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V. Krakoviack

Publications and source records attributed to V. Krakoviack.

17 recordsLinked to original sources

Tagged-particle dynamics in a fluid adsorbed in a disordered porous solid: interplay between the diffusion-localization and liquid-glass transitions

A mode-coupling theory for the slow single-particle dynamics in fluids adsorbed in disordered porous media is derived, which complements previous work on the collective dynamics [V. Krakoviack, Phys. Rev. E 75, 031503 (2007)]. Its equations, like the previous ones, reflect the interplay between confinement-induced relaxation phenomena and glassy dynamics through the presence of two contributions in the slow part of the memory kernel, which are linear and quadratic in the density correlation functions, respectively. From numerical solutions for two simple models with pure hard core interactions, it is shown that two different scenarios result for the diffusion-localization transition, depending on the strength of the confinement. For weak confinement, this transition is discontinuous and coincides with the ideal glass transition, like in one-component bulk systems, while, for strong confinement, it is continuous and occurs before the collective dynamics gets nonergodic. In the latter case, the glass transition manifests itself as a secondary transition, which can be either continuous or discontinuous, in the already arrested single-particle dynamics. The main features of the anomalous dynamics found in the vicinity of all these transitions are reviewed and illustrated with detailed computations.

cond-mat.dis-nn

Comment on ``Spherical 2 + p spin-glass model: An analytically solvable model with a glass-to-glass transition''

Guided by old results on simple mode-coupling models displaying glass-glass transitions, we demonstrate, through a crude analysis of the solution with one step of replica symmetry breaking (1RSB) derived by Crisanti and Leuzzi for the spherical $s+p$ mean-field spin glass [Phys. Rev. B 73, 014412 (2006)], that the phase behavior of these systems is not yet fully understood when $s$ and $p$ are well separated. First, there seems to be a possibility of glass-glass transition scenarios in these systems. Second, we find clear indications that the 1RSB solution cannot be correct in the full glassy phase. Therefore, while the proposed analysis is clearly naive and probably inexact, it definitely calls for a reassessment of the physics of these systems, with the promise of potentially interesting new developments in the theory of disordered and complex systems.

cond-mat.dis-nn

Mode-coupling theory for the slow collective dynamics of fluids adsorbed in disordered porous media

We derive a mode-coupling theory for the slow dynamics of fluids confined in disordered porous media represented by spherical particles randomly placed in space. Its equations display the usual nonlinear structure met in this theoretical framework, except for a linear contribution to the memory kernel which adds to the usual quadratic term. The coupling coefficients involve structural quantities which are specific of fluids evolving in random environments and have expressions which are consistent with those found in related problems. Numerical solutions for two simple models with pure hard core interactions lead to the prediction of a variety of glass transition scenarios, which are either continuous or discontinuous and include the possibility of higher-order singularities and glass-glass transitions. The main features of the dynamics in the two most generic cases are reviewed and illustrated with detailed computations. Moreover, a reentry phenomenon is predicted in the low fluid-high matrix density regime and is interpreted as the signature of a decorrelation mechanism by fluid-fluid collisions competing with the localization effect of the solid matrix.

cond-mat.soft

Relating monomer to center-of-mass distribution functions in macromolecular fluids: extension to arbitrary systems

In the framework of the polymer reference interaction site model (PRISM) extended to incorporate the centers of mass (CM) of the groups of monomers constitutive of the macromolecules as auxiliary sites, a general relationship between the monomer-monomer and CM-CM pair correlation functions is derived for arbitrary mixtures of macromolecules of arbitrary structure. It extends previous results for homopolymer fluids and should be useful to develop semi-analytic coarse-grained descriptions of complex fluids.

cond-mat.soft

Coarse-graining diblock copolymer solutions: a macromolecular version of the Widom-Rowlinson model

We propose a systematic coarse-grained representation of block copolymers, whereby each block is reduced to a single ``soft blob'' and effective intra- as well as intermolecular interactions act between centres of mass of the blocks. The coarse-graining approach is applied to simple athermal lattice models of symmetric AB diblock copolymers, in particular to a Widom-Rowlinson-like model where blocks of the same species behave as ideal polymers (i.e. freely interpenetrate), while blocks of opposite species are mutually avoiding walks. This incompatibility drives microphase separation for copolymer solutions in the semi-dilute regime. An appropriate, consistent inversion procedure is used to extract effective inter- and intramolecular potentials from Monte Carlo results for the pair distribution functions of the block centres of mass in the infinite dilution limit.

cond-mat.soft

Liquid-glass transition of confined fluids: Some insights from a mode-coupling theory

