Structure and Mechanical Properties of a Porous Polymer Material via Molecular Dynamics Simulations.

We characterize, using molecular dynamics simulations, the structure and mechanical response of a porous glassy system, obtained via arrested phase separation of a model polymer melt. In the absence of external driving, coarsening dynamics, with power-law time dependence, controls the slow structural evolution, in agreement with what was reported for other phase-separating systems. The mechanical response was investigated in athermal quasi-static conditions.

Fractional Coupling of Primary and Johari-Goldstein Relaxations in a Model Polymer.

A polymer model exhibiting heterogeneous Johari−Goldstein (JG) secondary relaxation is studied by extensive molecular-dynamics simulations of states with different temperature and pressure. Time−temperature−pressure superposition of the primary (segmental) relaxation is evidenced. The time scales of the primary and the JG relaxations are found to be highly correlated according to a power law.

Neural Networks Reveal the Impact of the Vibrational Dynamics in the Prediction of the Long-Time Mobility of Molecular Glassformers.

Two neural networks (NN) are designed to predict the particle mobility of a molecular glassformer in a wide time window ranging from vibrational dynamics to structural relaxation. Both NNs are trained by information concerning the local structure of the environment surrounding a given particle. The only difference in the learning procedure is the inclusion (NN ) or not (NN ) of the information provided by the fast, vibrational dynamics and quantified by the local Debye-Waller factor.

Nanoscale Elastoplastic Wrinkling of Ultrathin Molecular Films.

Ultrathin molecular films deposited on a substrate are ubiquitously used in electronics, photonics, and additive manufacturing methods. The nanoscale surface instability of these systems under uniaxial compression is investigated here by molecular dynamics simulations. We focus on deviations from the homogeneous macroscopic behavior due to the discrete, disordered nature of the deformed system, which might have critical importance for applications.

Mutual Information in Molecular and Macromolecular Systems.

The relaxation properties of viscous liquids close to their glass transition (GT) have been widely characterised by the statistical tool of time correlation functions. However, the strong influence of ubiquitous non-linearities calls for new, alternative tools of analysis. In this respect, information theory-based observables and, more specifically, mutual information (MI) are gaining increasing interest.

Open and Anisotropic Soft Regions in a Model Polymer Glass.

The vibrational dynamics of a model polymer glass is studied by Molecular Dynamics simulations. The focus is on the "soft" monomers with high participation to the lower-frequency vibrational modes contributing to the thermodynamic anomalies of glasses. To better evidence their role, the threshold to qualify monomers as soft is made severe, allowing for the use of systems with limited size.

Predictive relation for the α-relaxation time of a coarse-grained polymer melt under steady shear.

We examine the influence of steady shear on structural relaxation in a simulated coarse-grained unentangled polymer melt over a wide range of temperature and shear rates. Shear is found to progressively suppress the α-relaxation process observed in the intermediate scattering function, leading ultimately to a purely inertially dominated β-relaxation at high shear rates, a trend similar to increasing temperature. On the basis of a scaling argument emphasizing dynamic heterogeneity in cooled liquids and its alteration under material deformation, we deduce and validate a parameter-free scaling relation for both the structural relaxation time τ from the intermediate scattering function and the "stretching exponent" β quantifying the extent of dynamic heterogeneity over the entire range of temperatures and shear rates that we can simulate.

Coincident Correlation between Vibrational Dynamics and Primary Relaxation of Polymers with Strong or Weak Johari-Goldstein Relaxation.

The correlation between the vibrational dynamics, as sensed by the Debye-Waller factor, and the primary relaxation in the presence of secondary Johari-Goldstein (JG) relaxation, has been investigated through molecular dynamics simulations. Two melts of polymer chains with different bond length, resulting in rather different strength of the JG relaxation are studied. We focus on the bond-orientation correlation function, exhibiting higher JG sensitivity with respect to alternatives provided by torsional autocorrelation function and intermediate scattering function.

Vibrational scaling of the heterogeneous dynamics detected by mutual information.

