Molecular-dynamics simulation of a glassy polymer melt: Incoherent scattering function

We present simulation results for a model polymer melt, consisting of short, nonentangled chains, in the supercooled state. The analysis focuses on the monomer dynamics, which is monitored by the incoherent intermediate scattering function. The scattering function is recorded over six decades in time and for many different wave-vectors which range from the size of a chain to about three times the maximum position of the static structure factor. The lowest temperatures studied are slightly above , the critical temperature of mode-coupling theory (MCT), where was determined from a quantitative analysis of the - and -relaxations. We find evidence for the space-time factorization theorem in the -relaxation regime, and for the time-temperature superposition principle in the -regime, if the temperature is not too close to . The wave-vector (q-) dependence of the nonergodicity parameter, of the critical amplitude, and the -relaxation time are in qualitative agreement with calculations for hard spheres. For q larger than the maximum of the structure factor the -relaxation time already agrees fairly well with the asymptotic MCT-prediction . The behavior of the relaxation time at small q can be rationalized by the validity of the Gaussian approximation and the value of the Kohlrausch stretching exponent, as suggested in neutron-scattering experiments. Received 30 October 1998     

Renormalization group analysis of polymer cyclization with non-equilibrium initial conditions

We develop a renormalization group approach for cyclizing polymers for the case when chain ends are initially close together (ring initial conditions). We analyze the behavior at times much shorter than the longest polymer relaxation time. In agreement with our previous work (Europhys. Lett. 73, 621 (2006)) we find that the leading time dependence of the reaction rate k(t) for ring initial conditions and equilibrium initial conditions are related, namely k _ring(t) ∝ t ^-δ and k _eq(t) ∝ t ^1-δ for times less than the longest polymer relaxation time. Here δ is an effective exponent which approaches δ = 5/4 for very long Rouse chains. Our present analysis also suggests a “sub-leading” term proportional to (ln t)/t which should be particularly significant for smaller values of the renormalized reaction rate and early times. For Zimm dynamics, our RG analysis indicates that the leading time dependence for the reaction rate is k(t) ∼ 1/t for very long chains. The leading term is again consistent with the expected relation between ring and equilibrium initial conditions. We also find a logarithmic correction term which we “exponentiate” to a logarithmic form with a Landau pole. The presence of the logarithm is particularly important for smaller chains and, in the Zimm case, large values of the reaction rate.     

The -relaxation dynamics of a simple liquid

We present a detailed analysis of the -relaxation dynamics of a simple glass former, a binary Lennard-Jones system with a stochastic dynamics. By testing the various predictions of mode-coupling theory, including the recently proposed corrections to the asymptotic scaling laws, we come to the conclusion that in this time regime the dynamics is described very well by this theory. Received 5 February 1999 and Received in final form 7 June 1999     

Tagged Particle Diffusion in One-Dimensional Gas with Hamiltonian Dynamics

We consider a one-dimensional gas of hard point particles in a finite box that are in thermal equilibrium and evolving under Hamiltonian dynamics. Tagged particle correlation functions of the middle particle are studied. For the special case where all particles have the same mass, we obtain analytic results for the velocity auto-correlation function in the short time diffusive regime and the long time approach to the saturation value when finite-size effects become relevant. In the case where the masses are unequal, numerical simulations indicate sub-diffusive behaviour with mean square displacement of the tagged particle growing as t/ln(t) with time t. Also various correlation functions, involving the velocity and position of the tagged particle, show damped oscillations at long times that are absent for the equal mass case.     

Critical dynamics of the three-dimensional Ising model: A Monte Carlo study

Extensive Monte Carlo simulations have been performed to analyze the dynamical behavior of the three-dimensional Ising model with local dynamics. We have studied the equilibrium correlation functions and the power spectral densities of odd and even observables. The exponential relaxation times have been calculated in the asymptotic one-exponential time region. We find that the critical exponentz=2.09 ±0.02 characterizes the algebraic divergence with lattice size for all observables. The influence of scaling corrections has been analyzed. We have determined integrated relaxation times as well. Their dynamical exponentz _int agrees withz for correlations of the magnetization and its absolute value, but it is different for energy correlations. We have applied a scaling method to analyze the behavior of the correlation functions. This method verifies excellent scaling behavior and yields a dynamical exponentz _scal which perfectly agrees withz.     

