Search

Beyond well-documented confinement and surface effects arising from the large internal surface and severely confining porosity of nanoporous hosts, the transport of nanoconfined fluids remains puzzling in many aspects. With striking examples such as memory, i.e., non-viscous effects, intermittent dynamics, and surface barriers, the dynamics of fluids in nanoconfinement challenge classical formalisms (e.g., random walk, viscous/advective transport)—especially for molecular pore sizes. In this context, while molecular frameworks such as intermittent Brownian motion, free volume theory, and surface diffusion are available to describe the self-diffusion of a molecularly confined fluid, a microscopic theory for collective diffusion (i.e., permeability), which characterizes the flow induced by a thermodynamic gradient, is lacking. Here, to fill this knowledge gap, we invoke the concept of "De Gennes narrowing," which relates the wavevector-dependent collective diffusivity D0(q) to the fluid structure factor S(q). First, using molecular simulation for a simple yet representative fluid confined in a prototypical solid (zeolite), we unravel an essential coupling between the wavevector-dependent collective diffusivity and the structural ordering imposed on the fluid by the crystalline nanoporous host. Second, despite this complex interplay with marked Bragg peaks in the fluid structure, the fluid collective dynamics is shown to be accurately described through De Gennes narrowing. Moreover, in contrast to the bulk fluid, the departure from De Gennes narrowing for the confined fluid in the macroscopic limit remains small as the fluid/solid interactions in severe confinement screen collective effects and, hence, weaken the wavevector dependence of collective transport. [ABSTRACT FROM AUTHOR]

Quasi-two-dimensional (quasi-2D) colloidal hard-sphere suspensions confined in a slit geometry are widely used as two-dimensional (2D) model systems in experiments that probe the glassy relaxation dynamics of 2D systems. However, the question to what extent these quasi-2D systems indeed represent 2D systems is rarely brought up. Here, we use computer simulations that take into account hydrodynamic interactions to show that dense quasi-2D colloidal bi-disperse hard-sphere suspensions exhibit much more rapid diffusion and relaxation than their 2D counterparts at the same area fraction. This difference is induced by the additional vertical space in the quasi-2D samples in which the small colloids can move out of the 2D plane, therefore allowing overlap between particles in the projected trajectories. Surprisingly, this difference in the dynamics can be accounted for if, instead of using the surface density, one characterizes the systems by means of a suitable structural quantity related to the radial distribution function. This implies that in the two geometries, the relevant physics for glass formation is essentially identical. Our results provide not only practical implications on 2D colloidal experiments but also interesting insights into the 3D-to-2D crossover in glass-forming systems. [ABSTRACT FROM AUTHOR]

The quantum harmonic oscillator is the fundamental building block to compute thermal properties of virtually any dielectric crystal at low temperatures in terms of phonons, extended further to cases with anharmonic couplings, or even disordered solids. In general, Path Integral Monte Carlo or Path Integral Molecular Dynamics methods are powerful tools to determine stochastically thermodynamic quantities without systematic bias, not relying on perturbative schemes. Addressing transport properties, for instance calculating thermal conductivity from PIMC, however, is substantially more difficult. Although correlation functions of current operators can be determined by PIMC from analytic continuation on the imaginary time axis, Bayesian methods are usually employed for the numerical inversion back to real time response functions. This task not only strongly relies on the accuracy of the PIMC data but also introduces noticeable dependence on the model used for the inversion. Here, we address both difficulties with care. In particular, we first devise improved estimators for current correlations, which substantially reduce the variance of the PIMC data. Next, we provide a neat statistical approach to the inversion problem, blending into a fresh workflow the classical stochastic maximum entropy method together with recent notions borrowed from statistical learning theory. We test our ideas on a single harmonic oscillator and a collection of oscillators with a continuous distribution of frequencies and provide indications of the performance of our method in the case of a particle in a double well potential. This work establishes solid grounds for an unbiased, fully quantum mechanical calculation of transport properties in solids. [ABSTRACT FROM AUTHOR]

