Statistical mechanics of permanent random atomic and molecular networks: Structure and heterogeneity of the amorphous solid state

Under sufficient permanent random covalent bonding, a fluid of atoms or small molecules is transformed into an amorphous solid network. Being amorphous, local structural properties in such networks vary across the sample. A natural order parameter, resulting from a statistical-mechanical approach, captures information concerning this heterogeneity via a certain joint probability distribution. This joint probability distribution describes the variations in the positional and orientational localization of the particles, reflecting the random environments experienced by them, as well as further information characterizing the thermal motion of particles. A complete solution, valid in the vicinity of the amorphous solidification transition, is constructed essentially analytically for the amorphous solid order parameter, in the context of the random network model and approach introduced by Goldbart and Zippelius [Europhys. Lett. 27, 599 (1994)]. Knowledge of this order parameter allows us to draw certain conclusions about the stucture and heterogeneity of randomly covalently bonded atomic or molecular network solids in the vicinity of the amorphous solidification transition. Inter alia, the positional aspects of particle localization are established to have precisely the structure obtained perviously in the context of vulcanized media, and results are found for the analogue of the spin glass order parameter describing the orientational freezing of the bonds between particles.Comment: 31 pages, 5 figure

Quantal Andreev billiards: Semiclassical approach to mesoscale oscillations in the density of states

Andreev billiards are finite, arbitrarily-shaped, normal-state regions, surrounded by superconductor. At energies below the superconducting gap, single-quasiparticle excitations are confined to the normal region and its vicinity, the essential mechanism for this confinement being Andreev reflection. This Paper develops and implements a theoretical framework for the investigation of the short-wave quantal properties of these single-quasiparticle excitations. The focus is primarily on the relationship between the quasiparticle energy eigenvalue spectrum and the geometrical shape of the normal-state region, i.e., the question of spectral geometry in the novel setting of excitations confined by a superconducting pair-potential. Among the central results of this investigation are two semiclassical trace formulas for the density of states. The first, a lower-resolution formula, corresponds to the well-known quasiclassical approximation, conventionally invoked in settings involving superconductivity. The second, a higher-resolution formula, allows the density of states to be expressed in terms of: (i) An explicit formula for the level density, valid in the short-wave limit, for billiards of arbitrary shape and dimensionality. This level density depends on the billiard shape only through the set of stationary-length chords of the billiard and the curvature of the boundary at the endpoints of these chords; and (ii) Higher-resolution corrections to the level density, expressed as a sum over periodic orbits that creep around the billiard boundary. Owing to the fact that these creeping orbits are much longer than the stationary chords, one can, inter alia, hear the stationary chords of Andreev billiards.Comment: 52 pages, 15 figures, 1 table, RevTe

Universality and its Origins at the Amorphous Solidification Transition

Systems undergoing an equilibrium phase transition from a liquid state to an amorphous solid state exhibit certain universal characteristics. Chief among these are the fraction of particles that are randomly localized and the scaling functions that describe the order parameter and (equivalently) the statistical distribution of localization lengths for these localized particles. The purpose of this Paper is to discuss the origins and consequences of this universality, and in doing so, three themes are explored. First, a replica-Landau-type approach is formulated for the universality class of systems that are composed of extended objects connected by permanent random constraints and undergo amorphous solidification at a critical density of constraints. This formulation generalizes the cases of randomly cross-linked and end-linked macromolecular systems, discussed previously. The universal replica free energy is constructed, in terms of the replica order parameter appropriate to amorphous solidification, the value of the order parameter is obtained in the liquid and amorphous solid states, and the chief universal characteristics are determined. Second, the theory is reformulated in terms of the distribution of local static density fluctuations rather than the replica order parameter. It is shown that a suitable free energy can be constructed, depending on the distribution of static density fluctuations, and that this formulation yields precisely the same conclusions as the replica approach. Third, the universal predictions of the theory are compared with the results of extensive numerical simulations of randomly cross-linked macromolecular systems, due to Barsky and Plischke, and excellent agreement is found.Comment: 10 pages, including 3 figures (REVTEX

Cavity Approach to the Random Solid State

The cavity approach is used to address the physical properties of random solids in equilibrium. Particular attention is paid to the fraction of localized particles and the distribution of localization lengths characterizing their thermal motion. This approach is of relevance to a wide class of random solids, including rubbery media (formed via the vulcanization of polymer fluids) and chemical gels (formed by the random covalent bonding of fluids of atoms or small molecules). The cavity approach confirms results that have been obtained previously via replica mean-field theory, doing so in a way that sheds new light on their physical origin.Comment: 4 pages, 2 figure

