Microphase separation in polyelectrolytic diblock copolymer melt : weak segregation limit

We present a generalized theory of microphase separation for charged-neutral diblock copolymer melt. Stability limit of the disordered phase for salt-free melt has been calculated using Random Phase Approximation (RPA) and self-consistent field theory (SCFT). Explicit analytical free energy expressions for different classical ordered microstructures (lamellar, cylinder and sphere) are presented. We demonstrate that chemical mismatch required for the onset of microphase separation ($\chi^{\star} N$) in charged-neutral diblock melt is higher and the period of ordered microstructures is lower than those for the corresponding neutral-neutral diblock system. Theoretical predictions on the period of ordered structures in terms of Coulomb electrostatic interaction strength, chain length, block length, and the chemical mismatch between blocks are presented. SCFT has been used to go beyond the stability limit, where electrostatic potential and charge distribution are calculated self-consistently. Stability limits calculated using RPA are in perfect agreement with the corresponding SCFT calculations. Limiting laws for stability limit and the period of ordered structures are presented and comparisons are made with an earlier theory. Also, transition boundaries between different morphologies have been investigated

Orientations of the lamellar phase of block copolymer melts under oscillatory shear flow

We develop a theory to describe the reorientation phenomena in the lamellar phase of block copolymer melt under reciprocating shear flow. We show that similar to the steady-shear, the oscillating flow anisotropically suppresses fluctuations and gives rise to the parallel-perpendicular orientation transition. The experimentally observed high-frequency reverse transition is explained in terms of interaction between the melt and the shear-cell walls.Comment: RevTex, 3 pages, 1 figure, submitted to PR

Self-diffusion of Rod-like Viruses Through Smectic Layer

We report the direct visualization at the scale of single particles of mass transport between smectic layers, also called permeation, in a suspension of rod-like viruses. Self-diffusion takes place preferentially in the direction normal to the smectic layers, and occurs by quasi-quantized steps of one rod length. The diffusion rate corresponds with the rate calculated from the diffusion in the nematic state with a lamellar periodic ordering potential that is obtained experimentally.Comment: latex, 4 pages, 4 figures, accepted in Phys. Rev. Let

The Crystal Structure of the Extracellular 11-heme Cytochrome UndA Reveals a Conserved 10-heme Motif and Defined Binding Site for Soluble Iron Chelates

Members of the genus Shewanella translocate deca- or undeca-heme cytochromes to the external cell surface thus enabling respiration using extracellular minerals and polynuclear Fe(III) chelates. The high resolution structure of the first undeca-heme outer membrane cytochrome, UndA, reveals a crossed heme chain with four potential electron ingress/egress sites arranged within four domains. Sequence and structural alignment of UndA and the deca-heme MtrF reveals the extra heme of UndA is inserted between MtrF hemes 6 and 7. The remaining UndA hemes can be superposed over the heme chain of the decaheme MtrF, suggesting that a ten heme core is conserved between outer membrane cytochromes. The UndA structure has also been crystallographically resolved in complex with substrates, an Fe(III)-nitrilotriacetate dimer or an Fe(III)-citrate trimer. The structural resolution of these UndA-Fe(III)-chelate complexes provides a rationale for previous kinetic measurements on UndA and other outer membrane cytochromes

Orientational phase transitions in the hexagonal phase of a diblock copolymer melt under shear flow

We generalize the earlier theory by Fredrickson [J. Rheol. v.38, 1045 (1994)] to study the orientational behaviour of the hexagonal phase of diblock copolymer melt subjected to steady shear flow. We use symmetry arguments to show that the orientational ordering in the hexagonal phase is a much weaker effect than in the lamellae. We predict the parallel orientation to be stable at low and the perpendicular orientation at high shear rates. Our analysis reproduces the experimental results by Tepe et al. [Macromolecules v.28, 3008 (1995)] and explains the difficulties in experimental observation of the different orientations in the hexagonal phase.Comment: 21 pages, 6 eps figures, submitted to Physical Review

Determination of complex dielectric functions of ion implanted and implanted‐annealed amorphous silicon by spectroscopic ellipsometry