In this work using computer simulations of 3D model of dense disordered solids we show, for the first time, the appearance of shear localization in the stationary flow under homogeneous driving conditions. To rationalize our simulation results we develop a continuum model, that couples the dynamics of the local flow to the evolution of a kinetic temperature field related to the local inertial dynamics. Our model predicts that the coupling of the flow field to this additional destabilizing field appears only as a necessary condition for shear localization, a minimum system size is necessary to accommodate the flow instability. Moreover we show that this size criterion resulting from our continuum description is in quantitative agreement with our particle-based simulation results. [ABSTRACT FROM AUTHOR]

We investigate the temperature dependence of thermodynamic (density and isobaric heat capacity), dynamical (self-diffusion coefficient and shear viscosity), and dielectric properties of several water models, such as the commonly employed TIP3P water model, the well-established four-point water model TIP4P-2005, and the recently developed four-point water model TIP4P-D. We focus on the temperature range of interest for the field of computational biophysics and soft matter (280–350 K). The four-point water models lead to a spectacularly improved agreement with experimental data, strongly suggesting that the use of more modern parameterizations should be favored compared to the more traditional TIP3P for modeling temperature-dependent phenomena in biomolecular systems. [ABSTRACT FROM AUTHOR]

We present a computer simulation of entangled polymer solutions at equilibrium. The chains repel each other via a soft Gaussian potential, appropriate for semi-dilute solutions at the scale of a correlation blob. The key innovation to suppress chain crossings is to use a pseudo-continuous model of a backbone which effectively leaves no gaps between consecutive points on the chain, unlike the usual bead-and-spring model. Our algorithm is sufficiently fast to observe the entangled regime using a standard desktop computer. The simulated structural and mechanical correlations are in fair agreement with the expected predictions for a semi-dilute solution of entangled chains. [ABSTRACT FROM AUTHOR]

Diffusion of a particle through an energy and diffusivity landscape is a very general phenomenon in numerous systems of soft and condensed matter. On the one hand, theoretical frameworks such as Langevin and Fokker-Planck equations present valuable accounts to understand these motions in great detail, and numerous studies have exploited these approaches. On the other hand, analytical solutions for correlation functions, as, e.g., desired by experimentalists for data fitting, are only available for special cases. We explore the possibility to use different theoretical methods in the specific picture of time-dependent switching between diffusive states to derive analytical functions that allow to link experimental and simulation results to theoretical calculations. In particular, we present a closed formula for diffusion switching between two states, as well as a general recipe of how to generalize the formula to multiple states. [ABSTRACT FROM AUTHOR]

Electrokinetic flows of an aqueous NaCl solution in nanochannels with negatively charged surfaces are studied using molecular dynamics simulations. The four transport coefficients that characterize the response to weak electric and pressure fields, namely, the coefficients for the electrical current in response to the electric field (Mjj) and the pressure field (Mjm), and those for the mass flow in response to the same fields (Mmj and Mmm), are obtained in the linear regime using a Green-Kubo approach. Nonequilibrium simulations with explicit external fields are also carried out, and the current and mass flows are directly obtained. The two methods exhibit good agreement even for large external field strengths, and Onsager's reciprocal relation (Mjm = Mmj) is numerically confirmed in both approaches. The influence of the surface charge density on the flow is also considered. The values of the transport coefficients are found to be smaller for larger surface charge density, because the counter-ions strongly bound near the channel surface interfere with the charge and mass flows. A reversal of the streaming current and of the reciprocal electro-osmotic flow, with a change of sign of Mmj due to the excess co-ions, takes places for very high surface charge density. [ABSTRACT FROM AUTHOR]

We present a numerical study of the slip link model introduced by Likhtman for describing the dynamics of dense polymer melts. After reviewing the technical aspects associated with the implementation of the model, we extend previous work in several directions. The dependence of the relaxation modulus with the slip link density and the slip link stiffness is reported. Then the nonlinear rheological properties of the model, for a particular set of parameters, are explored. Finally, we introduce excluded volume interactions in a mean field such as manner in order to describe inhomogeneous systems, and we apply this description to a simple nanocomposite model. With this extension, the slip link model appears as a simple and generic model of a polymer melt, that can be used as an alternative to molecular dynamics for coarse grained simulations of complex polymeric systems. [ABSTRACT FROM AUTHOR]

