arXiv subjects

Peter Sollich

Publications and source records attributed to Peter Sollich.

173 records · Page 10Linked to original sources

arXiv2001

Predicting phase equilibria in polydisperse systems

Many materials containing colloids or polymers are polydisperse: They comprise particles with properties (such as particle diameter, charge, or polymer chain length) that depend continuously on one or several parameters. This review focusses on the theoretical prediction of phase equilibria in polydisperse systems; the presence of an effectively infinite number of distinguishable particle species makes this a highly nontrivial task. I first describe qualitatively some of the novel features of polydisperse phase behaviour, and outline a theoretical framework within which they can be explored. Current techniques for predicting polydisperse phase equilibria are then reviewed. I also discuss applications to some simple model systems including homopolymers and random copolymers, spherical colloids and colloid-polymer mixtures, and liquid crystals formed from rod- and plate-like colloidal particles; the results surveyed give an idea of the rich phenomenology of polydisperse phase behaviour. Extensions to the study of polydispersity effects on interfacial behaviour and phase separation kinetics are outlined briefly.

cond-mat.soft↗

arXiv2001

Observable-dependence of fluctuation-dissipation relations and effective temperatures

We study the non-equilibrium version of the fluctuation-dissipation theorem (FDT) within the glass phase of Bouchaud's trap model. We incorporate into the model an arbitrary observable m and obtain its correlation and response functions in closed form. A limiting non-equilibrium FDT plot (of correlator vs response) is approached at long times for most choices of m, with energy-temperature FDT a notable exception. In contrast to standard mean field models, however, the shape of the plot depends nontrivially on the observable, and its slope varies continuously even though there is a single scaling of relaxation times with age. Non-equilibrium FDT plots can therefore not be used to define a meaningful effective temperature T_eff in this model. Consequences for the wider applicability of an FDT-derived T_eff are discussed.

cond-mat.stat-mech↗

arXiv2001

Gaussian Process Regression with Mismatched Models

Learning curves for Gaussian process regression are well understood when the `student' model happens to match the `teacher' (true data generation process). I derive approximations to the learning curves for the more generic case of mismatched models, and find very rich behaviour: For large input space dimensionality, where the results become exact, there are universal (student-independent) plateaux in the learning curve, with transitions in between that can exhibit arbitrarily many over-fitting maxima. In lower dimensions, plateaux also appear, and the asymptotic decay of the learning curve becomes strongly student-dependent. All predictions are confirmed by simulations.

cond-mat.dis-nn↗

arXiv2001

Learning curves for Gaussian process regression: Approximations and bounds

We consider the problem of calculating learning curves (i.e., average generalization performance) of Gaussian processes used for regression. On the basis of a simple expression for the generalization error, in terms of the eigenvalue decomposition of the covariance function, we derive a number of approximation schemes. We identify where these become exact, and compare with existing bounds on learning curves; the new approximations, which can be used for any input space dimension, generally get substantially closer to the truth. We also study possible improvements to our approximations. Finally, we use a simple exactly solvable learning scenario to show that there are limits of principle on the quality of approximations and bounds expressible solely in terms of the eigenvalue spectrum of the covariance function.

cond-mat.dis-nn↗

arXiv2000

Phase equilibria in the polydisperse Zwanzig model of hard rods

We study the phase behaviour of the Zwanzig model of suspensions of hard rods, allowing for polydispersity in the lengths of the rods. In spite of the simplified nature of the model (rods are restricted to lie along one of three orthogonal axes), the results agree qualitatively with experimental observations: the coexistence region broadens significantly as the polydispersity increases, and strong fractionation occurs, with long rods found preferentially in the nematic phase. These conclusions are obtained from an analysis of the exact phase equilibrium equations. In the second part of the paper, we consider the application of the recently developed ``moment free energy method'' to the polydisperse Zwanzig model. Even though the model contains non-conserved densities due to the orientational degrees of freedom, most of the exactness statements (regarding the onset of phase coexistence, spinodals, and critical points) derived previously for systems with conserved densities remain valid. The accuracy of the results from the moment free energy increases as more and more additional moments are retained in the description. We show how this increase in accuracy can be monitored without relying on knowledge of the exact results, and discuss an adaptive technique for choosing the extra moments optimally.

