Slowdown Of Dynamics Research Articles

Structural origin of excitations in a colloidal glass-former.

Despite decades of intense research, whether the transformation of supercooled liquids into glass is a kinetic phenomenon or a thermodynamic phase transition remains unknown. Here, we analyzed optical microscopy experiments on 2D binary colloidal glass-forming liquids and investigated the structural links of a prominent kinetic theory of glass transition. We examined a possible structural origin for localized excitations, which are building blocks of the dynamical facilitation theory-a purely kinetic approach for the glass transition. To accomplish this, we utilize machine learning methods to identify a structural order parameter termed "softness" that has been found to be correlated with reorganization events in supercooled liquids. Both excitations and softness qualitatively capture the dynamical slowdown on approaching the glass transition and motivated us to explore spatial and temporal correlations between them. Our results show that excitations predominantly occur in regions with high softness and the appearance of these high softness regions precedes excitations, thus suggesting a causal connection between them. Thus, unifying dynamical and thermodynamical theories into a single structure-based framework may provide a route to understand the glass transition.

Local-Average Free Volume Correlates with Dynamics in Glass Formers.

Glass formers exhibit a pronounced slowdown in dynamics, accompanied by progressive heterogeneity as they approach the glass transition. There is intense debate over whether the dramatic slowdown is caused by dynamical heterogeneity and whether the enhanced dynamical heterogeneity originates from structural causes. However, the connection between dynamical heterogeneity and the spatial distribution of the single-particle free volume (a purely static structural quantity) was found to be rather weak, which raises the question of whether dynamic heterogeneity has a purely structural origin. Here, by introducing the concept of local-average free volume, we present numerical evidence that long-time dynamic heterogeneity shows significantly enhanced correlation with the average local free volume over a length scale of a few neighboring shells. Our results resolve the long-standing controversy about whether free volume plays an important role in particle rearrangements associated with the activated hopping relaxation. The concept of "local average" can be applied to other local structural descriptors to better correlate with dynamic heterogeneity in glass-forming liquids.

Electrically Tunable Nonequilibrium Optical Response of Graphene.

The ability to tune the optical response of a material via electrostatic gating is crucial for optoelectronic applications, such as electro-optic modulators, saturable absorbers, optical limiters, photodetectors, and transparent electrodes. The band structure of single layer graphene (SLG), with zero-gap, linearly dispersive conduction and valence bands, enables an easy control of the Fermi energy, EF, and of the threshold for interband optical absorption. Here, we report the tunability of the SLG nonequilibrium optical response in the near-infrared (1000–1700 nm/0.729–1.240 eV), exploring a range of EF from −650 to 250 meV by ionic liquid gating. As EF increases from the Dirac point to the threshold for Pauli blocking of interband absorption, we observe a slow-down of the photobleaching relaxation dynamics, which we attribute to the quenching of optical phonon emission from photoexcited charge carriers. For EF exceeding the Pauli blocking threshold, photobleaching eventually turns into photoinduced absorption, because the hot electrons’ excitation increases the SLG absorption. The ability to control both recovery time and sign of the nonequilibrium optical response by electrostatic gating makes SLG ideal for tunable saturable absorbers with controlled dynamics.

How Far Is "Bulk Water" from Interfaces? Depends on the Nature of the Surface and What We Measure.