The correlations detected by the mutual information in the propensities of a molecular viscous liquid are studied by molecular-dynamics simulations. Dynamic heterogeneity is evidenced and two particle fractions with different mobility and relaxation identified. The two fractions exhibit the scaling of their relaxation in terms of the rattling amplitude of the particle trapped in the cage of the first neighbours 〈u〉 .

Fast Vibrational Modes and Slow Heterogeneous Dynamics in Polymers and Viscous Liquids.

Many systems, including polymers and molecular liquids, when adequately cooled and/or compressed, solidify into a disordered solid, i.e., a glass.

Metallic glass-formers in 2D exhibit the same scaling as in 3D between vibrational dynamics and structural relaxation.

Glass-forming systems approaching their glass transition exhibit universal correlations between picosecond vibrational dynamics and long-time structural relaxation, which can be described by the same master curve in the bulk or confined conditions. In this work, we study at a fundamental level the effects of the reduction of spatial dimensionality on this phenomenon. We perform molecular dynamics simulations of a metallic glass-formers in two dimensions (2D).

Mutual information does not detect growing correlations in the propensity of a model molecular liquid.

The dynamical spatial correlations detected by the mutual information (MI) in the isoconfigurational particle displacements of a monodisperse molecular viscous liquid are studied via molecular-dynamics simulations by changing considerably both the molecular mobility and the degree of dynamical heterogeneity. Different from atomic liquids, the MI correlation length does not grow on approaching the glass transition by considering the liquid both in full detail as a collection of monomers and as a coarse-grained ensemble of molecular centers of mass. In the detailed picture, it is found that: (i) the MI correlations between monomers are largely due to inter-molecular correlations, (ii) the MI length scale is numerically identical, within the errors, to the correlation length scale of the displacement direction, as drawn by conventional correlation functions.

Boson Peak Decouples from Elasticity in Glasses with Low Connectivity.

We perform molecular-dynamics simulations of the vibrational and elastoplastic properties of polymeric glasses and crystals and the corresponding atomic systems. We evidence that the elastic scaling of the density of states in the low-frequency boson peak (BP) region is different in crystals and glasses. Also, we see that the BP of the polymeric glass is nearly coincident with the one of the atomic glasses, thus revealing that the former-unlike the elasticity-is controlled by nonbonding interactions only.

Molecular layers in thin supported films exhibit the same scaling as the bulk between slow relaxation and vibrational dynamics.

We perform molecular-dynamics simulations of a supported molecular thin film. By varying thickness and temperature, we observe anisotropic mobility as well as strong gradients of both the vibrational motion and the structural relaxation through film layers with monomer-size thickness. We show that the gradients of the fast and the slow dynamics across the layers (except the adherent layer to the substrate) comply, without any adjustment, with the same scaling between the structural relaxation time and the Debye-Waller factor originally observed in the bulk [Larini et al.

Communication: Fast dynamics perspective on the breakdown of the Stokes-Einstein law in fragile glassformers.

The breakdown of the Stokes-Einstein (SE) law in fragile glassformers is examined by Molecular-Dynamics simulations of atomic liquids and polymers and consideration of the experimental data concerning the archetypical ortho-terphenyl glassformer. All the four systems comply with the universal scaling between the viscosity (or the structural relaxation) and the Debye-Waller factor ⟨u⟩, the mean square amplitude of the particle rattling in the cage formed by the surrounding neighbors. It is found that the SE breakdown is scaled in a master curve by a reduced ⟨u⟩.

Thermodynamic scaling of relaxation: insights from anharmonic elasticity.

Using molecular dynamics simulations of a molecular liquid, we investigate the thermodynamic scaling (TS) of the structural relaxation time [Formula: see text] in terms of the quantity [Formula: see text], where T and ρ are the temperature and density, respectively. The liquid does not exhibit strong virial-energy correlations. We propose a method for evaluating both the characteristic exponent [Formula: see text] and the TS master curve that uses experimentally accessible quantities that characterise the anharmonic elasticity and does not use details about the microscopic interactions.

