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Peter Sollich

Publications and source records attributed to Peter Sollich.

At least 163 records · Page 9Linked to original sources
arXiv2005

Effects of polymer polydispersity on the phase behaviour of colloid-polymer mixtures

We study the equilibrium behaviour of a mixture of monodisperse hard sphere colloids and polydisperse non-adsorbing polymers at their $θ$-point, using the Asakura-Oosawa model treated within the free-volume approximation. Our focus is the experimentally relevant scenario where the distribution of polymer chain lengths across the system is fixed. Phase diagrams are calculated using the moment free energy method, and we show that the mean polymer size $ξ_{\rm c}$ at which gas-liquid phase separation first occurs decreases with increasing polymer polydispersity $δ$. Correspondingly, at fixed mean polymer size, polydispersity favours gas-liquid coexistence but delays the onset of fluid-solid separation. On the other hand, we find that systems with different $δ$ but the same {\em mass-averaged} polymer chain length have nearly polydispersity-independent phase diagrams. We conclude with a comparison to previous calculations for a semi-grandcanonical scenario, where the polymer chemical potentials are imposed, which predicted that fluid-solid coexistence was over gas-liquid in some areas of the phase diagram. Our results show that this somewhat counter-intuitive result arose because the actual polymer size distribution in the system is shifted to smaller sizes relative to the polymer reservoir distribution.

cond-mat.soft↗
arXiv2005

Nematic-nematic demixing in polydisperse thermotropic liquid crystals

We consider the effects of polydispersity on isotropic-nematic phase equilibria in thermotropic liquid crystals, using a Maier-Saupe theory with factorized interactions. A sufficient spread (approx. 50%) in the interaction strengths of the particles leads to phase separation into two or more nematic phases, which can in addition coexist with an isotropic phase. The isotropic-nematic coexistence region widens dramatically as polydispersity is increased, leading to re-entrant isotropic-nematic phase separation in some regions of the phase diagram. We show that similar phenomena will occur also for non-factorized interactions as long as the interaction strength between any two particle species is lower than the mean of the intra-species interactions.

cond-mat.soft↗
arXiv2004

Heterogeneous Dynamics of Coarsening Systems

We show by means of experiments, theory and simulations, that the slow dynamics of coarsening systems displays dynamic heterogeneity similar to that observed in glass-forming systems. We measure dynamic heterogeneity via novel multi-point functions which quantify the emergence of dynamic, as opposed to static, correlations of fluctuations. Experiments are performed on a coarsening foam using Time Resolved Correlation, a recently introduced light scattering method. Theoretically we study the Ising model, and present exact results in one dimension, and numerical results in two dimensions. For all systems the same dynamic scaling of fluctuations with domain size is observed.

cond-mat.stat-mech↗
arXiv2004

Liquid-gas coexistence and critical point shifts in size-disperse fluids

Specialized Monte Carlo simulations and the moment free energy (MFE) method are employed to study liquid-gas phase equilibria in size-disperse fluids. The investigation is made subject to the constraint of fixed polydispersity, i.e. the form of the `parent' density distribution $ρ^0(σ)$ of the particle diameters $σ$, is prescribed. This is the experimentally realistic scenario for e.g. colloidal dispersions. The simulations are used to obtain the cloud and shadow curve properties of a Lennard-Jones fluid having diameters distributed according to a Schulz form with a large (40%) degree of polydispersity. Good qualitative accord is found with the results from a MFE method study of a corresponding van der Waals model that incorporates size-dispersity both in the hard core reference and the attractive parts of the free energy. The results show that polydispersity engenders considerable broadening of the coexistence region between the cloud curves. The principal effect of fractionation in this region is a common overall scaling of the particle sizes and typical inter-particle distances, and we discuss why this effect is rather specific to systems with Schulz diameter distributions. Next, by studying a family of such systems with distributions of various widths, we estimate the dependence of the critical point parameters on $δ$. In contrast to a previous theoretical prediction, size-dispersity is found to raise the critical temperature above its monodisperse value. Unusually for a polydisperse system, the critical point is found to lie at or very close to the extremum of the coexistence region in all cases. We outline an argument showing that such behaviour will occur whenever size polydispersity affects only the range, rather than the strength of the inter-particle interactions.

cond-mat.soft↗
arXiv2004

Error counting in a quantum error-correcting code and the ground-state energy of a spin glass

Upper and lower bounds are given for the number of equivalence classes of error patterns in the toric code for quantum memory. The results are used to derive a lower bound on the ground-state energy of the +/-J Ising spin glass model on the square lattice with symmetric and asymmetric bond distributions. This is a highly non-trivial example in which insights from quantum information lead directly to an explicit result on a physical quantity in the statistical mechanics of disordered systems.