Using systematic molecular dynamics (MD) simulations, we revisit the question: At what distance from an interface do the properties of "bulk water" get recovered? We have considered three different kinds of interfaces: nonpolar (hydrophobic; isooctane-water interface), charged (negative; AOT bilayer), and polar (zwitterionic; POPC bilayer). In order to interrogate the extent of perturbation of the interfacial water molecules as a function of the distance from the interface, we utilize a diverse range of structural and dynamical parameters. To capture the structural perturbations, we look into local density (translational order), local tetrahedral order parameter, and dipolar orientation of the water molecules. We also explore the anisotropic diffusion of the water molecules in the direction perpendicular to the interface as well as the planar diffusion parallel to the interface in a distance dependent manner. In addition, the orientational time correlation functions have been computed to understand the extent of slowdown in the rotational dynamics. As expected, the electrostatic field emanating from the charged AOT interface seems to have the highest long-range effect on the orientational order and dynamics of the water molecules, whereas specific interactions like hydrogen bonding and electrostatic interaction lead to significant trapping and kinetic slowdown for both AOT and POPC (zwitterionic) very close to the interface. Our analysis highlights that not only the length-scale of perturbation depends on the nature of the interfaces and specific interactions but also the type of water property that we measure/calculate. Different water properties seem to have widely different length-scale of perturbation. Orientational order parameters seem to be perturbed to a much longer length-scale as compared to translational order parameters. The global orientational order of water can be perturbed even up to ∼4-5 nm near the negatively charged AOT surface in the absence of any extra electrolyte. This observation has significant implication toward the interpretation of experimental measurements as well since different spectroscopic techniques would probe different parameters or water properties with possible mutual disagreement and inconsistency between different types of measurements. Thus, our study provides a broader and unifying perspective toward the aspect of "context dependent" structural and dynamical perturbation of "interfacial water".

Effect of ring stiffness and ambient pressure on the dynamical slowdown in ring polymers.

Using extensive molecular dynamics simulations, we investigate the slowdown of dynamics in a 3D system of ring polymers by varying the ambient pressure and the stiffness of the rings. Our study demonstrates that the stiffness of the rings determines the dynamics of the ring polymers, leading to glassiness at lower pressures for stiffer rings. The threading of the ring polymers, a unique feature that emerges only due to the topological nature of such polymers in three dimensions, is shown to be the determinant feature of dynamical slowdown, albeit only in a certain stiffness range. Our results suggest a possible framework for exploring the phase space spanned by ring stiffness and pressure to obtain spontaneously emerging topologically constrained polymer glasses.

Cage Length Controls the Nonmonotonic Dynamics of Active Glassy Matter.

Dense active matter is gaining widespread interest due to its remarkable similarity with conventional glass-forming materials. However, active matter is inherently out of equilibrium and even simple models such as active Brownian particles (ABPs) and active Ornstein-Uhlenbeck particles (AOUPs) behave markedly differently from their passive counterparts. Controversially, this difference has been shown to manifest itself via either a speedup, slowdown, or nonmonotonic change of the glassy relaxation dynamics. Here we rationalize these seemingly contrasting views on the departure from equilibrium by identifying the ratio of the short-time length scale to the cage length, i.e., the length scale of local particle caging, as a vital and unifying control parameter for active glassy matter. In particular, we explore the glassy dynamics of both thermal and athermal ABPs and AOUPs upon increasing the persistence time. We find that for all studied systems there is an optimum of the dynamics; this optimum occurs when the cage length coincides with the corresponding short-time length scale of the system, which is either the persistence length for athermal systems or a combination of the persistence length and a diffusive length scale for thermal systems. This new insight, for which we also provide a simple physical argument, allows us to reconcile and explain the manifestly disparate departures from equilibrium reported in many previous studies of dense active materials.

Glassy feature in melts of 3-dimensional architectured polymer blends

3-dimensional architectured polymers, for example, giant molecules, present distinct dynamics from chain-like polymers and are coarse-grained as soft-clusters. There is a critical number of beads, above which their melts cannot relax under thermal energy and become cooperative glass. To reveal the role of dispersity, we study the dynamics of binary blends of giant molecules with the same glass transition temperature by rheological experiments and by molecular dynamics simulations. The large component of the blend, OPOSS24 or 141335, contains more beads than the critical number and forms cooperative glass, while the small component contains less beads than the critical number. The gradual change of volume fraction allows us to fine-adjust the average number of beads. An abrupt slowdown happens only if the volume fraction of the large component reaches 80%. Both experimental and simulated data can be described by a Vogel–Fulcher–Tammann-like equation against volume fractions with only one fitting parameter. The divergent relaxation times can also be rewritten as a function of the average number of beads. Such abrupt dynamic slowdown has to be induced by the glass-like cooperative dynamics. The cooperative glass state may only be reached when the majority of giant molecules or generally speaking, soft-clusters, are large enough. If we regard binary blends of soft-clusters as large and small cooperative rearranging regions, this may provide a direct approach to glass problems and may shed light on our understanding.