Mechanical deformation of amorphous solids can be described as consisting of an elastic part in which the stress increases linearly with strain, up to a yield point at which the solid either fractures or starts deforming plastically. It is well established, however, that the apparent linearity of stress with strain is actually a proxy for a much more complex behavior, with a microscopic plasticity that is reflected in diverging nonlinear elastic coefficients. Very generally, the complex structure of the energy landscape is expected to induce a singular response to small perturbations. In the athermal quasistatic regime, this response manifests itself in the form of a scale-free plastic activity. The distribution of the corresponding avalanches should reflect, according to theoretical mean-field calculations [S. Franz and S. Spigler, Phys. Rev. E 95, 022139 (2017)], the geometry of phase space in the vicinity of a typical local minimum. In this work, we characterize this distribution for simple models of glass-forming systems, and we find that its scaling is compatible with the mean-field predictions for systems above the jamming transition. These systems exhibit marginal stability, and scaling relations that hold in the stationary state are examined and confirmed in the elastic regime. By studying the respective influence of system size and age, we suggest that marginal stability is systematic in the thermodynamic limit. [ABSTRACT FROM AUTHOR]

We investigate the problem of heat conduction across molecular junctions connecting two nanoparticles, both in vacuum and in a liquid environment, using classical molecular dynamics simulations. In vacuum, the well-known result of a length independent conductance is recovered; its precise value, however, is found to depend sensitively on the overlap between the vibrational spectrum of the junction and the density of states of the nanoparticles that act as thermal contacts. In a liquid environment, the conductance is constant up to a crossover length, above which a standard Fourier regime is recovered. [ABSTRACT FROM AUTHOR]

We use coarse-grained molecular dynamics simulations to perform tensile test deformation on glassy and rubbery polymer samples using two types of driving for the deformation. We compare the outcome from a standard homogeneous deformation procedure with that of a boundary driven procedure in which the sample is driven by the nanometric equivalent of grips. No significant difference is observed in both uniaxial and triaxial tensile experiments. Implications for testing the behavior of nonhomogeneous polymer materials are briefly discussed. [ABSTRACT FROM AUTHOR]

Polymer nanocomposites have been widely studied in efforts to engineer materials with mechanical properties superior to those of the pure polymer, but the molecular origins of the sought-after improved properties have remained elusive. An ideal polymer nanocomposite model has been conceived in which the nanoparticles are dispersed throughout the polymeric matrix. A detailed examination of topological constraints (or entanglements) in a nanocomposite glass provides new insights into the molecular origin of the improved properties in polymer nanocomposites by revealing that the nanoparticles impart significant enhancements to the entanglement network. Nanoparticles are found to serve as entanglement attractors, particularly at large deformations, altering the topological constraint network that arises in the composite material. [ABSTRACT FROM AUTHOR]

We report results of nonequilibrium molecular dynamics simulations of a one-component glassy system under the influence of a shear flow, with the aim of investigating shear-induced ordering of this system. In spite of the very low temperature, the system transforms into a strained crystalline state through well defined nucleation events. Various characteristics of the observed ordering at different strain rates and temperatures are discussed. We also define and discuss the transition rates. [ABSTRACT FROM AUTHOR]

A versatile method is proposed to generate configurations of coarse-grained models for polymer melts. This method, largely inspired by chemical “radical polymerization,” is divided in three stages: (i) nucleation of radicals (reacting molecules caching monomers), (ii) growth of chains within a solvent of monomers and (iii) termination: annihilation of radicals and removal of residual monomers. The main interest of this method is that relaxation is performed while chains are generated. Pure mono and polydisperse polymer melts are generated and compared to the configurations generated by the push off method from Auhl et al. [J. Chem. Phys. 119, 12718 (2003)]. A detailed study of the static properties (radius of gyration, mean square internal distance, entanglement length) confirms that the radical-like polymerization technique is suitable to generate equilibrated melts. Moreover, the method is flexible and can be adapted to generate nanostructured polymers, namely, diblock and triblock copolymers. [ABSTRACT FROM AUTHOR]