cond-mat.dis-nn↗
arXiv2004

Phase equilibria and fractionation in a polydisperse fluid

We describe how Monte Carlo simulation within the grand canonical ensemble can be applied to the study of phase behaviour in polydisperse fluids. Attention is focused on the case of fixed polydispersity in which the form of the `parent' density distribution $ρ^\circ(σ)$ of the polydisperse attribute $σ$ is prescribed. Recently proposed computational methods facilitate determination of the chemical potential distribution conjugate to $ρ^\circ(σ)$. By additionally incorporating extended sampling techniques within this approach, the compositions of coexisting (`daughter') phases can be obtained and fractionation effects quantified. As a case study, we investigate the liquid-vapor phase equilibria of a size-disperse Lennard-Jones fluid exhibiting a large ($δ=40%$) degree of polydispersity. Cloud and shadow curves are obtained, the latter of which exhibit a high degree of fractionation with respect to the parent. Additionally, we observe considerable broadening of the coexistence region relative to the monodisperse limit.

cond-mat.stat-mech↗
arXiv2003

Reply to Comment on "Fluctuation-dissipation relations in the non-equilibrium critical dynamics of Ising models"

We have recently shown that in non-equilibrium spin systems at criticality the limit $\Xin$ of the fluctuation-dissipation ratio X(t,tw) for t >> tw >> 1 can be measured using observables such as magnetization or energy [Phys. Rev.\ E {\bf 68}, 016116 (2003)]. Pleimling argues in a Comment [cond-mat/0309652] on our paper that for such observables correlation and response functions are dominated by one-time quantities dependent only on t, and are therefore not suitable for a determination of $\Xin$. Using standard scaling forms of correlation and response functions, as used by Pleimling, we show that our data do have a genuine two-time dependence and allow X(t,tw) and $\Xin$ to be measured, so that Pleimling's criticisms are easily refuted. We also compare with predictions from renormalization-group calculations, which are consistent with our numerical observation of a fluctuation-dissipation plot for the magnetization that is very close to a straight line. A key point remains that coherent observables make measurements of $\Xin$ easier than the traditionally used incoherent ones, producing fluctuation-dissipation plots whose slope is close to $\Xin$ over a much larger range.

cond-mat.stat-mech↗
arXiv2003

Fluctuation-dissipation relations in trap models

Trap models are intuitively appealing and often solvable models of glassy dynamics. In particular, they have been used to study aging and the resulting out-of-equilibrium fluctuation-dissipation relations between correlations and response functions. In this note I show briefly that one such relation, first given by Bouchaud and Dean, is valid for a general class of mean-field trap models: it relies only on the way a perturbation affects the transition rates, but is independent of the distribution of trap depths and the form of the unperturbed transition rates, and holds for all observables that are uncorrelated with the energy. The model with Glauber dynamics and an exponential distribution of trap depths, as considered by Barrat and Mezard, does not fall into this class if the perturbation is introduced in the standard way by shifting all trap energies. I show that a similar relation between response and correlation nevertheless holds for the out-of-equilibrium dynamics at low temperatures. The results point to intriguing parallels between trap models with energetic and entropic barriers.

cond-mat.dis-nn↗
arXiv2003

General Solutions for Multispin Two-Time Correlation and Response Functions in the Glauber-Ising Chain

The kinetic Glauber-Ising spin chain is one of the very few exactly solvable models of non-equilibrium statistical mechanics. Nevertheless, existing solutions do not yield tractable expressions for two-time correlation and response functions of observables involving products of more than one or two spins. We use a new approach to solve explicitly the full hierarchy of differential equations for the correlation and response functions. From this general solution follow closed expressions for arbitrary multispin two-time correlation and response functions, for the case where the system is quenched from equilibrium at T_i > 0 to some arbitrary T >= 0. By way of application, we give the results for two and four-spin two-time correlation and response functions. From the standard mapping, these also imply new exact results for two-time particle correlation and response functions in one-dimensional diffusion limited annihilation.

cond-mat.stat-mech↗
arXiv2003

Fluctuation-dissipation relations in the non-equilibrium critical dynamics of Ising models