Kinetics of shape equilibration for two dimensional islands

We study the relaxation to equilibrium of two dimensional islands containing up to 20 000 atoms by Kinetic Monte Carlo simulations. We find that the commonly assumed relaxation mechanism - curvature-driven relaxation via atom diffusion - cannot explain the results obtained at low temperatures, where the island edges consist in large facets. Specifically, our simulations show that the exponent characterizing the dependence of the equilibration time on the island size is different at high and low temperatures, in contradiction with the above cited assumptions. Instead, we propose that - at low temperatures - the relaxation is limited by the nucleation of new atomic rows on the large facets: this allows us to explain both the activation energy and the island size dependence of the equilibration time. Received 7 December 1998 and Received in final form 18 March 1999     

Stretched exponential relaxation on the hypercube and the glass transition

We study random walks on the dilute hypercube using an exact enumeration Master equation technique, which is much more efficient than Monte Carlo methods for this problem. For each dilution p the form of the relaxation of the memory function q(t) can be accurately parametrized by a stretched exponential over several orders of magnitude in q(t). As the critical dilution for percolation is approached, the time constant tends to diverge and the stretching exponent drops towards 1/3. As the same pattern of relaxation is observed in a wide class of glass formers, the fractal like morphology of the giant cluster in the dilute hypercube appears to be a good representation of the coarse grained phase space in these systems. For these glass formers the glass transition may be pictured as a percolation transition in phase space. Received 16 June 2000 and Received in final form 13 October 2000     

Non-equilibrium relaxation and tumbling times of polymers in semidilute solution

The end-over-end tumbling dynamics of individual polymers in dilute and semidilute solutions is studied under shear flow by large-scale mesoscale hydrodynamic simulations. End-to-end vector relaxation times are determined along the flow, gradient, and vorticity directions. Along the flow and gradient directions, the correlation functions decay exponentially with sinusoidal modulations at short times. In dilute solution, the decay times of the various directions are very similar. However, in semidilute solutions, the relaxation behaviors are rather different along the various directions, with the longest relaxation time in the vorticity direction and the shortest time in the flow direction. The various relaxation times exhibit a power-law shear-rate dependence with the exponent -?2/3 at high shear rates. Quantitatively, the relaxation times are equal to the tumbling times extracted from cross-correlation functions of fluctuations of radius-of-gyration components along the flow and gradient direction.     

Reaction kinetics in polymer melts

We study the reaction kinetics of end-functionalized polymer chains dispersed in an unreactive polymer melt. Starting from an infinite hierarchy of coupled equations for many-chain correlation functions, a closed equation is derived for the 2nd order rate constant k after postulating simple physical bounds. Our results generalize previous 2-chain treatments (valid in dilute reactants limit) by Doi [#!doi:inter2!#], de Gennes [#!gennes:polreactionsiandii!#], and Friedman and O'Shaughnessy [#!ben:interdil_all_aip!#], to arbitrary initial reactive group density n₀ and local chemical reactivity Q. Simple mean field (MF) kinetics apply at short times, .For high Q, a transition occurs to diffusion-controlled (DC) kinetics with (where x_t is rms monomer displacement in time t) leading to a density decay . If n₀ exceeds the chain overlap threshold, this behavior is followed by a regime where during which k has the same power law dependence in time, , but possibly different numerical coefficient. For unentangled melts this gives while for entangled cases one or more of the successive regimes ,t ^-3/8 and t ^-3/4 may be realized depending on the magnitudes of Q and n₀. Kinetics at times longer than the longest polymer relaxation time are always MF. If a DC regime has developed before then the long time rate constant is where R is the coil radius. We propose measuring the above kinetics in a model experiment where radical end groups are generated by photolysis. Received: 2 June 1998 / Revised: 9 July 1998 / Accepted: 10 July 1998     

Sub-aging in a domain growth model

We study analytically the aging dynamics of the O(n) model in the limit of , with conserved and with non-conserved order parameter. While in the non-conserved dynamics, the autocorrelation function scales in the usual way , in the case of a conserved order parameter, `multiscaling' manifests itself in the form , with a relaxation time growing more slowly than the age of the system (sub-aging), and h(t) a function growing faster than any length scale of the problem. In both cases, the effective temperature associated to the violation of the fluctuation theorem tends to infinity in the asymptotic limit of large waiting times. Received 15 May 2000 and Received in final form 5 July 2000     

