Strain correlation functions in isotropic elastic bodies: large wavelength limit for two-dimensional systems.

Strain correlation functions in two-dimensional isotropic elastic bodies are shown both theoretically (using the general structure of isotropic tensor fields) and numerically (using a glass-forming model system) to depend on the coordinates of the field variable (position vector r in real space or wavevector q in reciprocal space) and thus on the direction of the field vector and the orientation of the coordinate system. Since the fluctuations of the longitudinal and transverse components of the strain field in reciprocal space are known in the long-wavelength limit from the equipartition theorem, all components of the correlation function tensor field are imposed and no additional physical assumptions are needed. An observed dependence on the field vector direction thus cannot be used as an indication for anisotropy or for a plastic rearrangement. This dependence is different for the associated strain response field containing also information on the localized stress perturbation.

Different types of spatial correlation functions for non-ergodic stochastic processes of macroscopic systems.

Focusing on non-ergodic macroscopic systems, we reconsider the variances [Formula: see text] of time averages [Formula: see text] of time-series [Formula: see text]. The total variance [Formula: see text] (direct average over all time series) is known to be the sum of an internal variance [Formula: see text] (fluctuations within the meta-basins) and an external variance [Formula: see text] (fluctuations between meta-basins). It is shown that whenever [Formula: see text] can be expressed as a volume average of a local field [Formula: see text] the three variances can be written as volume averages of correlation functions [Formula: see text], [Formula: see text] and [Formula: see text] with [Formula: see text]. The dependences of the [Formula: see text] on the sampling time [Formula: see text] and the system volume V can thus be traced back to [Formula: see text] and [Formula: see text]. Various relations are illustrated using lattice spring models with spatially correlated spring constants. .

Theory of length-scale dependent relaxation moduli and stress fluctuations in glass-forming and viscoelastic liquids.

The spatiotemporal correlations of the local stress tensor in supercooled liquids are studied both theoretically and by molecular dynamics simulations of a two-dimensional (2D) polydisperse Lennard-Jones system. Asymptotically exact theoretical equations defining the dynamical structure factor and all components of the stress correlation tensor for low wave-vector q are presented in terms of the generalized (q-dependent) shear and longitudinal relaxation moduli, G(q, t) and K(q, t). We developed a rigorous approach (valid for low q) to calculate K(q, t) in terms of certain bulk correlation functions (for q = 0), the static structure factor S(q), and thermal conductivity κ. The proposed approach takes into account both the thermostatting effect and the effect of polydispersity. The theoretical results for the (q, t)-dependent stress correlation functions are compared with our simulation data, and an excellent agreement is found for qb̄≲0.5 (with b̄ being the mean particle diameter) both above and below the glass transition without any fitting parameters. Our data are consistent with recently predicted (both theoretically and by simulations) long-range correlations of the shear stress quenched in heterogeneous glassy structures.

Relaxation moduli of glass-forming systems: temperature effects and fluctuations.

Equilibrium and dynamical properties of a two-dimensional polydisperse colloidal model system are characterized by means of molecular dynamics (MD) and Monte Carlo (MC) simulations. We employed several methods to prepare quasi-equilibrated systems: in particular, by slow cooling and tempering with MD (method SC-MD), and by tempering with MC dynamics involving swaps of particle diameters (methods Sw-MD, Sw-MC). It is revealed that the Sw-methods are much more efficient for equilibration below the glass transition temperature Tg leading to denser and more rigid systems which show much slower self-diffusion and shear-stress relaxation than their counterparts prepared with the SC-MD method. The shear-stress relaxation modulus G(t) is obtained based on the classical stress-fluctuation relation. We demonstrate that the α-relaxation time τα obtained using a time-temperature superposition of G(t) shows a super-Arrhenius behavior with the VFT temperature T0 well below Tg. We also derive novel rigorous fluctuation relations providing isothermic and adiabatic compression relaxation moduli in the whole time range (including the short-time inertial regime) based on correlation data for thermostatted systems. It is also shown that: (i) the assumption of Gaussian statistics for stress fluctuations leads to accurate predictions of the variances of the fluctuation moduli for both shear (µF) and compression (ηF) at T⪆Tg. (ii) The long-time (quasi-static) isothermic and adiabatic moduli increase on cooling faster than the affine compression modulus ηA, and this leads to a monotonic temperature dependence of ηF which is qualitatively different from µF(T) showing a maximum near Tg.

Simple models for strictly non-ergodic stochastic processes of macroscopic systems.