High-dimensional percolation criticality and hints of mean-field-like caging of the random Lorentz gas.

The random Lorentz gas (RLG) is a minimal model for transport in disordered media. Despite the broad relevance of the model, theoretical grasp over its properties remains weak. For instance, the scaling with dimension d of its localization transition at the void percolation threshold is not well controlled analytically nor computationally. A recent study [Biroli et al., Phys. Rev. E 103, L030104 (2021)2470-004510.1103/PhysRevE.103.L030104] of the caging behavior of the RLG motivated by the mean-field theory of glasses has uncovered physical inconsistencies in that scaling that heighten the need for guidance. Here we first extend analytical expectations for asymptotic high-d bounds on the void percolation threshold and then computationally evaluate both the threshold and its criticality in various d. In high-d systems, we observe that the standard percolation physics is complemented by a dynamical slowdown of the tracer dynamics reminiscent of mean-field caging. A simple modification of the RLG is found to bring the interplay between percolation and mean-field-like caging down to d=3.

Revealing the role of hydrogen bonding in polyurea with multiscale simulations

ABSTRACT Typically, polyurea is a polymer forming microphase-separated structures. Various coarse-grained (CG) simulation models have been developed to study the microphase structure and viscoelastic properties of polyurea. However, since the hydrogen atoms were modelled implicitly in the existing CG models, the anisotropic hydrogen bonding between urea groups in the hard domain might not be treated properly. Here, we introduce a hybrid all-atom/coarse-grained (AA/CG) model for polyurea, the CGU model, in which atomistic resolution are preserved for the urea groups. This model is proven to reproduce the results of the AA model, despite 24 times faster to run. By comparing the traditional CG model and the CGU model, we found that hydrogen bonding leads to a head-to-tail arrangement of the urea groups and a significant slowdown of the hard segment dynamics. Non-equilibrium simulations of stress relaxation process indicate that hydrogen bonding causes a broad relaxation time spectrum, which is consistent with experiment results.

Thermoresponsivity of poly(N-isopropylacrylamide) microgels in water-trehalose solution and its relation to protein behavior

HypothesesAdditives are commonly used to tune macromolecular conformational transitions. Among additives, trehalose is an excellent bioprotectant and among responsive polymers, PNIPAM is the most studied material. Nevertheless, their interaction mechanism so far has only been hinted without direct investigation, and, crucially, never elucidated in comparison to proteins. Detailed insights would help understand to what extent PNIPAM microgels can effectively be used as synthetic biomimetic materials, to reproduce and study, at the colloidal scale, isolated protein behavior and its sensitivity to interactions with specific cosolvents or cosolutes. ExperimentsThe effect of trehalose on the swelling behavior of PNIPAM microgels was monitored by dynamic light scattering; Raman spectroscopy and molecular dynamics simulations were used to explore changes of solvation and dynamics across the swelling-deswelling transition at the molecular scale. FindingsStrongly hydrated trehalose molecules develop water-mediated interactions with PNIPAM microgels, thereby preserving polymer hydration below and above the transition while drastically inhibiting local motions of the polymer and of its hydration shell. Our study, for the first time, demonstrates that slowdown of dynamics and preferential exclusion are the principal mechanisms governing trehalose effect on PNIPAM microgels, at odds with preferential adsorption of alcohols, but in full analogy with the behavior observed in trehalose-protein systems.

Slowdown of Water Dynamics from the Top to the Bottom of the GroEL Cavity.

The GroE molecular chaperone system is a critical protein machine that assists the folding of substrate proteins in its cavity. Water in the cavity is suspected to play a role in substrate protein folding, but the mechanism is currently unknown. Herein, we report measurements of water dynamics in the equatorial and apical domains of the GroEL cavity in the apo and football states, using site-specific tryptophanyl mutagenesis as an intrinsic optical probe with femtosecond resolution combined with molecular dynamics simulations. We observed clearly different water dynamics in the two domains with a slowdown of the cavity water from the apical to equatorial region in the football state. The results suggest that the GroEL cavity provides a unique water environment that may facilitate substrate protein folding.