The dynamics of confined glassforming liquids is discussed on the basis of the recent extension of the mode coupling theory for the liquid-glass transition to the model of the quenched-annealed binary mixture. It is in particular shown that, in confinement, the density correlation functions always decay to a non-zero infinite time value, even in the fluid state, and some clarification is given about the question of the relation between structure and dynamics in confined fluids.

cond-mat.dis-nn

Liquid-glass transition of a fluid confined in a disordered porous matrix: A mode-coupling theory

We derive an extension of the mode coupling theory for the liquid-glass transition to a class of models of confined fluids, where the fluid particles evolve in a disordered array of interaction sites. We find that the corresponding equations are similar to those describing the bulk, implying that the methods of investigation which were developed there are directly transferable to this new domain of application. We then compute the dynamical phase diagram of a simple model system and show that new and nontrivial transition scenarios, including reentrant glass transitions and higher-order singularities, can be predicted from the proposed theory.

cond-mat.dis-nn

An integral equation approach to effective interactions between polymers in solution

We use the thread model for linear chains of interacting monomers, and the ``polymer reference interaction site model'' (PRISM) formalism to determine the monomer-monomer pair correlation function $h_{mm}(r)$ for dilute and semi-dilute polymer solutions, over a range of temperatures from very high (where the chains behave as self-avoiding walks) to below the $θ$ temperature, where phase separation sets in. An inversion procedure, based on the HNC integral equation, is used to extract the effective pair potential between ``average'' monomers on different chains. An accurate relation between $h_{mm}(r)$, $h_{cc}(r)$ [the pair correlation function between the polymer centers of mass (c.m.)], and the intramolecular form factors is then used to determine $h_{cc}(r)$, and subsequently extract the effective c.m.-c.m. pair potential $v_{cc}(r)$ by a similar inversion procedure. $v_{cc}(r)$ depends on temperature and polymer concentration, and the predicted variations are in reasonable agreement with recent simulation data, except at very high temperatures, and below the $θ$ temperature.

cond-mat.soft

Influence of solvent quality on effective pair potentials between polymers in solution

Solutions of interacting linear polymers are mapped onto a system of ``soft'' spherical particles interacting via an effective pair potential. This coarse-graining reduces the individual monomer-level description to a problem involving only the centers of mass (CM) of the polymer coils. The effective pair potentials are derived by inverting the CM pair distribution function, generated in Monte Carlo simulations, using the hypernetted chain (HNC) closure. The method, previously devised for the self-avoiding walk model of polymers in good solvent, is extended to the case of polymers in solvents of variable quality by adding a finite nearest-neighbor monomer-monomer attraction to the previous model and varying the temperature. The resulting effective pair potential is found to depend strongly on temperature and polymer concentration. At low concentration the effective interaction becomes increasingly attractive as the temperature decreases, eventually violating thermodynamic stability criteria. However, as polymer concentration is increased at fixed temperature, the effective interaction reverts to mostly repulsive behavior. These issues help illustrate some fundamental difficulties encountered when coarse-graining complex systems via effective pair potentials.

cond-mat.soft

Site-averaging in the integral equation theory of interaction site models of macromolecular fluids: An exact approach

A simple "trick" is proposed, which allows to perform exactly the site-averaging procedure required when developing integral equation theories of interaction site models of macromolecular fluids. It shows that no approximation is involved when the number of Ornstein-Zernike equations coupling the site-site correlation functions is reduced to one. Its potential practical interest for future theoretical developments is illustrated with a rederivation of the so-called molecular closures.

cond-mat.soft

Relating monomer to centre-of-mass distribution functions in polymer solutions

A relationship between the measurable monomer-monomer structure factor, and the centre-of-mass (CM) structure factor of dilute or semi-dilute polymer solutions is derived from Ornstein-Zernike relations within the ``polymer reference interaction site model'' (PRISM) formalism, by considering the CM of each polymer as an auxiliary site and neglecting direct correlations between the latter and the CM and monomers of neighbouring polymers. The predictions agree well with Monte Carlo data for self-avoiding walk polymers, and are considerably more accurate than the predictions of simple factorization approximations.

cond-mat.soft

Langevin dynamics of the Coulomb frustrated ferromagnet: a mode-coupling analysis

We study the Langevin dynamics of the soft-spin, continuum version of the Coulomb frustrated Ising ferromagnet. By using the dynamical mode-coupling approximation, supplemented by reasonable approximations for describing the equilibrium static correlation function, and the somewhat improved dynamical self-consistent screening approximation, we find that the system displays a transition from an ergodic to a non-ergodic behavior. This transition is similar to that obtained in the idealized mode-coupling theory of glassforming liquids and in the mean-field generalized spin glasses with one-step replica symmetry breaking. The significance of this result and the relation to the appearance of a complex free-energy landscape are also discussed.

cond-mat.dis-nn

What can be learned from the schematic mode-coupling approach to experimental data ?