We investigate the relation between two-time, multi-spin, correlation and response functions in the non-equilibrium critical dynamics of Ising models in d=1 and d=2 spatial dimensions. In these non-equilibrium situations, the fluctuation-dissipation theorem (FDT) is not satisfied. We find FDT `violations' qualitatively similar to those reported in various glassy materials, but quantitatively dependent on the chosen observable, in contrast to the results obtained in infinite-range glass models. Nevertheless, all FDT violations can be understood by considering separately the contributions from large wavevectors, which are at quasi-equilibrium and obey FDT, and from small wavevectors where a generalized FDT holds with a non-trivial limit fluctuation-dissipation ratio X. In d=1, we get X = 1/2 for spin observables, which measure the orientation of domains, while X = 0 for observables that are sensitive to the domain-wall motion. Numerical simulations in d=2 reveal a unique X = 0.34 for all observables. Measurement protocols for X are discussed in detail. Our results suggest that the definition of an effective temperature Teff = T / X for large length scales is generically possible in non-equilibrium critical dynamics.

cond-mat.stat-mech↗
arXiv2003

Glassy dynamics of kinetically constrained models

We review the use of kinetically constrained models (KCMs) for the study of dynamics in glassy systems. The characteristic feature of KCMs is that they have trivial, often non-interacting, equilibrium behaviour but interesting slow dynamics due to restrictions on the allowed transitions between configurations. The basic question which KCMs ask is therefore how much glassy physics can be understood without an underlying ``equilibrium glass transition''. After a brief review of glassy phenomenology, we describe the main model classes, which include spin-facilitated (Ising) models, constrained lattice gases, models inspired by cellular structures such as soap froths, models obtained via mappings from interacting systems without constraints, and finally related models such as urn, oscillator, tiling and needle models. We then describe the broad range of techniques that have been applied to KCMs, including exact solutions, adiabatic approximations, projection and mode-coupling techniques, diagrammatic approaches and mappings to quantum systems or effective models. Finally, we give a survey of the known results for the dynamics of KCMs both in and out of equilibrium, including topics such as relaxation time divergences and dynamical transitions, nonlinear relaxation, aging and effective temperatures, cooperativity and dynamical heterogeneities, and finally non-equilibrium stationary states generated by external driving. We conclude with a discussion of open questions and possibilities for future work.

cond-mat.stat-mech↗
arXiv2002

Isotropic-nematic phase equilibria in the Onsager theory of hard rods with length polydispersity

We analyse the effect of a continuous spread of particle lengths on the phase behavior of rodlike particles, using the Onsager theory of hard rods. Our aim is to establish whether ``unusual'' effects such as isotropic-nematic-nematic (I-N-N) phase separation can occur even for length distributions with a single peak. We focus on the onset of I-N coexistence. For a log-normal distribution we find that a finite upper cutoff on rod lengths is required to make this problem well-posed. The cloud curve, which tracks the density at the onset of I-N coexistence as a function of the width of the length distribution, exhibits a kink; this demonstrates that the phase diagram must contain a three-phase I-N-N region. Theoretical analysis shows that in the limit of large cutoff the cloud point density actually converges to zero, so that phase separation results at any nonzero density; this conclusion applies to all length distributions with fatter-than-exponentail tails. Finally we consider the case of a Schulz distribution, with its exponential tail. Surprisingly, even here the long rods (and hence the cutoff) can dominate the phase behaviour, and a kink in the cloud curve and I-N-N coexistence again result. Theory establishes that there is a nonzero threshold for the width of the length distribution above which these long rod effects occur, and shows that the cloud and shadow curves approach nonzero limits for large cutoff, both in good agreement with the numerical results.

cond-mat.soft↗
arXiv2002

Equivalence of driven and ageing fluctuation-dissipation relations in the trap model

We study the non-equilibrium version of the fluctuation dissipation (FD) relation in the glass phase of a trap model that is driven into a non-equilibrium steady state by external ``shear''. This extends our recent study of ageing FD relations in the same model, where we found limiting, observable independent FD relations for ``neutral'' observables that are uncorrelated with the system's average energy. In this work, for such neutral observables, we find the FD relation for a stationary weakly driven system to be the same, to within small corrections, as for an infinitely aged system. We analyse the robustness of this correspondence with respect to non-neutrality of the observable, and with respect to changes in the driving mechanism.

cond-mat.stat-mech↗
arXiv2002

Isotropic-nematic phase equilibria of polydisperse hard rods: The effect of fat tails in the length distribution