We investigate simple models for strictly non-ergodic stochastic processes [Formula: see text] (t being the discrete time step) focusing on the expectation value v and the standard deviation [Formula: see text] of the empirical variance [Formula: see text] of finite time series [Formula: see text]. [Formula: see text] is averaged over a fluctuating field [Formula: see text] ([Formula: see text] being the microcell position) characterized by a quenched spatially correlated Gaussian field [Formula: see text]. Due to the quenched [Formula: see text]-field [Formula: see text] becomes a finite constant, [Formula: see text], for large sampling times [Formula: see text]. The volume dependence of the non-ergodicity parameter [Formula: see text] is investigated for different spatial correlations. Models with marginally long-ranged [Formula: see text]-correlations are successfully mapped on shear stress data from simulated amorphous glasses of polydisperse beads.

Fluctuations of non-ergodic stochastic processes.

We investigate the standard deviation [Formula: see text] of the variance [Formula: see text] of time series [Formula: see text] measured over a finite sampling time [Formula: see text] focusing on non-ergodic systems where independent "configurations" c get trapped in meta-basins of a generalized phase space. It is thus relevant in which order averages over the configurations c and over time series k of a configuration c are performed. Three variances of [Formula: see text] must be distinguished: the total variance [Formula: see text] and its contributions [Formula: see text], the typical internal variance within the meta-basins, and [Formula: see text], characterizing the dispersion between the different basins. We discuss simplifications for physical systems where the stochastic variable x(t) is due to a density field averaged over a large system volume V. The relations are illustrated for the shear-stress fluctuations in quenched elastic networks and low-temperature glasses formed by polydisperse particles and free-standing polymer films. The different statistics of [Formula: see text] and [Formula: see text] are manifested by their different system-size dependences.

Ensemble fluctuations matter for variances of macroscopic variables.

Extending recent work on stress fluctuations in complex fluids and amorphous solids we describe in general terms the ensemble average [Formula: see text] and the standard deviation [Formula: see text] of the variance [Formula: see text] of time series [Formula: see text] of a stochastic process x(t) measured over a finite sampling time [Formula: see text]. Assuming a stationary, Gaussian and ergodic process, [Formula: see text] is given by a functional [Formula: see text] of the autocorrelation function h(t). [Formula: see text] is shown to become large and similar to [Formula: see text] if [Formula: see text] corresponds to a fast relaxation process. Albeit [Formula: see text] does not hold in general for non-ergodic systems, the deviations for common systems with many microstates are merely finite-size corrections. Various issues are illustrated for shear-stress fluctuations in simple coarse-grained model systems.

General relations to obtain the time-dependent heat capacity from isothermal simulations.

It is well-known that time-dependent correlation functions related to temperature and energy can crucially depend on the thermostatting mechanism used in computer simulations of molecular systems. We argue, however, that linear response functions must be considered as universal properties of physical systems. This implies that the classical fluctuation equation for the transient heat capacity, cv(t), is not applicable to the thermostatted molecular dynamics (apart from long enough times). To improve on this point, we derive a number of exact general expressions for the frequency-dependent heat capacity in terms of energy correlation functions, valid for the Nosé-Hoover and some other thermostats. We also establish a general relation between auto- and cross correlation functions of energy and temperature. Recommendations on how to use these relations to maximize the numerical precision are provided. It is demonstrated that our approach allows us to obtain cv(t) for a supercooled liquid system with high precision and over many decades in time reflecting all pertinent relaxation processes.

Long-range stress correlations in viscoelastic and glass-forming fluids.

A simple and rigorous approach to obtain stress correlations in viscoelastic liquids (including supercooled liquid and equilibrium amorphous systems) is proposed. The long-range dynamical correlations of local shear stress are calculated and analyzed in 2-dimensional space. It is established how the long-range character of the stress correlations gradually emerges as the relevant dynamical correlation length l grows in time. The correlation range l is defined by momentum propagation due to acoustic waves and vorticity diffusion which are the basic mechanisms for transmission of shear stress perturbations. We obtain the general expression defining the time- and distance-dependent stress correlation tensor in terms of material functions (generalized relaxation moduli). The effect of liquid compressibility is quantitatively analyzed; it is shown to be important at large distances and/or short times. The revealed long-range stress correlation effect is shown to be dynamical in nature and unconnected with static structural correlations in liquids (correlation length ξs). Our approach is based on the assumption that ξs is small enough as reflected in weak wave-number dependencies of the generalized relaxation moduli. We provide a simple physical picture connecting the elucidated long-range fluctuation effect with anisotropic correlations of the (transient) inherent stress field, and discuss its implications.

Shear Modulus and Shear-Stress Fluctuations in Polymer Glasses.

Using molecular dynamics simulation of a standard coarse-grained polymer glass model, we investigate by means of the stress-fluctuation formalism the shear modulus µ as a function of temperature T and sampling time Δt. While the ensemble-averaged modulus µ(T) is found to decrease continuously for all Δt sampled, its standard deviation δµ(T) is nonmonotonic, with a striking peak at the glass transition. Confirming the effective time-translational invariance of our systems, µ(Δt) can be understood using a weighted integral over the shear-stress relaxation modulus G(t). While the crossover of µ(T) gets sharper with an increasing Δt, the peak of δµ(T) becomes more singular. It is thus elusive to predict the modulus of a single configuration at the glass transition.