Goldstone fluctuations in the amorphous solid state

Goldstone modes in the amorphous solid state, resulting from the spontaneous breaking of translational symmetry due to random localisation of particles, are discussed. Starting from a microscopic model with quenched disorder, the broken symmetry is identified to be that of relative translations of the replicas. Goldstone excitations, corresponding to pure shear deformations, are constructed from long wavelength distortions of the order parameter. The elastic free energy is computed, and it is shown that Goldstone fluctuations destroy localisation in two spatial dimensions, yielding a two-dimensional amorphous solid state characterised by power-law correlations.Comment: 7 pages, 2 figure

Impact of single-particle compressibility on the fluid-solid phase transition for ionic microgel suspensions

We study ionic microgel suspensions composed of swollen particles for various single-particle stiffnesses. We measure the osmotic pressure $\pi$ of these suspensions and show that it is dominated by the contribution of free ions in solution. As this ionic osmotic pressure depends on the volume fraction of the suspension $\phi$, we can determine $\phi$ from $\pi$, even at volume fractions so high that the microgel particles are compressed. We find that the width of the fluid-solid phase coexistence, measured using $\phi$, is larger than its hard-sphere value for the stiffer microgels that we study and progressively decreases for softer microgels. For sufficiently soft microgels, the suspensions are fluid-like, irrespective of volume fraction. By calculating the dependence on $\phi$ of the mean volume of a microgel particle, we show that the behavior of the phase-coexistence width correlates with whether or not the microgel particles are compressed at the volume fractions corresponding to fluid-solid coexistence.Comment: 5 pages, 3 figure

Random solids and random solidification: What can be learned by exploring systems obeying permanent random constraints?

In many interesting physical settings, such as the vulcanization of rubber, the introduction of permanent random constraints between the constituents of a homogeneous fluid can cause a phase transition to a random solid state. In this random solid state, particles are permanently but randomly localized in space, and a rigidity to shear deformations emerges. Owing to the permanence of the random constraints, this phase transition is an equilibrium transition, which confers on it a simplicity (at least relative to the conventional glass transition) in the sense that it is amenable to established techniques of equilibrium statistical mechanics. In this Paper I shall review recent developments in the theory of random solidification for systems obeying permanent random constraints, with the aim of bringing to the fore the similarities and differences between such systems and those exhibiting the conventional glass transition. I shall also report new results, obtained in collaboration with Weiqun Peng, on equilibrium correlations and susceptibilities that signal the approach of the random solidification transition, discussing the physical interpretation and values of these quantities both at the Gaussian level of approximation and, via a renormalization-group approach, beyond.Comment: Paper presented at the "Unifying Concepts in Glass Physics" workshop, International Centre for Theoretical Physics, Trieste, Italy (September 15-18, 1999

On the relevance of percolation theory to the vulcanization transition

The relationship between vulcanization and percolation is explored from the perspective of renormalized local field theory. We show rigorously that the vulcanization and percolation correlation functions are governed by the same Gell--Mann-Low renormalization group equation. Hence, all scaling aspects of the vulcanization transition are reigned by the critical exponents of the percolation universality class.Comment: 9 pages, 2 figure

Elasticity near the vulcanization transition

Signatures of the vulcanization transition--amorphous solidification induced by the random crosslinking of macromolecules--include the random localization of a fraction of the particles and the emergence of a nonzero static shear modulus. A semi-microscopic statistical-mechanical theory is presented of the latter signature that accounts for both thermal fluctuations and quenched disorder. It is found (i) that the shear modulus grows continuously from zero at the transition, and does so with the classical exponent, i.e., with the third power of the excess cross-link density and, quite surprisingly, (ii) that near the transition the external stresses do not spoil the spherical symmetry of the localization clouds of the particles.Comment: REVTEX, 5 pages. Minor change

Glassy correlations and microstructures in randomly crosslinked homopolymer blends

We consider a microscopic model of a polymer blend that is prone to phase separation. Permanent crosslinks are introduced between randomly chosen pairs of monomers, drawn from the Deam-Edwards distribution. Thereby, not only density but also concentration fluctuations of the melt are quenched-in in the gel state, which emerges upon sufficient crosslinking. We derive a Landau expansion in terms of the order parameters for gelation and phase separation, and analyze it on the mean-field level, including Gaussian fluctuations. The mixed gel is characterized by thermal as well as time-persistent (glassy) concentration fluctuations. Whereas the former are independent of the preparation state, the latter reflect the concentration fluctuations at the instant of crosslinking, provided the mesh size is smaller than the correlation length of phase separation. The mixed gel becomes unstable to microphase separation upon lowering the temperature in the gel phase. Whereas the length scale of microphase separation is given by the mesh size, at least close to the transition, the emergent microstructure depends on the composition and compressibility of the melt. Hexagonal structures, as well as lamellae or random structures with a unique wavelength, can be energetically favorable.Comment: 19 pages, 10 figures. Submitted to the Journal of Chemical Physics (http://jcp.aip.org