We study the phase behaviour of hard rods with length polydispersity, treated within a simplified version of the Onsager model. We give a detailed description of the unusual phase behaviour of the system when the rod length distribution has a "fat" (e.g. log-normal) tail up to some finite cutoff. The relatively large number of long rods in the system strongly influences the phase behaviour: the isotropic cloud curve, which defines the where a nematic phase first occurs as density is increased, exhibits a kink; at this point the properties of the coexisting nematic shadow phase change discontinuously. A narrow three-phase isotropic-nematic-nematic coexistence region exists near the kink in the cloud curve, even though the length distribution is unimodal. A theoretical derivation of the isotropic cloud curve and nematic shadow curve, in the limit of large cutoff, is also given. The two curves are shown to collapse onto each other in the limit. The coexisting isotropic and nematic phases are essentially identical, the only difference being that the nematic contains a larger number of the longest rods; the longer rods are also the only ones that show any significant nematic ordering. Numerical results for finite but large cutoff support the theoretical predictions for the asymptotic scaling of all quantities with the cutoff length.

cond-mat.soft↗
arXiv2002

Simplified Onsager theory for isotropic-nematic phase equilibria of length polydisperse hard rods

Polydispersity is believed to have important effects on the formation of liquid crystal phases in suspensions of rod-like particles. To understand such effects, we analyse the phase behaviour of thin hard rods with length polydispersity. Our treatment is based on a simplified Onsager theory, obtained by truncating the series expansion of the angular dependence of the excluded volume. We describe the model and give the full phase equilibrium equations; these are then solved numerically using the moment free energy method which reduces the problem from one with an infinite number of conserved densities to one with a finite number of effective densities that are moments of the full density distribution. The method yields exactly the onset of nematic ordering. Beyond this, results are approximate but we show that they can be made essentially arbitrarily precise by adding adaptively chosen extra moments, while still avoiding the numerical complications of a direct solution of the full phase equilibrium conditions. We investigate in detail the phase behaviour of systems with three different length distributions: a (unimodal) Schulz distribution, a bidisperse distribution and a bimodal mixture of two Schulz distributions which interpolates between these two cases. A three-phase isotropic-nematic-nematic coexistence region is shown to exist for the bimodal and bidisperse length distributions if the ratio of long and short rod lengths is sufficiently large, but not for the unimodal one. We systematically explore the topology of the phase diagram as a function of the width of the length distribution and of the rod length ratio in the bidisperse and bimodal cases.

cond-mat.soft↗
arXiv2002

Model Selection for Support Vector Machine Classification

We address the problem of model selection for Support Vector Machine (SVM) classification. For fixed functional form of the kernel, model selection amounts to tuning kernel parameters and the slack penalty coefficient $C$. We begin by reviewing a recently developed probabilistic framework for SVM classification. An extension to the case of SVMs with quadratic slack penalties is given and a simple approximation for the evidence is derived, which can be used as a criterion for model selection. We also derive the exact gradients of the evidence in terms of posterior averages and describe how they can be estimated numerically using Hybrid Monte Carlo techniques. Though computationally demanding, the resulting gradient ascent algorithm is a useful baseline tool for probabilistic SVM model selection, since it can locate maxima of the exact (unapproximated) evidence. We then perform extensive experiments on several benchmark data sets. The aim of these experiments is to compare the performance of probabilistic model selection criteria with alternatives based on estimates of the test error, namely the so-called ``span estimate'' and Wahba's Generalized Approximate Cross-Validation (GACV) error. We find that all the ``simple'' model criteria (Laplace evidence approximations, and the Span and GACV error estimates) exhibit multiple local optima with respect to the hyperparameters. While some of these give performance that is competitive with results from other approaches in the literature, a significant fraction lead to rather higher test errors. The results for the evidence gradient ascent method show that also the exact evidence exhibits local optima, but these give test errors which are much less variable and also consistently lower than for the simpler model selection criteria.

cond-mat.dis-nn↗
arXiv2001

Grand canonical ensemble simulation studies of polydisperse fluids

We describe a Monte Carlo scheme for simulating polydisperse fluids within the grand canonical ensemble. Given some polydisperse attribute $σ$, the state of the system is described by a density distribution $ρ(σ)$ whose form is controlled by the imposed chemical potential distribution $μ(σ)$. We detail how histogram extrapolation techniques can be employed to tune $μ(σ)$ such as to traverse some particular desired path in the space of $ρ(σ)$. The method is applied in simulations of size-disperse hard spheres with densities distributed according to Schulz and log-normal forms. In each case, the equation of state is obtained along the dilution line, i.e. the path along which the scale of $ρ(σ)$ changes but not its shape. The results are compared with the moment-based expressions of Boublik et al (J. Chem. Phys. {\bf 54}, 1523 (1971)) and Salacuse and Stell (J. Chem. Phys. {\bf 77}, 3714 (1982)). It is found that for high degrees of polydispersity, both expressions fail to give a quantitatively accurate description of the equation of state when the overall volume fraction is large.

cond-mat.stat-mech↗