A statistical-mechanical theory of self-diffusion in glass-forming liquids

A statistical-mechanical theory of self-diffusion in glass-forming liquids is presented. A non-Markov linear Langevin equation is derived from a Newton equation by employing the Tokuyama-Mori projection operator method. The memory function is explicitly written in terms of the force-force correlation functions. The equations for the mean-square displacement, the mean-fourth displacement, and the non-Gaussian parameter are then formally derived. The present theory is applied to the glass transitions in the glass-forming liquids to discuss the crossover phenomena in the dynamics of a single particle from a short-time ballistic motion to a long-time self-diffusion process via a β (caging) stage. The effects of the renormalized friction coefficient on self-diffusion are thus explored with the aid of analyses of the simulation results by the mean-field theory proposed recently by the present author. It is thus shown that the relaxation time of the renormalized memory function is given by the β-relaxation time. It is also shown that for times longer than the β-relaxation time the dynamics of a single particle is identical to that discussed in the suspensions.     

Static and dynamic properties of supercooled thin polymer films

The dynamic and static properties of a supercooled (non-entangled) polymer melt are investigated via molecular-dynamics (MD) simulations. The system is confined between two completely smooth and purely repulsive walls. The wall-to-wall separation (film thickness), D, is varied from about 3 to about 14 times the bulk radius of gyration. Despite the geometric confinement, the supercooled films exhibit many qualitative features which were also observed in the bulk and could be analyzed in terms of mode-coupling theory (MCT). Examples are the two-step relaxation of the incoherent intermediate scattering function, the time-temperature superposition property of the late time α-process and the space-time factorization of the scattering function on the intermediate time scale of the MCT β-process. An analysis of the temperature dependence of the α-relaxation time suggests that the critical temperature, T _c, of MCT decreases with D. If the confinement is not too strong ( D≥10monomer diameter), the static structure factor of the film coincides with that of the bulk when compared for the same distance, T - T _c(D), to the critical temperature. This suggests that T - T _c(D) is an important temperature scale of our model both in the bulk and in the films. Received 12 September 2001     

Stretched exponential relaxation in the Coulomb glass

The relaxation of the specific heat and the entropy to their equilibrium values is investigated numerically for the three-dimensional Coulomb glass at very low temperatures. The long time relaxation follows a stretched exponential function, f (t) = f ₀exp - (t/τ)^β , with the exponent β increasing with the temperature. The relaxation time diverges as an Arrhenius law when T→ 0. Received 24 May 2001 and Received in final form 12 September 2001     

MD simulation of concentrated polymer solutions: Structural relaxation near the glass transition

We examine by molecular dynamics simulations the relaxation of polymer-solvent mixtures close to the glass transition. The simulations employ a coarse-grained model in which polymers are represented by bead-spring chains and solvent particles by monomers. The interaction parameters between polymer and solvent are adjusted such that mixing is favored. We find that the mixtures have one glass transition temperature T _g or critical temperature T _c of mode-coupling theory (MCT). Both T _g and T _c (> T _g decrease with increasing solvent concentration . The decrease is linear for the concentrations studied (up to = 25%. Above T _c we explore the structure and relaxation of the polymer-solvent mixtures on cooling. We find that, if the polymer solution is compared to the pure polymer melt at the same T, local spatial correlations on the length scale of the first peak of the static structure factor S(q) are reduced. This difference between melt and solution is largely removed when comparing the S(q) of both systems at similar distance to the respective T _c. Near T _c we investigate dynamic correlation functions, such as the incoherent intermediate scattering function (t), mean-square displacements of the monomers and solvent particles, two non-Gaussian parameters, and the probability distribution P(ln r;t) of the logarithm of single-particle displacements. In accordance with MCT we find, for instance, that (t) obeys the time-temperature superposition principle and has relaxation times which are compatible with a power law increase close (but not too close) to T _c. In divergence to MCT, however, the increase of depends on the wavelength q, small q values having weaker increase than large ones. This decoupling of local and large-length scale relaxation could be related to the emergence of dynamic heterogeneity at low T. In the time window of the relaxation an analysis of P(ln r;t) reveals a double-peak structure close to T _c. The first peak correponds to “slow” particles (monomer or solvent) which have not moved much farther than 10% of their diameter in time t, whereas the second occurs at distances of the order of the particle diameter. These “fast” particles have succeeded in leaving their nearest-neighbor cage in time t. The simulation thus demonstrates that large fluctuations in particle mobility accompany the final structural relaxation of the cold polymer solution in the vicinity of the extrapolated T _c.     