The nonequilibrium dynamics of a binary Lennard-Jones mixture in a simple shear flow is investigated by means of molecular dynamics simulations. The range of temperature T investigated covers both the liquid, supercooled, and glassy states, while the shear rate γ covers both the linear and nonlinear regimes of rheology. The results can be interpreted in the context of a nonequilibrium, schematic mode-coupling theory developed recently, which makes the theory applicable to a wide range of soft glassy materials. The behavior of the viscosity η(T, γ) is first investigated. In the nonlinear regime, strong shear-thinning is obtained, η∼γ[sup -α(T)], with α(T)...⅔ in the supercooled regime. Scaling properties of the intermediate scattering functions are studied. Standard "mode-coupling properties" of factorization and time superposition hold in this nonequilibrium situation. The fluctuation-dissipation relation is violated in the shear flow in a way very similar to that predicted theoretically, allowing for the definition of an effective temperature T[sub eff] for the slow modes of the fluid. Temperature and shear rate dependencies of T[sub eff] are studied using density fluctuations as an observable. The observable dependence of T[sub eff] is also investigated. Many different observables are found to lead to the same value of T[sub eff], suggesting several experimental procedures to access T[sub eff]. It is proposed that a tracer particle of large mass m[sub tr] may play the role of an "effective thermometer." When the Einstein frequency of the tracers becomes smaller than the inverse 〈m[sub tr]ν²[sub z]〉 = k[sub B]T[sub eff], relaxation time of the fluid, a nonequilibrium equipartition theorem holds with where ν[sub z] is the velocity in the direction transverse to the flow. This last result gives strong support to the thermodynamic interpretation of T[sub eff] and makes it experimentally... [ABSTRACT FROM AUTHOR]

Sedimentation equilibria in concentrated colloidal suspensions are studied within the framework of density functional theory for inhomogeneous fluids. The density profile in the gravitational field is calculated exactly for the one-dimensional model of hard rods. The predictions of the local density approximation agree very well with coarse-grained density profiles derived from extensive Monte Carlo simulations of three-dimensional systems of hard spheres and charge-stabilized colloidal particles. The simulations show that the shape of the density profiles is very sensitive to the nature of the interactions between colloidal particles, and allow a direct test of a simple inversion procedure, which extracts the osmotic equation of state of colloidal suspensions from a measurement of their density profile. The method is sufficiently sensitive to allow the crystal-fluid tie line to be located at high colloid concentrations. The local density approximation is generalized to calculate density profiles of bidisperse hard sphere suspensions; the competition between gravity and entropy leads to nonmonotonic density profiles which are sensitive to the mass ratio, for a given size ratio. The density functional approach and Monte Carlo simulations are finally extended to study the effect of interparticle attractions on the density profiles, which exhibit a region of rapid variation corresponding to the ‘‘liquid-gas’’ interface for sufficiently strong attractive interactions. [ABSTRACT FROM AUTHOR]

The stability of the stoichiometric solid structures Xe(He)2 and Xe(He)13 is investigated up to 30 GPa pressure at room temperature, T=300 K. The Gibbs free energy of these so-called van der Waals compounds is computed using simple semianalytical methods that are in good agreement with molecular dynamics computer simulations. The interatomic interactions are described by empirical pair potentials adjusted to fit high pressure experimental data. The Xe(He)2 phase is found to be stable with respect to phase separation into pure components, while Xe(He)13 is unstable. These results agree with simple packing considerations, but are rather sensitive to the precise form of the helium–xenon interaction. A brief comment is made about the occurrence of a Ne(He)2 compound, that was recently found by Jean-Louis et al. [ABSTRACT FROM AUTHOR]

