Dynamics of fluids in quenched-random potential energy landscapes: a mode-coupling theory approach.

Motivated by a number of recent experimental and computational studies of the dynamics of fluids plunged in quenched-disordered external fields, we report on a theoretical investigation of this topic within the framework of the mode-coupling theory, based on the simple model of the hard-sphere fluid in a Gaussian random field. The possible dynamical arrest scenarios driven by an increase of the disorder strength and/or of the fluid density are mapped, and the corresponding evolutions of time-dependent quantities typically used for the characterization of anomalous self-diffusion are illustrated with detailed computations. Overall, a fairly reasonable picture of the dynamics of the system at hand is outlined, which in particular involves a non-monotonicity of the self-diffusion coefficient with fluid density at fixed disorder strength, in agreement with experiments. The disorder correlation length is shown to have a strong influence on the latter feature.

Comment on "Static correlations functions and domain walls in glass-forming liquids: The case of a sandwich geometry" [J. Chem. Phys. 138, 12A509 (2013)].

In this Comment, we argue that the behavior of the overlap functions reported in the commented paper can be fully understood in terms of the physics of simple liquids in contact with disordered substrates, without appealing to any particular glassy phenomenology. This suggestion is further supported by an analytic study of the one-dimensional Ising model provided as Supplementary Material.

Simple physics of the partly pinned fluid systems.

In this paper, we consider some aspects of the physics of the partly pinned (PP) systems obtained by freezing in place particles in equilibrium bulk fluid configurations in the normal (nonglassy) state. We first discuss the configurational overlap and the disconnected density correlation functions, both in the homogeneous and heterogeneous cases, using the tools of the theory of adsorption in disordered porous solids. The relevant Ornstein-Zernike equations are derived, and asymptotic results valid in the regime where the perturbation due to the pinning process is small are obtained. Second, we consider the homogeneous PP lattice gas as a means to make contact between pinning processes in particle and spin systems and show that it can be straightforwardly mapped onto a random field Ising model with a strongly asymmetric bimodal distribution of the field. Possible implications of these results for studies of the glass transition based on PP systems are also discussed.

Mode-coupling theory of the glass transition for confined fluids.

We present a detailed derivation of a microscopic theory for the glass transition of a liquid enclosed between two parallel walls relying on a mode-coupling approximation. This geometry lacks translational invariance perpendicular to the walls, which implies that the density profile and the density-density correlation function depends explicitly on the distances to the walls. We discuss the residual symmetry properties in slab geometry and introduce a symmetry adapted complete set of two-point correlation functions. Since the currents naturally split into components parallel and perpendicular to the walls the mathematical structure of the theory differs from the established mode-coupling equations in bulk. We prove that the equations for the nonergodicity parameters still display a covariance property similar to bulk liquids.

Mode-coupling theory predictions for the dynamical transitions of partly pinned fluid systems.

The predictions of the mode-coupling theory (MCT) for the dynamical arrest scenarios in a partly pinned (PP) fluid system are reported. The corresponding dynamical phase diagram is found to be very similar to that of a related quenched-annealed (QA) system. The only significant qualitative difference lies in the shape of the diffusion-localization lines at high matrix densities, with a reentry phenomenon for the PP system but not for the QA model, in full agreement with recent computer simulation results. This finding clearly lends support to the predictive power of the MCT for fluid-matrix systems. In addition, the predictions of the MCT are shown to be in stark contrast with those of the random first-order transition theory. The PP systems are thus confirmed as very promising models for differentiating tests of theories of the glass transition.

Statistical mechanics of homogeneous partly pinned fluid systems.

The homogeneous partly pinned fluid systems are simple models of a fluid confined in a disordered porous matrix obtained by arresting randomly chosen particles in a one-component bulk fluid or one of the two components of a binary mixture. In this paper, their configurational properties are investigated. It is shown that a peculiar complementarity exists between the mobile and immobile phases, which originates from the fact that the solid is prepared in presence of and in equilibrium with the adsorbed fluid. Simple identities follow, which connect different types of configurational averages, either relative to the fluid-matrix system or to the bulk fluid from which it is prepared. Crucial simplifications result for the computation of important structural quantities, both in computer simulations and in theoretical approaches. Finally, possible applications of the model in the field of dynamics in confinement or in strongly asymmetric mixtures are suggested.

Entropic self-assembly of diblock copolymers into disordered and ordered micellar phases.

We investigate the self-assembly of an athermal model of AB diblock copolymers into disordered and ordered micellar microphases. The original microscopic lattice model with ideal A strands and self-avoiding B strands is mapped onto a system of ultrasoft dumbbells, with monomer-averaged effective interactions between the centers of mass (CMs) of the two blocks. Extensive Monte Carlo simulations of this coarse-grained model are reported for several length ratios f = L(A)/(L(A) + L(B)) of the two strands of lengths L(A) and L(B). Clear-cut evidence is found for clustering and self-assembly into micelles with a mean aggregation number of n approximately equal 100 beyond a critical micellar concentration (cmc) in the semidilute regime. The cmc is found to decrease with increasing f, as predicted by an analytic calculation based on the random phase approximation. The initially disordered dispersion of polydisperse spherical micelles undergoes a disorder-order transition to a micellar crystal phase at higher copolymer concentrations. The effective pair potential between the micellar CMs is determined by inverting the measured CM-CM pair distribution function and is found to become steeper with increasing density.

Heterolytic splitting of H2 and CH4 on gamma-alumina as a structural probe for defect sites.

A combined use of DFT periodic calculations and spectroscopic studies (IR and solid-state NMR) shows that a gamma-alumina treated at 500 degrees C under high vacuum contains surface defects, which are very reactive toward H2 or CH4. The reaction of H2 on defect sites occurs at low temperature (ca. 25 degrees C) on two types of Al atoms of low coordination numbers, AlIII or AlIV, to give AlIV-H and AlV-H, respectively. The amount of defects as titrated by H2 at 25 and 150 degrees C is 0.043 and 0.069 site/nm2, respectively, in comparison with 4 OH/nm2). In contrast, CH4 reacts selectively at 100-150 degrees C on the most reactive AlIII sites to form the corresponding AlIV-CH3 (0.030 site/nm2). The difference of reactivity of H2 and CH4 is fully consistent with calculations (reaction and activation energy, DeltaE and DeltaE++).

Multiscale coarse graining of diblock copolymer self-assembly: from monomers to ordered micelles.

Starting from a microscopic lattice model, we investigate clustering, micellization, and micelle ordering in semidilute solutions of AB diblock copolymers in a selective solvent. To bridge the gap in length scales, from monomers to ordered micellar structures, we implement a two-step coarse-graining strategy, whereby the AB copolymers are mapped onto ultrasoft dumbells with monomer-averaged effective interactions between the centers of mass of the blocks. Monte Carlo simulations of this coarse-grained model yield clear-cut evidence for self-assembly into micelles with a mean aggregation number n approximately 100 beyond a critical concentration. At a slightly higher concentration the micelles spontaneously undergo a disorder-order transition to a cubic phase. We determine the effective potential between these micelles from first principles.