Spin Dynamics Slowdown near the Antiferromagnetic Critical Point in Atomically Thin FePS3.

Two-dimensional (2D) magnetic materials have attracted much recent interest with unique properties emerging at the few-layer limit. Beyond the reported impacts on the static magnetic properties, the effects of reducing the dimensionality on the magnetization dynamics are also of fundamental interest and importance for 2D device development. In this report, we investigate the spin dynamics in atomically thin antiferromagnetic FePS3 of varying layer numbers using ultrafast pump-probe spectroscopy. Following the absorption of an optical pump pulse, the time evolution of the antiferromagnetic order parameter is probed by magnetic linear birefringence. We observe a strong divergence in the demagnetization time near the Néel temperature. The divergence can be characterized by a power-law dependence on the reduced temperature, with an exponent decreasing with sample thickness. We compare our results to expectations from critical slowing down and a two-temperature model involving spins and phonons and discuss the possible relevance of spin-substrate phonon interactions.

Does Electric Friction Matter in Living Cells?

The thermal motion of charged proteins causes randomly fluctuating electric fields inside cells. According to the fluctuation–dissipation theorem, there is an additional friction force associated with such fluctuations. However, the impact of these fluctuations on the diffusion and dynamics of proteins in the cytoplasm is unclear. Here, we provide an order-of-magnitude estimate of this effect by treating electric field fluctuations within a generalized Langevin equation model with a time-dependent friction memory kernel. We find that electric friction is generally negligible compared to solvent friction. However, a significant slowdown of protein diffusion and dynamics is expected for biomolecules with high net charges such as intrinsically disordered proteins and RNA. The results show that direct contacts between biomolecules in a cell are not necessarily required to alter their dynamics.

Hydrogen-induced dynamic slowdown of metallic glass-forming liquids* *Project supported by the National Natural Science Foundation of China (Grant No. 52071029). The computer resources at the Shanghai and Tianjin Supercomputer Centers are gratefully acknowledged.

Dynamics of hydrogen doped Cu50Zr50 glass-forming liquids are investigated by using the newly developed modified embedded atomic method (MEAM) potential based on molecular dynamics simulations. We find that the doping of hydrogen atoms slows down the relaxation dynamics, reduces the fragility of supercooled melts, and promotes the occurrence of glass transitions. The dynamic slowdown is suggested to be closely related to the effect of hydrogen atoms on locally ordered structure of melts. With increasing concentration of hydrogen, the five-fold symmetry associated with Cu- and Zr-centered polyhedrons is lowered, on the other hand, the local order featuring metal hydrides is enhanced. The latter dominates the dynamic behaviors of glass-forming liquids, especially for Zr atoms, and results in the dynamic slowdown.

Mechanisms of bulk and surface diffusion in metallic glasses determined from molecular dynamics simulations

The bulk and surface dynamics of Cu50Zr50 metallic glass were studied using classical molecular dynamics (MD) simulations. As the alloy undergoes cooling, it passes through liquid, supercooled, and glassy states. While bulk dynamics showed a marked slowing down prior to glass formation, with increasing activation energy, the slowdown in surface dynamics was relatively subtle. The surface exhibited a lower glass transition temperature than the bulk, and the dynamics preceding the transition were accurately described by a temperature-independent activation energy. Surface dynamics were much faster than bulk at a given temperature in the supercooled state, but surface and bulk dynamics were found to be very similar when compared at their respective glass transition temperatures. The manifestation of dynamical heterogeneity, as characterized by the non-Gaussian parameter and breakdown of the Stokes-Einstein equation, was also similar between bulk and surface for temperatures scaled by their respective glass transition temperatures. Individual atom motion was dominated by a cage and jump mechanism in the glassy state for both the bulk and surface. We utilize this cage and jump mechanisms to separate the activation energy for diffusion into two parts: (i) cage-breaking barrier (Q1), associated with the rearrangement of neighboring atoms to free up space and (ii) the subsequent jump barrier (Q2). It was observed that Q1 dominates Q2 for both bulk and surface diffusion, and the difference in activation energies for bulk and surface diffusion mainly arose from the differences in cage-breaking barrier Q1.