Aging phenomena in nonlinear dissipative chains

We study the energy relaxation in a one-dimensional nonlinear lattice with dissipative couplings. After thermalisation of this system, the extremities of the chain are put in contact with a zero-temperature reservoir, showing the existence of surprising quasi-stationary states with non zero energy, tough the dissipative coupling is high. This strange behavior, due to long-lived nonlinear localized modes, induces stretched exponential relaxation laws. Furthermore, we observe a strong dependence on the waiting time t_w after the quench of the two-time intermediate correlation function C(t_w+t, t_w). This function can be scaled onto a master curve, similar to the case of spin or Lennard-Jones glasses.Received: 11 February 2003, Published online: 4 August 2003PACS: 05.20.-y Classical statistical mechanics - 05.45.-a Nonlinear dynamics and nonlinear dynamical systems     

Computer simulation of a diatomic molecule dissolved in a monatomic fluid—Correlation functions,band shapes,and relaxation times

Four N₂-Ar ‘solute-solvent’ systems representing different temperatures and densities were simulated on a computer by the molecular dynamics technique. From the data for each system, the dipole, angular velocity, force-on-the-bond, and P ₂ correlation functions were calculated. These functions were used to determine rovibrational infra-red and Raman band-shapes, and N.M.R. relaxation times for quadrupolar, magnetic dipole-dipole and spin-rotation relaxation mechanisms. The P ₂ and dipole correlation functions were compared with those calculated by Gordon from experimental data. The lack of agreement was examined to determine restrictions on the application of Gordon's method for obtaining these correlation functions. Also, the band shapes were compared with the experimental data to help determine these restrictions. The N.M.R. relaxation times were examined for temperature dependence and for dominant contributions to the total relaxation time. The force-on-the-bond correlation function was found to require an extra term that takes into account the average force field to which the N₂ molecule is subjected. A three-parameter model for rotational diffusion of a diatomic molecule is tested and compared with existing models.     

Dielectric relaxation of poly(ethylenglycol)- b-poly(propylenglycol)-b-poly(ethylenglycol) copolymers above the glass transition temperature

The complex dielectric permittivity has been measured for three poly(ethylenglycol)-b-poly(propylenglycol)-b-poly(ethylenglycol) copolymers with different content of poly(ethylenglycol) (15%, 33% and 80%), and increasing degree of crystallinity (0%, 10% and 20%, respectively). Only the non-crystalline sample shows the normal mode relaxation together with the segmental (α-relaxation) and the Johari-Goldstein (β-relaxation) modes. The crystalline samples show also polarization contributions due to the existence of interfaces between the crystallites and the amorphous phase. The relaxation times of the (α and normal modes can be described by a VFT equation with the same value of T₀. There is a slowing-down of the segmental mode due to the presence of crystallites. The temperature dependence of the α and β relaxations in the copolymers is very similar to that found in pure PPG, while there are significant differences in the case of the normal mode of the non-crystalline sample. The size of the cooperatively rearranging regions CRR, and the width of the glass transition region increase slightly with the degree of crystallinity. The temperature dependence of the size of CRRs is compatible with the prediction of fluctuation theory. No systematic effect of the degree of crystallinity on the β-relaxation has been found. Near T _g the β-relaxation time is close to the primitive time of the coupling model. Received: 31 May 2000     

Intrinsic spin fluctuations reveal the dynamical response function of holes coupled to nuclear spin baths in (In,Ga)As quantum dots

The problem of how single central spins interact with a nuclear spin bath is essential for understanding decoherence and relaxation in many quantum systems, yet is highly nontrivial owing to the many-body couplings involved. Different models yield widely varying time scales and dynamical responses (exponential, power-law, gaussian, etc.). Here we detect the small random fluctuations of central spins in thermal equilibrium [holes in singly charged (In,Ga)As quantum dots] to reveal the time scales and functional form of bath-induced spin relaxation. This spin noise indicates long (400 ns) spin correlation times at a zero magnetic field that increase to ～5 μs as dominant hole-nuclear relaxation channels are suppressed with small (100 G) applied fields. Concomitantly, the noise line shape evolves from Lorentzian to power law, indicating a crossover from exponential to slow [～1/log(t)] dynamics.