The concentration pair correlation function and the order–disorder transition in a diblock copolymer melt are studied in the framework of a self-consistent one-loop approximation. In contrast with earlier work, no simplifying assumption on the wave vector dependence of the correlation functions is made. This allows us to calculate the shift in the peak of the fluctuation spectrum recently observed in neutron scattering experiments. Quantitative agreement with experimental results is found. We also present a new calculation of how the collective concentration fluctuations influence single chain statistics in the copolymer melt. It is shown that even in the disordered phase, strong deviations from Gaussian statistics can be expected for finite molecular weights. A local segregation between monomers of the two different blocks results in an increase in the copolymer radius of gyration. [ABSTRACT FROM AUTHOR]

Molecular dynamics calculations have been used to study structural relaxation and dynamical correlations near the glass transition in the system [Ca(NO3)2]0.4[KNO3]0.6. As in a typical molten salt, the overall structure is determined by charge ordering. However, the radial distribution function for Ca2+ ions is unusual in that even at high temperatures it shows a split first peak due to specific spatial correlations of the cations with the nitrate anions. Structural relaxation that accompanies cooling of the system has been characterized with the aid of the van Hove real-space correlation functions Gs (r,t) for the constituent atoms (Ca, K, N, O). The relaxation of the incoherent structure factor Fs (k,t), with a wave vector k near the peak of the static structure factor, has been investigated as a function of temperature. The results clearly reveal both the α and β relaxation processes; the former can be well represented by a master curve with a stretched exponential shape. An analysis of the susceptibility, which agrees qualitatively with neutron spin-echo data, suggests that the glass transition for the model occurs around 400 K. The relatively small discrepancy with the experimental transition temperature derived from neutron scattering data (366 K) is likely related to inadequacies in the model employed for the interionic interactions. The functions C1(t) and C2(t), which describe the reorientational relaxation of the threefold symmetry axes of the nitrate ions, are shown to exhibit a scaling behavior analogous to that of the structure factor. In the region of the glass transition, where translational diffusion has essentially stopped, the nitrate ions continue to flip predominantly about their twofold axes. [ABSTRACT FROM AUTHOR]

The path integral Monte Carlo method is used to estimate the difference in the melting pressures of 4He and 3He. Thermodynamic and structural properties of both isotopes are also computed using an effective pair potential for the interaction between helium atoms. At low temperature, calculations predict the lighter isotope has the higher melting pressure in almost quantitative agreement with available experimental data. The melting curves of 3He and 4He are found to intersect at T[bar_over_tilde:_approx._equal_to]100 K. [ABSTRACT FROM AUTHOR]

We present a short perspective on some of the contributions made by Jean-Pierre Hansen to our theoretical understanding of soft matter static structure and dynamics, using the tools developed for simple liquids within the rigorous framework of statistical physics. [ABSTRACT FROM PUBLISHER]

We show that, at least at a mean-field level, the effect of structural disorder in sheared amorphous media is very dissimilar depending on the thermal or athermal nature of their underlying dynamics. We first introduce a toy model, including explicitly two types of noise (thermal versus athermal). Within this interpretation framework, we argue that mean-field athermal dynamics can be accounted for by the so-called Hébraud-Lequeux (HL) model, in which the mechanical noise stems explicitly from the plastic activity in the sheared medium. Then, we show that the inclusion of structural disorder, by means of a distribution of yield energy barriers, has no qualitative effect in the HL model, while such a disorder is known to be one of the key ingredients leading kinematically to a finite macroscopic yield stress in other mean-field descriptions, such as the Soft-Glassy-Rheology model. We conclude that the statistical mechanisms at play in the emergence of a macroscopic yield stress, and a complex stationary dynamics at low shear rate, are different in thermal and athermal amorphous systems. Graphical abstract: [ABSTRACT FROM AUTHOR]

In the recent years, much attention has been devoted to the in-homogeneous nature of the mechanical response at the nanoscale in disordered solids. Clearly, the elastic heterogeneities that have been characterized in this context are expected to strongly affect the nature of the sound waves which, in contrast to the case of perfect crystals, cannot be completely rationalized in terms of phonons. Building on previous work on a toy model showing an amorphization transition, we investigate the relationship between sound waves and elastic heterogeneities in a unified framework by continuously interpolating from the perfect crystal, through increasingly defective phases, to fully developed glasses. We provide strong evidence of a direct correlation between sound wave features and the extent of the heterogeneous mechanical response at the nanoscale. [ABSTRACT FROM AUTHOR]