Measuring with a spectroscopic ellipsometer (SE) in the 1.8–4.5 eV photon energy region we determined the complex dielectric function (ϵ = ϵ1 + iϵ2) of different kinds of amorphous silicon prepared by self‐implantation and thermal relaxation (500 °C, 3 h). These measurements show that the complex dielectric function (and thus the complex refractive index) of implanted a‐Si (i‐a‐Si) differs from that of relaxed (annealed) a‐Si (r‐a‐Si). Moreover, its ϵ differs from the ϵ of evaporated a‐Si (e‐a‐Si) found in the handbooks as ϵ for a‐Si. If we use this ϵ to evaluate SE measurements of ion implanted silicon then the fit is very poor. We deduced the optical band gap of these materials using the Davis–Mott plot based on the relation: (ϵ2E2)1/3 ∼ (E− Eg). The results are: 0.85 eV (i‐a‐Si), 1.12 eV (e‐a‐Si), 1.30 eV (r‐a‐Si). We attribute the optical change to annihilation of point defects

Global Stationary Phase and the Sign Problem

We present a computational strategy for reducing the sign problem in the evaluation of high dimensional integrals with non-positive definite weights. The method involves stochastic sampling with a positive semidefinite weight that is adaptively and optimally determined during the course of a simulation. The optimal criterion, which follows from a variational principle for analytic actions S(z), is a global stationary phase condition that the average gradient of the phase Im(S) along the sampling path vanishes. Numerical results are presented from simulations of a model adapted from statistical field theories of classical fluids.Comment: 9 pages, 3 figures, submitted for publicatio

Interfaces of Modulated Phases

Numerically minimizing a continuous free-energy functional which yields several modulated phases, we obtain the order-parameter profiles and interfacial free energies of symmetric and non-symmetric tilt boundaries within the lamellar phase, and of interfaces between coexisting lamellar, hexagonal, and disordered phases. Our findings agree well with chevron, omega, and T-junction tilt-boundary morphologies observed in diblock copolymers and magnetic garnet films.Comment: 4 page

Jamming percolation and glassy dynamics

We present a detailed physical analysis of the dynamical glass-jamming transition which occurs for the so called Knight models recently introduced and analyzed in a joint work with D.S.Fisher \cite{letterTBF}. Furthermore, we review some of our previous works on Kinetically Constrained Models. The Knights models correspond to a new class of kinetically constrained models which provide the first example of finite dimensional models with an ideal glass-jamming transition. This is due to the underlying percolation transition of particles which are mutually blocked by the constraints. This jamming percolation has unconventional features: it is discontinuous (i.e. the percolating cluster is compact at the transition) and the typical size of the clusters diverges faster than any power law when $\rho\nearrow\rho_c$. These properties give rise for Knight models to an ergodicity breaking transition at $\rho_c$: at and above $\rho_{c}$ a finite fraction of the system is frozen. In turn, this finite jump in the density of frozen sites leads to a two step relaxation for dynamic correlations in the unjammed phase, analogous to that of glass forming liquids. Also, due to the faster than power law divergence of the dynamical correlation length, relaxation times diverge in a way similar to the Vogel-Fulcher law.Comment: Submitted to the special issue of Journal of Statistical Physics on Spin glasses and related topic

Negative emotional stimuli reduce contextual cueing but not response times in inefficient search

In visual search, previous work has shown that negative stimuli narrow the focus of attention and speed reaction times (RTs). This paper investigates these two effects by first asking whether negative emotional stimuli narrow the focus of attention to reduce the learning of a display context in a contextual cueing task and, second, whether exposure to negative stimuli also reduces RTs in inefficient search tasks. In Experiment 1, participants viewed either negative or neutral images (faces or scenes) prior to a contextual cueing task. In a typical contextual cueing experiment, RTs are reduced if displays are repeated across the experiment compared with novel displays that are not repeated. The results showed that a smaller contextual cueing effect was obtained after participants viewed negative stimuli than when they viewed neutral stimuli. However, in contrast to previous work, overall search RTs were not faster after viewing negative stimuli (Experiments 2 to 4). The findings are discussed in terms of the impact of emotional content on visual processing and the ability to use scene context to help facilitate search