Marginally compact hyperbranched polymer trees.

Assuming Gaussian chain statistics along the chain contour, we generate by means of a proper fractal generator hyperbranched polymer trees which are marginally compact. Static and dynamical properties, such as the radial intrachain pair density distribution ρpair(r) or the shear-stress relaxation modulus G(t), are investigated theoretically and by means of computer simulations. We emphasize that albeit the self-contact density diverges logarithmically with the total mass N, this effect becomes rapidly irrelevant with increasing spacer length S. In addition to this it is seen that the standard Rouse analysis must necessarily become inappropriate for compact objects for which the relaxation time τp of mode p must scale as τp ∼ (N/p)5/3 rather than the usual square power law for linear chains.

Numerical determination of shear stress relaxation modulus of polymer glasses.

Focusing on simulated polymer glasses well below the glass transition, we confirm the validity and the efficiency of the recently proposed simple-average expression [Formula: see text] for the computational determination of the shear stress relaxation modulus G(t). Here, [Formula: see text] characterizes the affine shear transformation of the system at t = 0 and h(t) the mean-square displacement of the instantaneous shear stress as a function of time t. This relation is seen to be particulary useful for systems with quenched or sluggish transient shear stresses which necessarily arise below the glass transition. The commonly accepted relation [Formula: see text] using the shear stress auto-correlation function c(t) becomes incorrect in this limit.

Hyperbranched polymer stars with Gaussian chain statistics revisited.

Conformational properties of regular dendrimers and more general hyperbranched polymer stars with Gaussian statistics for the spacer chains between branching points are revisited numerically. We investigate the scaling for asymptotically long chains especially for fractal dimensions df = 3 (marginally compact) and df = 2.5 (diffusion limited aggregation). Power-law stars obtained by imposing the number of additional arms per generation are compared to truly self-similar stars. We discuss effects of weak excluded-volume interactions and sketch the regime where the Gaussian approximation should hold in dense solutions and melts for sufficiently large spacer chains.

Compressibility and pressure correlations in isotropic solids and fluids.

Presenting simple coarse-grained models of isotropic solids and fluids in d = 1 , 2 and 3 dimensions we investigate the correlations of the instantaneous pressure and its ideal and excess contributions at either imposed pressure (NPT-ensemble, λ = 0 or volume (NVT-ensemble, λ = 1 and for more general values of the dimensionless parameter λ characterizing the constant-volume constraint. The stress fluctuation representation F(Row)|λ=1 of the compression modulus K in the NVT-ensemble is derived directly (without a microscopic displacement field) using the well-known thermodynamic transformation rules between conjugated ensembles. The transform is made manifest by computing the Rowlinson functional F(Row)| also in the NPT-ensemble where F(Row)|λ=1 = K f 0(x) with x = P id/K being a scaling variable, P id the ideal pressure and f 0(x) = x(2-x) a universal function. By gradually increasing λ by means of an external spring potential, the crossover between both classical ensemble limits is monitored. This demonstrates, e.g., the lever rule F(Row)|λ= K[λ = (1 - λ)f 0(x)].

Shear modulus of simulated glass-forming model systems: effects of boundary condition, temperature, and sampling time.

The shear modulus G of two glass-forming colloidal model systems in d = 3 and d = 2 dimensions is investigated by means of, respectively, molecular dynamics and Monte Carlo simulations. Comparing ensembles where either the shear strain γ or the conjugated (mean) shear stress τ are imposed, we compute G from the respective stress and strain fluctuations as a function of temperature T while keeping a constant normal pressure P. The choice of the ensemble is seen to be highly relevant for the shear stress fluctuations µ(F)(T) which at constant τ decay monotonously with T following the affine shear elasticity µ(A)(T), i.e., a simple two-point correlation function. At variance, non-monotonous behavior with a maximum at the glass transition temperature T(g) is demonstrated for µF(T) at constant γ. The increase of G below T(g) is reasonably fitted for both models by a continuous cusp singularity, G(T) ∝ (1 - T∕T(g))(1∕2), in qualitative agreement with recent theoretical predictions. It is argued, however, that longer sampling times may lead to a sharper transition.

Communication: Pressure fluctuations in isotropic solids and fluids.

Comparing isotropic solids and fluids at either imposed volume or pressure, we investigate various correlations of the instantaneous pressure and its ideal and excess contributions. Focusing on the compression modulus K, it is emphasized that the stress fluctuation representation of the elastic moduli may be obtained directly (without a microscopic displacement field) by comparing the stress fluctuations in conjugated ensembles. This is made manifest by computing the Rowlinson stress fluctuation expression K(row) of the compression modulus for NPT-ensembles. It is shown theoretically and numerically that K(row∣P) = P(id)(2 - P(id)∕K) with P(id) being the ideal pressure contribution.