The slow flow of amorphous solids exhibits striking heterogeneities: swift localised particle rearrangements take place in the midst of a more or less homogeneously deforming medium. Recently, experimental as well as numerical work has revealed spatial correlations between these flow heterogeneities. Here, we use molecular dynamics (MD) simulations to characterise the rearrangements and systematically probe their correlations both in time and in space. In particular, these correlations display a four-fold azimuthal symmetry characteristic of shear stress redistribution in an elastic medium and we unambiguously detect their increase in range with time. With increasing shear rate, correlations become shorter-ranged. In addition, we study a coarse-grained model motivated by the observed flow characteristics and challenge its predictions directly with the MD simulations. While the model captures both macroscopic and local properties rather satisfactorily, the agreement with respect to the spatiotemporal correlations is at most qualitative. The discrepancies provide important insight into relevant physics that is missing in all related coarse-grained models that have been developed for the flow of amorphous materials so far, namely the finite shear wave velocity and the impact of elastic heterogeneities on stress redistribution. Graphical abstract: [ABSTRACT FROM AUTHOR]

Disordered solids exhibit unusual properties of their vibrational states and thermal conductivities. Recent progresses have well established the concept of “elastic heterogeneity”, i.e., disordered materials show spatially inhomogeneous elastic moduli. In this study, by using molecular-dynamics simulations, we gradually introduce “disorder” into a numerical system to control its modulus heterogeneity. The system starts from a perfect crystalline state, progressively transforms into an increasingly disordered crystalline state, and finally undergoes structural amorphisation. We monitor independently the elastic heterogeneity, the vibrational states, and the thermal conductivity across this transition, and show that the heterogeneity in elastic moduli is well correlated to vibrational and thermal anomalies of the disordered system. [ABSTRACT FROM AUTHOR]

We have studied a mesoscopic model for the flow of amorphous solids. The model is based on key features identified at the microscopic level, namely periods of elastic deformation interspersed with localised rearrangements of particles that induce long-range elastic deformations. These long-range deformations are derived following a continuum mechanics approach, in the presence of solid boundaries, and are included in full in the model. Indeed, they mediate spatial cooperativity in the flow, whereby a localised rearrangement may lead a distant region to yield. In particular, we have simulated a channel flow and found manifestations of spatial cooperativity that are consistent with published experimental observations for concentrated emulsions in microchannels. Two categories of effects are distinguished. On the one hand, the coupling of regions subject to different shear rates, for instance, leads to finite shear rate fluctuations in the seemingly unsheared “plug” in the centre of the channel. On the other hand, there is convincing experimental evidence of a specific rheology near rough walls. We discuss the diverse possible physical origins for this effect, and we suggest that it may be associated with the bumps of particles into surface asperities as they slide along the wall. [ABSTRACT FROM AUTHOR]

In layered materials, a common mode of deformation involves buckling of the layers under tensile deformation in the direction perpendicular to the layers. The instability mechanism, which operates in elastic materials from geological to nanometer scales, involves the elastic contrast between different layers. In a regular stacking of "hard" and "soft" layers, the tensile stress is first accommodated by a large deformation of the soft layers. The inhibited Poisson contraction results in a compressive stress in the direction transverse to the tensile deformation axis. The hard layers sustain this transverse compression until buckling takes place and results in an undulated structure. Using molecular simulations, we demonstrate this scenario for a material made of triblock copolymers. The buckling deformation is observed to take place at the nanoscale, at a wavelength that depends on strain rate. In contrast to what is commonly assumed, the wavelength of the undulation is not determined by defects in the microstructure. Rather, it results from kinetic effects, with a competition between the rate of strain and the growth rate of the instability. [ABSTRACT FROM AUTHOR]