Thermodynamic scaling of vibrational dynamics and relaxation.

We investigate by thorough molecular dynamics simulations the thermodynamic scaling (TS) of a polymer melt. Two distinct models, with strong and weak virial-energy correlations, are considered. Both evidence the joint TS with the same characteristic exponent γ of the fast mobility-the mean square amplitude of the picosecond rattling motion inside the cage-and the much slower structural relaxation and chain reorientation.

Cage effect in supercooled molecular liquids: Local anisotropies and collective solid-like response.

Both local geometry and collective extended excitations drive the moves of a particle in the cage of its neighbours in dense liquids. The strength of their influence is investigated by the molecular dynamics simulations of a supercooled liquid of fully flexible trimers with semirigid or rigid bonds. The rattling in the cage is investigated on different length scales.

Anisotropy of the monomer random walk in a polymer melt: local-order and connectivity effects.

The random walk of a bonded monomer in a polymer melt is anisotropic due to local order and bond connectivity. We investigate both effects by molecular-dynamics simulations on melts of fully-flexible linear chains ranging from dimers (M  =  2) up to entangled polymers (M  =  200). The corresponding atomic liquid is also considered a reference system.

The kinetic fragility of liquids as manifestation of the elastic softening.

We show that the fragility m , the steepness of the viscosity and relaxation time close to the vitrification, increases with the degree of elastic softening, i.e. the decrease of the elastic modulus with increasing temperature, in a universal way.

Weak links between fast mobility and local structure in molecular and atomic liquids.

We investigate by molecular-dynamics simulations, the fast mobility-the rattling amplitude of the particles temporarily trapped by the cage of the neighbors-in mildly supercooled states of dense molecular (linear trimers) and atomic (binary mixtures) liquids. The mixture particles interact by the Lennard-Jones potential. The non-bonded particles of the molecular system are coupled by the more general Mie potential with variable repulsive and attractive exponents in a range which is a characteristic of small n-alkanes and n-alcohols.

Competition of the connectivity with the local and the global order in polymer melts and crystals.

The competition between the connectivity and the local or global order in model fully flexible chain molecules is investigated by molecular-dynamics simulations. States with both missing (melts) and high (crystal) global order are considered. Local order is characterized within the first coordination shell (FCS) of a tagged monomer and found to be lower than in atomic systems in both melt and crystal.

Scaling between relaxation, transport and caged dynamics in a binary mixture on a per-component basis.

The universal scaling between the average slow relaxation/transport and the average picosecond rattling motion inside the cage of the first neighbors has been evidenced in a variety of numerical simulations and experiments. Here, we first show that the scaling does not need information concerning the arbitrarily-defined glass transition region and relies on a single characteristic length scale a(2)(1/2) which is determined even far from that region. This prompts the definition of a novel reduced rattling amplitude (1/2) which has been investigated by extensive molecular-dynamics simulations addressing the slow relaxation, the diffusivity, and the fast cage-dynamics of both components of an atomic binary mixture.

Molecular probe dynamics reveals suppression of ice-like regions in strongly confined supercooled water.

The structure of the hydrogen bond network is a key element for understanding water's thermodynamic and kinetic anomalies. While ambient water is strongly believed to be a uniform, continuous hydrogen-bonded liquid, there is growing consensus that supercooled water is better described in terms of distinct domains with either a low-density ice-like structure or a high-density disordered one. We evidenced two distinct rotational mobilities of probe molecules in interstitial supercooled water of polycrystalline ice [Banerjee D, et al.

Communication: Fast and local predictors of the violation of the Stokes-Einstein law in polymers and supercooled liquids.

The violation of the Stokes-Einstein (SE) law is investigated in a melt of linear chains by extensive molecular-dynamics simulations. It is found that the SE breakdown is signaled (with 5% uncertainty) by the monomer mean-square displacement on the picosecond time scale. On this time scale the displacements of the next-next-nearest neighbors are uncorrelated.