Correlations of tensor field components in isotropic systems with an application to stress correlations in elastic bodies.

Correlation functions of components of second-order tensor fields in isotropic systems can be reduced to an isotropic fourth-order tensor field characterized by a few invariant correlation functions (ICFs). It is emphasized that components of this field depend in general on the coordinates of the field vector variable and thus on the orientation of the coordinate system. These angular dependencies are distinct from those of ordinary anisotropic systems. As a simple example of the procedure to obtain the ICFs we discuss correlations of time-averaged stresses in isotropic glasses where only one ICF in reciprocal space becomes a finite constant e for large sampling times and small wave vectors. It is shown that e is set by the typical size of the frozen-in stress components normal to the wave vectors, i.e., it is caused by the symmetry breaking of the stress for each independent configuration. Using the presented general mathematical formalism for isotropic tensor fields this finding explains in turn the observed long-range stress correlations in real space. Under additional but rather general assumptions e is shown to be given by a thermodynamic quantity, the equilibrium Young modulus E. We thus relate for certain isotropic amorphous bodies the existence of finite Young or shear moduli to the symmetry breaking of a stress component in reciprocal space.

Strictly two-dimensional self-avoiding walks: thermodynamic properties revisited.

The density crossover scaling of various thermodynamic properties of solutions and melts of self-avoiding and highly flexible polymer chains without chain intersections confined to strictly two dimensions is investigated by means of molecular dynamics and Monte Carlo simulations of a standard coarse-grained bead-spring model. In the semidilute regime we confirm over an order of magnitude of the monomer density ρ the expected power law scaling for the interaction energy between different chains e(int) ~ ρ(21/8), the total pressure P ~ ρ(3) and the dimensionless compressibility g(T) = lim(q→0)S(q) ~ 1/ρ(2). Various elastic contributions associated to the affine and non-affine response to an infinitesimal strain are analyzed as functions of density and sampling time. We show how the size ξ(ρ) of the semidilute blob may be determined experimentally from the total monomer structure factor S(q) characterizing the compressibility of the solution at a given wave vector q. We comment briefly on finite persistence length effects.

Simulated glass-forming polymer melts: glass transition temperature and elastic constants of the glassy state.

By means of molecular-dynamics simulation we study a flexible and a semiflexible bead-spring model for a polymer melt on cooling through the glass transition. Results for the glass transition temperature T(g) and for the elastic properties of the glassy state are presented. We find that T(g) increases with chain length N and is for all N larger for the semiflexible model. The N dependence of T(g) is compared to experimental results from the literature. Furthermore, we characterize the polymer glass below T(g) via its elastic properties, i.e., via the Lamé coefficients λ and µ. The Lamé coefficients are determined from the fluctuation formalism which allows to split λ and µ into affine (Born term) and nonaffine (fluctuation term) contributions. We find that the fluctuation term represents a substantial correction to the Born term. Since the Born terms for λ and µ are identical, the fluctuation terms are responsible for the different temperature dependence of the Lamé coefficients. While λ decreases linearly on approaching T(g) from below, the shear modulus µ displays a much stronger decrease near T(g). From the present simulation data it is not possible to decide whether µ takes a finite value at T(g), as would be expected from mode-coupling theory, or vanishes continuously, as suggested by recent work from replica theory.

Scale-free center-of-mass displacement correlations in polymer melts without topological constraints and momentum conservation: a bond-fluctuation model study.

By Monte Carlo simulations of a variant of the bond-fluctuation model without topological constraints, we examine the center-of-mass (COM) dynamics of polymer melts in d = 3 dimensions. Our analysis focuses on the COM displacement correlation function C(N)(t)≈∂(t) (2)h(N)(t)/2, measuring the curvature of the COM mean-square displacement h(N)(t). We demonstrate that C(N)(t) ≈ -(R(N)∕T(N))(2)(ρ∗/ρ) f(x = t/T(N)) with N being the chain length (16 ≤ N ≤ 8192), R(N) ∼ N(1/2) is the typical chain size, T(N) ∼ N(2) is the longest chain relaxation time, ρ is the monomer density, ρ(*)≈N/R(N) (d) is the self-density, and f(x) is a universal function decaying asymptotically as f(x) ∼ x(-ω) with ω = (d + 2) × α, where α = 1/4 for x ≪ 1 and α = 1/2 for x ≫ 1. We argue that the algebraic decay NC(N)(t) ∼ -t(-5/4) for t ≪ T(N) results from an interplay of chain connectivity and melt incompressibility giving rise to the correlated motion of chains and subchains.