Effective Electrostatic Interactions in Suspensions of Polyelectrolyte Brush-Coated Colloids

Effective electrostatic interactions between colloidal particles, coated with polyelectrolyte brushes and suspended in an electrolyte solvent, are described via linear response theory. The inner cores of the macroions are modeled as hard spheres, the outer brushes as spherical shells of continuously distributed charge, the microions (counterions and salt ions) as point charges, and the solvent as a dielectric continuum. The multi-component mixture of macroions and microions is formally mapped onto an equivalent one-component suspension by integrating out from the partition function the microion degrees of freedom. Applying second-order perturbation theory and a random phase approximation, analytical expressions are derived for the effective pair interaction and a one-body volume energy, which is a natural by-product of the one-component reduction. The combination of an inner core and an outer shell, respectively impenetrable and penetrable to microions, allows the interactions between macroions to be tuned by varying the core diameter and brush thickness. In the limiting cases of vanishing core diameter and vanishing shell thickness, the interactions reduce to those derived previously for star polyelectrolytes and charged colloids, respectively.Comment: 20 pages, 5 figures, Phys. Rev. E (in press

Universal Elasticity and Fluctuations of Nematic Gels

We study elasticity of spontaneously orientationally-ordered amorphous solids, characterized by a vanishing transverse shear modulus, as realized for example by nematic elastomers and gels. We show that local heterogeneities and elastic nonlinearities conspire to lead to anomalous nonlocal universal elasticity controlled by a nontrivial infared fixed point. Namely, at long scales, such solids are characterized by universal shear and bending moduli that, respectively, vanish and diverge at long scales, are universally incompressible and exhibit a universal negative Poisson ratio and a non-Hookean elasticity down to arbitrarily low strains. Based on expansion about five dimensions, we argue that the nematic order is stable to thermal fluctuation and local hetergeneities down to d_lc < 3.Comment: 4 RevTeX pgs, submitted to PR

Attraction between like-charged colloidal particles induced by a surface a density - functional analysis

We show that the first non-linear correction to the linearised Poisson-Boltzman n (or DLVO) theory of effective pair interactions between charge-stabilised, co lloidal particles near a charged wall leads to an attractive component of entro pic origin. The position and depth of the potential compare favourably with rec ent experimental measurementsComment: 12 pages including 2 figures. submitted to physical review letter

Order parameters in the Verwey phase transition

The Verwey phase transition in magnetite is analyzed on the basis of the Landau theory. The free energy functional is expanded in a series of components belonging to the primary and secondary order parameters. A low-temperature phase with the monoclinic P2/c symmetry is a result of condensation of two order parameters X_3 and \Delta_5 . The temperature dependence of the shear elastic constant C_44 is derived and the mechanism of its softening is discussed.Comment: 4 pages, 1 figur

Modulation and correlations lengths in systems with competing interactions

We examine correlation functions in the presence of competing long and short ranged interactions to find multiple correlation and modulation lengths. We calculate the ground state stripe width of an Ising ferromagnet, frustrated by an arbitrary long range interaction. In large $n$ systems, we demonstrate that for a short range system frustrated by a general competing long range interaction, the crossover temperature $T^*$ veers towards the critical temperature of the unfrustrated short range system (i.e., that in which the frustrating long range interaction is removed). We also show that apart from certain special crossover points, the total number of correlation and modulation lengths remains conserved. We derive an expression for the change in modulation length with temperature for a general system near the ground state with a ferromagnetic interaction and an opposing long range interaction. We illustrate that the correlation functions associated with the exact dipolar interactions differ substantially from those in which a scalar product form between the dipoles is assumed.Comment: 17 pages, 9 figure

Discrete charge patterns, Coulomb correlations and interactions in protein solutions

The effective Coulomb interaction between globular proteins is calculated as a function of monovalent salt concentration $c_s$, by explicit Molecular Dynamics simulations of pairs of model proteins in the presence of microscopic co and counterions. For discrete charge patterns of monovalent sites on the surface, the resulting osmotic virial coefficient $B_2$ is found to be a strikingly non-monotonic function of $c_s$. The non-monotonicity follows from a subtle Coulomb correlation effect which is completely missed by conventional non-linear Poisson-Boltzmann theory and explains various experimental findings.Comment: 4 twocolumn pages with 4 figure

Uniaxial and biaxial soft deformations of nematic elastomers

We give a geometric interpretation of the soft elastic deformation modes of nematic elastomers, with explicit examples, for both uniaxial and biaxial nematic order. We show the importance of body rotations in this non-classical elasticity and how the invariance under rotations of the reference and target states gives soft elasticity (the Golubovic and Lubensky theorem). The role of rotations makes the Polar Decomposition Theorem vital for decomposing general deformations into body rotations and symmetric strains. The role of the square roots of tensors is discussed in this context and that of finding explicit forms for soft deformations (the approach of Olmsted).Comment: 10 pages, 10 figures, RevTex, AmsTe

Effect of many-body interactions on the solid-liquid phase-behavior of charge-stabilized colloidal suspensions

The solid-liquid phase-diagram of charge-stabilized colloidal suspensions is calculated using a technique that combines a continuous Poisson-Boltzmann description for the microscopic electrolyte ions with a molecular-dynamics simulation for the macroionic colloidal spheres. While correlations between the microions are neglected in this approach, many-body interactions between the colloids are fully included. The solid-liquid transition is determined at a high colloid volume fraction where many-body interactions are expected to be strong. With a view to the Derjaguin-Landau-Verwey-Overbeek theory predicting that colloids interact via Yukawa pair-potentials, we compare our results with the phase diagram of a simple Yukawa liquid. Good agreement is found at high salt conditions, while at low ionic strength considerable deviations are observed. By calculating effective colloid-colloid pair-interactions it is demonstrated that these differences are due to many-body interactions. We suggest a density-dependent pair-potential in the form of a truncated Yukawa potential, and show that it offers a considerably improved description of the solid-liquid phase-behavior of concentrated colloidal suspensions

Charge ordering in the spinels AlV2_2O4_4 and LiV2_2O4_4

We develop a microscopic theory for the charge ordering (CO) transitions in the spinels AlV$_2$O$_4$ and LiV$_2$O$_4$ (under pressure). The high degeneracy of CO states is lifted by a coupling to the rhombohedral lattice deformations which favors transition to a CO state with inequivalent V(1) and V(2) sites forming Kagom\'e and trigonal planes respectively. We construct an extended Hubbard type model including a deformation potential which is treated in unrestricted Hartree Fock approximation and describes correctly the observed first-order CO transition. We also discuss the influence of associated orbital order. Furthermore we suggest that due to different band fillings AlV$_2$O$_4$ should remain metallic while LiV$_2$O$_4$ under pressure should become a semiconductor when charge disproportionation sets in

Charge Order Superstructure with Integer Iron Valence in Fe2OBO3

Solution-grown single crystals of Fe2OBO3 were characterized by specific heat, Mossbauer spectroscopy, and x-ray diffraction. A peak in the specific heat at 340 K indicates the onset of charge order. Evidence for a doubling of the unit cell at low temperature is presented. Combining structural refinement of diffraction data and Mossbauer spectra, domains with diagonal charge order are established. Bond-valence-sum analysis indicates integer valence states of the Fe ions in the charge ordered phase, suggesting Fe2OBO3 is the clearest example of ionic charge order so far.Comment: 4 pages, 5 figures. Fig. 3 is available in higher resolution from the authors. PRL in prin