation and fragility in a model glass forming liquid, a binary mixture of soft spheres with a harmonic interaction potential for spatial dimensions from 3 to 8. The dynamical heterogeneity is quantified through the dynamical susceptibility χ4 and the non-Gaussian parameter α2. We find that the fragility, the degree of breakdown of the Stokes-Einstein relation, and the heterogeneity of the dynamics decrease with increasing spatial dimensionality. We briefly describe the dependence of fragility on the density and use it to resolve an apparent inconsistency with previous results.

Translational dynamics of a rod-like probe in supercooled liquids: an experimentally realizable method to study Stokes-Einstein breakdown, dynamic heterogeneity, and amorphous order.

The use of probe molecules to extract the local dynamical and structural properties of complex dynamical systems is an age-old technique both in simulations and in experiments. A lot of important information which is not immediately accessible from bulk measurements can be accessed via these local measurements. Still, a detailed understanding of how a probe particle dynamics is affected by the surrounding liquid medium is lacking, especially in the supercooled temperature regime. This work shows how the translational dynamics of a rod-like particle immersed in a supercooled liquid can give us information on the growth of the correlation length scales associated with dynamical heterogeneity and the multi-body static correlations in the medium. This work also provides an understanding of the breakdown of Stokes-Einstein and Stokes-Einstein-Debye relations in supercooled liquids along with a unified scaling theory that rationalizes all the observed results. Finally, this work proposes a novel yet simple method accessible in experiments to measure the growth of these important length scales in molecular glass-forming liquids.

Understanding Slow and Heterogeneous Dynamics in Model Supercooled Glass-Forming Liquids.

Glasses are ubiquitous in nature. Many common items such as ketchups, cosmetic products, toothpaste, etc. and metallic glasses are examples of such glassy materials whose dynamical and rheological properties matter in our daily life. The dynamics of these glass-forming systems are known to be very sluggish and heterogeneous, but a detailed understanding of the origin of such slowing down is still lacking. Slow heterogeneous dynamics occur in a wide variety of systems at scales ranging from microscopic to macroscopic. Polymeric liquids, granular material, such as powder and sand, gels, and foams and also metallic alloys show such complex glassy dynamics at appropriate conditions. Recently, the existence of dynamical heterogeneity has also been found in biological systems starting from collective cell migration in a monolayer of cells to embryonic morphogenesis, cancer invasion, and wound healing. Extensive research in the past decade or so lead to the understanding that there are growing dynamic and static correlation lengths associated with the observed dynamical heterogeneity and rapid rise in viscosity. In this review, we have highlighted the recent developments on measuring these correlation lengths in glass-forming liquids and their possible implications in the physics of the glass transition.

Dynamic coupling of a hydration layer to a fluid phospholipid membrane: intermittency and multiple time-scale relaxations.

Understanding the coupling of a hydration layer and a lipid membrane is crucial to gaining access to membrane dynamics and understanding its functionality towards various biological processes. To find out how significant the mutual influence of the hydration layer and bilayer dynamics is, a fully hydrated 1,2-dimyristoyl-sn-glycero-3-phosphorylcholine (DMPC) lipid bilayer is simulated atomistically in the presence of the TIP4P/2005 water model at 308 K. Interface water (IW) molecules are classified based on their continuous physical proximity or ability to form hydrogen bonds with different moieties of lipid heads. A gradient in retardation of translational mean square displacements is found to operate coherently for both IW and lipid components across the bilayer normal. Deviations from Gaussianity in van Hove correlation functions increase for the lipids and decrease for the IW from the tails to the heads. The IW molecules exhibit Fickian but intermittent dynamics due to coupled vibrations in the local cage formed by the hydrogen bonds with the lipid heads followed by decoupled translational jumps. Importantly, the differences in regional dynamics of lipid heads are clearly reflected in the dynamics of spatially resolved IW molecules physically close to the lipid heads, but not to the dynamics of the hydrogen bonded IW molecules far from the lipid heads. These analyses imply that spatially resolved interface water dynamics can act as a sensitive reflector of regional membrane dynamics occurring at sub ps to hundreds of ps time-scales for several important biological functions at physiological temperature in the future.

Particle pinning suppresses spinodal criticality in the shear-banding instability.

Strained amorphous solids often fail mechanically by creating a shear band. It had been understood that the shear-banding instability is usefully described as crossing a spinodal point (with disorder) in an appropriate thermodynamic description. It remained contested, however, whether the spinodal is critical (with divergent correlation length) or not. Here we offer evidence for critical spinodal by using particle pinning. For a finite concentration of pinned particles the correlation length is bounded by the average distance between pinned particles, but without pinning it is bounded by the system size.

Effect of Pinning on the Yielding Transition of Amorphous Solids.

Using numerical simulations, we have studied the yielding response, in the athermal quasistatic limit, of a model amorphous material having inclusions in the form of randomly pinned particles. We show that, with increasing pinning concentration, the plastic activity becomes more spatially localized, resulting in smaller stress drops, and a corresponding increase in the magnitude of strain where yielding occurs. We demonstrate that, unlike the spatially heterogeneous and avalanche led yielding in the case of the unpinned glass, for the case of large pinning concentration, yielding takes place via a spatially homogeneous proliferation of localized events.

Quantification of spatio-temporal scales of dynamical heterogeneity of water near lipid membranes above supercooling.

A hydrated 1,2-dimyristoyl-sn-glycero-3-phosphorylcholine (DMPC) lipid membrane is investigated using an all atom molecular dynamics simulation at 308 K to determine the physical sources of universal slow relaxations of hydration layers and length-scale of the spatially heterogeneous dynamics. Continuously residing interface water (IW) molecules hydrogen bonded to different moieties of lipid heads in the membrane are identified. The non-Gaussian parameters of all classes of IW molecules show a cross-over from cage vibration to translational diffusion. A significant non-Gaussianity is observed for the IW molecules exhibiting large length correlations in translational van Hove functions. Two time-scales for the ballistic motions and hopping transitions are obtained from the self intermediate scattering functions of the IW molecules with an additional long relaxation, which disappears for bulk water. The long relaxation time-scales for the IW molecules obtained from the self intermediate scattering functions are in good accordance with the hydrogen bond relaxation time-scales irrespective of the nature of the chemical confinement and the confinement lifetime. Employing a block analysis approach, the length-scale of dynamical heterogeneities is captured from a transition from non-Gaussianity to Gaussianity in van Hove correlation functions of the IW molecules. The heterogeneity length-scale is comparable to the wave-length of the small and weak undulations of the membrane calculated by Fourier transforms of lipid tilts. This opens up a new avenue towards a possible correlation between heterogeneity length-scale and membrane curvature more significant for rippled membranes. Thus, our analyses provide a measure towards the spatio-temporal scale of dynamical heterogeneity of confined water near membranes.