We propose a detailed investigation of the schematic mode-coupling approach to experimental data, a method based on the use of simple mode-coupling equations to analyze the dynamics of supercooled liquids. Our aim here is to clarify different aspects of this approach that appeared so far uncontrolled or arbitrary, and to validate the results obtained from previous works. Analyzing the theoretical foundations of the approach, we first identify the parameters of the theory playing a key role and obtain simple requirements to be met by a schematic model for its use in this context. Then we compare the results obtained from the schematic analysis of a given set of experimental data with a variety of models and show that they are all perfectly consistent. A number of potential biases in the method are identified and ruled out by the choice of appropriate models. Finally, reference spectra computed from the mode-coupling theory for a model simple liquid are analyzed along the same lines as experimental data, allowing us to show that, despite the strong simplification in the description of the dynamics it involves, the method is free from spurious artifacts and provides accurate estimates of important parameters of the theory. The only exception is the exponent parameter, the evaluation of which is hindered, as for other methods, by corrections to the asymptotic laws of the theory present when the dynamics is known only in a limited time or frequency range.

cond-mat.dis-nn

Coarse-graining polymers as soft colloids

We show how to coarse grain polymers in a good solvent as single particles, interacting with density-independent or density-dependent interactions. These interactions can be between the centres of mass, the mid-points or end-points of the polymers. We also show how to extend these methods to polymers in poor solvents and mixtures of polymers. Treating polymers as soft colloids can greatly speed up the simulation of complex many-polymer systems, including polymer-colloid mixtures.

cond-mat.soft

Adsorption of a fluid in an aerogel: integral equation approach

We present a theoretical study of the phase diagram and the structure of a fluid adsorbed in high-porosity aerogels by means of an integral-equation approach combined with the replica formalism. To simulate a realistic gel environment, we use an aerogel structure factor obtained from an off-lattice diffusion-limited cluster-cluster aggregation process. The predictions of the theory are in qualitative agreement with the experimental results, showing a substantial narrowing of the gas-liquid coexistence curve (compared to that of the bulk fluid), associated with weak changes in the critical density and temperature. The influence of the aerogel structure (nontrivial short-range correlations due to connectedness, long-range fractal behavior of the silica strands) is shown to be important at low fluid densities.

cond-mat.dis-nn

Quantitative investigation of the mean-field scenario for the structural glass transition from a schematic mode-coupling analysis of experimental data

A quantitative application to real supercooled liquids of the mean-field scenario for the glass transition ($T_g$) is proposed. This scenario, based on an analogy with spin-glass models, suggests a unified picture of the mode-coupling dynamical singularity ($T_c$) and of the entropy crisis at the Kauzmann temperature ($T_K$), with $T_c>T_g>T_K$. Fitting a simple set of mode-coupling equations to experimental light-scattering spectra of two fragile liquids and deriving the equivalent spin-glass model, we can estimate not only $T_c$, but also the static transition temperature $T_s$ corresponding supposedly to $T_K$. For the models and systems considered here, $T_s$ is always found above $T_g$, in the fluid phase. A comparison with recent theoretical calculations shows that this overestimation of the ability of a liquid to form a glass seems to be a generic feature of the mean-field approach.

cond-mat.dis-nn

Study of the Depolarized Light Scattering Spectra of Supercooled Liquids by a Simple Mode-Coupling Model

By using simple mode coupling equations, we investigate the depolarized light scattering spectra of two so-called "fragile" glassforming liquids, salol (phenylsalicylate) and CKN (Ca_{0.4}K_{0.6}(NO_3)_{1.4}), measured by Cummins and coworkers. Nonlinear integrodifferential equations for the time evolution of the density-fluctuations autocorrelation functions are the basic input of the mode coupling theory. Restricting ourselves to a small set of such equations, we fit the numerical solution to the experimental spectra. It leads to a good agreement between model and experiment, which allows us to determine how a real system explores the parameter space of the model, but it also leads to unrealistic effective vertices in a temperature range where the theory makes critical asymptotic predictions. We finally discuss the relevance and the range of validity of these universal asymptotic predictions when applied to experimental data on supercooled liquids.

cond-mat.stat-mech