cond-mat.soft↗

arXiv2000

Moment free energies for polydisperse systems

A polydisperse system contains particles with at least one attribute $σ$ (such as particle size in colloids or chain length in polymers) which takes values in a continuous range. It therefore has an infinite number of conserved densities, described by a density {\em distribution} $ρ(σ)$. The free energy depends on all details of $ρ(σ)$, making the analysis of phase equilibria in such systems intractable. However, in many (especially mean-field) models the {\em excess} free energy only depends on a finite number of (generalized) moments of $ρ(σ)$; we call these models truncatable. We show, for these models, how to derive approximate expressions for the {\em total} free energy which only depend on such moment densities. Our treatment unifies and explores in detail two recent separate proposals by the authors for the construction of such moment free energies. We show that even though the moment free energy only depends on a finite number of density variables, it gives the same spinodals and critical points as the original free energy and also correctly locates the onset of phase coexistence. Results from the moment free energy for the coexistence of two or more phases occupying comparable volumes are only approximate, but can be refined arbitrarily by retaining additional moment densities. Applications to Flory-Huggins theory for length-polydisperse homopolymers, and for chemically polydisperse copolymers, show that the moment free energy approach is computationally robust and gives new geometrical insights into the thermodynamics of polydispersity.

cond-mat.soft↗

arXiv1999

Glassy timescale divergence and anomalous coarsening in a kinetically constrained spin chain

We analyse the out of equilibrium behavior of an Ising spin chain with an asymmetric kinetic constraint after a quench to a low temperature T. In the limit T\to 0, we provide an exact solution of the resulting coarsening process. The equilibration time exhibits a `glassy' divergence \teq=\exp(const/T^2) (popular as an alternative to the Vogel-Fulcher law), while the average domain length grows with a temperature dependent exponent, \dbar ~ t^{T\ln 2}. We show that the equilibration time \teq also sets the timescale for the linear response of the system at low temperatures.

cond-mat.stat-mech↗

arXiv1998

Rheological constitutive equation for model of soft glassy materials

We solve exactly and describe in detail a simplified scalar model for the low frequency shear rheology of foams, emulsions, slurries, etc. [P. Sollich, F. Lequeux, P. Hebraud, M.E. Cates, Phys. Rev. Lett. 78, 2020 (1997)]. The model attributes similarities in the rheology of such ``soft glassy materials'' to the shared features of structural disorder and metastability. By focusing on the dynamics of mesoscopic elements, it retains a generic character. Interactions are represented by a mean-field noise temperature x, with a glass transition occurring at x=1 (in appropriate units). The exact solution of the model takes the form of a constitutive equation relating stress to strain history, from which all rheological properties can be derived. For the linear response, we find that both the storage modulus G' and the loss modulus G'' vary with frequency as ω^{x-1} for 1<x<2, becoming flat near the glass transition. In the glass phase, aging of the moduli is predicted. The steady shear flow curves show power law fluid behavior for x<2, with a nonzero yield stress in the glass phase; the Cox-Merz rule does not hold in this non-Newtonian regime. Single and double step strains further probe the nonlinear behavior of the model, which is not well represented by the BKZ relation. Finally, we consider measurements of G' and G'' at finite strain amplitude γ. Near the glass transition, G'' exhibits a maximum as γis increased in a strain sweep. Its value can be strongly overestimated due to nonlinear effects, which can be present even when the stress response is very nearly harmonic. The largest strain γ_c at which measurements still probe the linear response is predicted to be roughly frequency-independent.

cond-mat.soft↗

arXiv1997

Projected free energies for polydisperse phase equilibria

A `polydisperse' system has an infinite number of conserved densities. We give a rational procedure for projecting its infinite-dimensional free energy surface onto a subspace comprising a finite number of linear combinations of densities (`moments'), in which the phase behavior is then found as usual. If the excess free energy of the system depends only on the moments used, exact cloud, shadow and spinodal curves result; two- and multi-phase regions are approximate, but refinable indefinitely by adding extra moments. The approach is computationally robust and gives new geometrical insights into the thermodynamics of polydispersity.

cond-mat.stat-mech↗

arXiv1996

Rheology of Soft Glassy Materials

We attribute similarities in the rheology of many soft materials (foams, emulsions, slurries, etc.) to the shared features of structural disorder and metastability. A generic model for the mesoscopic dynamics of ``soft glassy matter'' is introduced, with interactions represented by a mean-field noise temperature x. We find power law fluid behavior either with (x<1) or without (1<x<2) a yield stress. For 1<x<2, both storage and loss modulus vary with frequency as $ω^{x-1}$, becoming flat near a glass transition (x=1). Values of $x\approx 1$ may result from marginal dynamics as seen in some spin glass models.

cond-mat.soft↗

arXiv1996

Learning from Minimum Entropy Queries in a Large Committee Machine

In supervised learning, the redundancy contained in random examples can be avoided by learning from queries. Using statistical mechanics, we study learning from minimum entropy queries in a large tree-committee machine. The generalization error decreases exponentially with the number of training examples, providing a significant improvement over the algebraic decay for random examples. The connection between entropy and generalization error in multi-layer networks is discussed, and a computationally cheap algorithm for constructing queries is suggested and analysed.

adap-org↗