Factors correlating to enhanced surface diffusion in metallic glasses.

The enhancement of surface diffusion (DS) over the bulk (DV) in metallic glasses (MGs) is well documented and likely to strongly influence the properties of glasses grown by vapor deposition. Here, we use classical molecular dynamics (MD) simulations to identify different factors influencing the enhancement of surface diffusion in MGs. MGs have a simple atomic structure and belong to the category of moderately fragile glasses that undergo pronounced slowdown of bulk dynamics with cooling close to the glass transition temperature (Tg). We observe that DS exhibits a much more moderate slowdown compared to DV when approaching Tg, and DS/DV at Tg varies by two orders of magnitude among the MGs investigated. We demonstrate that both the surface energy and the fraction of missing bonds for surface atoms show good correlation to DS/DV, implying that the loss of nearest neighbors at the surface directly translates into higher mobility, unlike the behavior of network-bonded and hydrogen-bonded organic glasses. Fragility, a measure of the slowdown of bulk dynamics close to Tg, also correlates to DS/DV, with more fragile systems having larger surface enhancement of mobility. The deviations observed in the fragility-DS/DV relationship are shown to be correlated to the extent of segregation or depletion of the mobile element at the surface. Finally, we explore the relationship between the diffusion pre-exponential factor (D0) and the activation energy (Q) and compare it to a ln(D0)-Q correlation previously established for bulk glasses, demonstrating similar correlations from MD as in the experiments and that the surface and bulk have very similar ln(D0)-Q correlations.

Dynamics of a fractal set of first-order magnetic phase transitions in frustrated Lu2CoMnO6

Magnetic frustration can produce exotic spin configurations and dynamics. Here, the authors explore the seemingly simple competition between ferromagnetic nearest- and antiferromagnetic next-nearest neighbor interactions along Ising spin chains, as realized in the magnetoelectric compound Lu${}_{2}$CoMnO${}_{6}$. Commonly, this situation is described by the axial next-nearest-neighbor Ising model. For the first time, the authors measure and calculate its correlated magnetic dynamics, resulting from a characteristic fractal set of first-order phase boundaries. Experiments and Monte Carlo simulations reveal a dynamics slowdown while approaching the phase transition regime.

Dispersion at Single Unit TiO2 Nanoparticles Reduced Tg, Induced Chain Disentanglement and Reduced Tensile Modulus in Waterborne Acrylic Coatings

AbstractSpatially distributed TiO2 nanoparticles induced an order of magnitude decrease of glass transition temperature, Tg, and chain disentanglement in waterborne acrylic coatings. Acrylic/TiO2 coatings are synthesized in situ by batch emulsion polymerization. The copolymer is based on butyl acrylate (BA), methyl methacrylate (MMA), and acrylic acid (AA) with composition 56:42:2 mol%, and nano‐TiO2 (ca. 12 nm) is incorporated up to 3 wt% content. Transmission electron microscopy (TEM) showed that TiO2 is dispersed at nearly single unit throughout the acrylic matrix. The nanoparticle reduced Tg and broadened the temperature range of the glass transition, δTg. The considerable increase of δTg suggests gradients of dynamics. Shear rheometry demonstrated that TiO2 induced chain disentanglement, the rubbery modulus Ge decreased two orders of magnitude with only 1 wt% TiO2 content thus increasing the packing length p (and the reptation tube diameter as dt = kp, k > 1). Consequently, the tensile Young's modulus E decreased an order of magnitude, relative to the neat copolymer. The reduction of Tg, the slowdown of macromolecular dynamics, the chain disentanglement and the increase of dt suggests dynamics modification due to intercalation of the entangled web by the TiO2 nanoparticles, and these results may be ascribed to a nanoconfinement effect.

How mobile is the water in the reverse micelles? A 2DIR study with an ultrasmall IR probe

Water molecules in reverse micelle serve as an excellent model for biological water. However, it has been argued previously that water molecules at the centre, even for smaller sized water pools of reverse micelles, behave like bulk water, using ultrafast vibrational lifetime measurements of azide ion. In the present investigation, the vibrational dynamics of an ultrasmall IR probe, azide ion, has been studied in AOT reverse micelle, at various w0 (radius of water pool), using linear IR measurements, vibrational lifetime measurements and 2D-IR measurements. While linear IR measurements show gradual variation in spectral parameters, such as, peak position and width of the vibrational transition, suggesting a gradual change in the micro environment of the probe with variation in radius of the water pool, the vibrational lifetime remains indistinguishable with variation in w0, which has been ascribed earlier to the location of azide ion in the centre of the water pool. Herein, ultrafast 2DIR spectroscopy convincingly demonstrates that, for a smaller sized water pool, the water molecules, even at the centre of the water pool, behave significantly different as compared to bulk water, an inference, which is missed by the previous vibrational lifetime measurements, and suggest an extensive slowdown of the hydrogen bond relaxation dynamics as compared to bulk water.

Thermodynamic and Kinetic Transitions of Liquids in Nanoconfinement.

Core principles of chemistry are ubiquitously invoked to shed light on the nature of molecular level interactions in nanoconfined fluids, which play a pivotal role in a wide range of processes in geochemistry, biology, and engineering. A detailed understanding of the physicochemical processes involved in the flow, structural transitions, and freezing or melting behavior of fluids confined within nanometer-sized pores of solid materials is thus of enormous importance for both basic research and technological applications.This Account provides a perspective on new insights into the thermodynamic and kinetic transitions of nanoconfined fluids in their stable and metastable forms. After briefly introducing the unique properties of mesoporous silicas from the SBA, MCM, and FDU families that serve as the confinement matrices, combining highly ordered single and bimodal mesopore architectures with tunable pore sizes in the ∼2-15 nm range and narrow size distributions, recent studies on melting/freezing behavior of water confined in these host matrices are reviewed. While differential scanning calorimetry (DSC) reveals a linear relationship between melting point depression and pore size (independent of the pore shape), as predicted by the Gibbs-Thomson relation, variable temperature 2H wide-line nuclear magnetic resonance (NMR) spectroscopy studies confirm the core-shell model of water and give evidence for a layer-by-layer freezing mechanism, which gives rise to an apparent fragile-to-strong transition in the solidification dynamics.In contrast to the freezing/melting behavior of water, the effect of nanoconfinement on the glass transition of supercooled liquids is nonuniversal and the glass transition temperature Tg can either increase or decrease with the dimensionality and extent of confinement. This nonuniversal behavior is exemplified by the two glass-forming molecular liquids, glycerol and ortho-terphenyl (OTP). While glycerol shows an increase in Tg and a pronounced slowdown of the rotational dynamics of the constituent molecules due to a change in the molecular packing between the bulk and the confined liquid, OTP displays a linear and confining-media-dependent depression of Tg with increased confinement that is strongly influenced by the pore-liquid interface characteristics.This Account concludes with a focus on recent experimental evidence of extreme spatial and dynamical heterogeneity in both freezing and glass transition processes. This discovery was enabled by the unique mesoporous structures of SBA-16 and FDU-5, possessing bimodal architectures with two interconnected pore types of different size and shape (spherical and cylindrical). For the very first time, two melting points for water and two glass transitions for supercooled OTP, corresponding to a specific pore type, were observed. Collectively, these observations strongly suggest a close mechanistic connection between the local fluctuations in the structure and dynamics of nanoconfined liquids. While the findings reviewed in this Account provide new insights into thermodynamic and kinetic transitions of fluids, there remain many unanswered questions regarding the effects of nanoconfinement on the fundamental properties of fluids, which offer exciting future opportunities in chemical research.