Entropy-induced Microphase Separation in Hard Diblock Copolymers

Whereas entropy can induce phase behavior that is as rich as seen in energetic systems, microphase separation remains a very rare phenomenon in entropic systems. In this paper, we present a density functional approach to study the possibility of entropy-driven microphase separation in diblock copolymers. Our model system consists of copolymers composed of freely-jointed slender hard rods. The two types of monomeric segments have comparable lengths, but a significantly different diameter, the latter difference providing the driving force for the phase separation. At the same time these systems can also exhibit liquid crystalline phases. We treat this system in the appropriate generalization of the Onsager approximation to chain-like particles. Using a linear stability (bifurcation) analysis, we analytically determine the onset of the microseparated and the nematic phases for long chains. We find that for very long chains the microseparated phase always preempts the nematic. In the limit of infinitely long chains, the correlations within the chain become Gaussian and the approach becomes exact. This allows us to define a Gaussian limit in which the theory strongly simplifies and the competition between microphase separation and liquid crystal formation can be studied essentially analytically. Our main results are phase diagrams as a function of the effective diameter difference, the segment composition and the length ratio of the segments. We also determine the amplitude of the positional order as a function of position along the chain at the onset of the microphase separation instability. Finally, we give suggestions as to how this type of entropy-induced microphase separation could be observed experimentally.Comment: 16 pages, 7 figure

Preservation of equilibrium in orthograde and inverted body positions

The mechanism for regulation of the vertical pose with retention of equilibrium in the inverted body position was investigated

Mixed Quantum/Classical Approach for Description of Molecular Collisions in Astrophysical Environments

An efficient and accurate mixed quantum/classical theory approach for computational treatment of inelastic scattering is extended to describe collision of an atom with a general asymmetric-top rotor polyatomic molecule. Quantum mechanics, employed to describe transitions between the internal states of the molecule, and classical mechanics, employed for description of scattering of the atom, are used in a self-consistent manner. Such calculations for rotational excitation of HCOOCH3 in collisions with He produce accurate results at scattering energies above 15 cm–1, although resonances near threshold, below 5 cm–1, cannot be reproduced. Importantly, the method remains computationally affordable at high scattering energies (here up to 1000 cm–1), which enables calculations for larger molecules and at higher collision energies than was possible previously with the standard full-quantum approach. Theoretical prediction of inelastic cross sections for a number of complex organic molecules observed in space becomes feasible using this new computational tool

Weak localization, Aharonov-Bohm oscillations and decoherence in arrays of quantum dots

Combining scattering matrix theory with non-linear $\sigma$-model and Keldysh technique we develop a unified theoretical approach enabling one to non-perturbatively study the effect of electron-electron interactions on weak localization and Aharonov-Bohm oscillations in arbitrary arrays of quantum dots. Our model embraces (i) weakly disordered conductors (ii) strongly disordered conductors and (iii) metallic quantum dots. In all these cases at $T \to 0$ the electron decoherence time is found to saturate to a finite value determined by the universal formula which agrees quantitatively with numerous experimental results. Our analysis provides overwhelming evidence in favor of electron-electron interactions as a universal mechanism for zero temperature electron decoherence in disordered conductors.Comment: 19 pages, 13 figures, invited paper, published in a special issue of Fiz. Nizk. Temp. (Kharkov) dedicated to Prof. Igor Kuli

Determination of quantum-noise parameters of realistic cavities

A procedure is developed which allows one to measure all the parameters occurring in a complete model [A.A. Semenov et al., Phys. Rev. A 74, 033803 (2006); quant-ph/0603043] of realistic leaky cavities with unwanted noise. The method is based on the reflection of properly chosen test pulses by the cavity.Comment: 5 pages, 2 figure

Thermal budget of superconducting digital circuits at sub-kelvin temperatures

Superconducting single-flux-quantum (SFQ) circuits have so far been developed and optimized for operation at or above helium temperatures. The SFQ approach, however, should also provide potentially viable and scalable control and read-out circuits for Josephson-junction qubits and other applications with much lower, milli-kelvin, operating temperatures. This paper analyzes the overheating problem which becomes important in this new temperature range. We suggest a thermal model of the SFQ circuits at sub-kelvin temperatures and present experimental results on overheating of electrons and silicon substrate which support this model. The model establishes quantitative limitations on the dissipated power both for "local" electron overheating in resistors and "global" overheating due to ballistic phonon propagation along the substrate. Possible changes in the thermal design of SFQ circuits in view of the overheating problem are also discussed.Comment: 10 pages, 8 figures, submitted to J. Appl. Phy

Spreading of Block Copolymer Films and Domain Alignment at Moving Terrace Steps

We investigate spreading of phase separated copolymer films, where domain walls and thickness steps influence polymer flow. We show that at early stages of spreading its rate is determined by slow activated flow at terrace steps (i.e. thickness steps). At late stages of spreading, on the other hand, the rate is determined by the flow along terraces, with diffusion-like time dependence $t^{-1/2}$. This dependence is similar to de Gennes and Cazabat's prediction for generic layered liquids, as opposed to the classical Tanner's law of drop spreading. We also argue that chain hopping at the spreading terrace steps should lead to the formation of aligned, defect-free domain patterns on the growing terraces.Comment: 11 pages, 7 figures, submitted to J. Chem. Phy

Self-Consistent Field Theory of Brushes of Neutral Water-Soluble Polymers

The Self-Consistent Field theory of brushes of neutral water-soluble polymers described by two-state models is formulated in terms of the effective Flory interaction parameter $\chi_{eff}(T,\phi)$ that depends on both temperature, T and the monomer volume fraction, $\phi$. The concentration profiles, distribution of free ends and compression force profiles are obtained in the presence and in the absence of a vertical phase separation. A vertical phase separation within the layer leads to a distinctive compression force profile and a minimum in the plot of the moments of the concentration profile vs. the grafting density. The analysis is applied explicitly to the Karalstrom model. The relevance to brushes of Poly(N-isopropylacrylamide)(PNIPAM) is discussed.Comment: Accepted for publication in the Journal of Chemical Physic

Designing high-yielding wheat ideotypes for a changing climate

Global warming is characterized by shifts in weather patterns and increases in climatic variability and extreme events. New wheat cultivars will be required for a rapidly changing environment, putting severe pressure on breeders who must select for climate conditions which can only be predicted with a great degree of uncertainty. To assist breeders to identify key wheat traits for improvements under climate change, wheat ideotypes can be designed and tested in silico using a wheat simulation model for a wide range of future climate scenarios predicted by global climate models. A wheat ideotype is represented by a set of cultivar parameters in a model, which could be optimized for best wheat performance under projected climate change. As an example, high‐yielding wheat ideotypes were designed at two contrasting European sites for the 2050 (A1B) climate scenario. Simulations showed that wheat yield potential can be substantially increased for new ideotypes compared with current wheat varieties under climate change. The main factors contributing to yield increase were improvement in light conversion efficiency, extended duration of grain filling resulting in a higher harvest index, and optimal phenology

Adapting wheat ideotypes for climate change: accounting for uncertainties in CMIP5 climate projections

This study describes integration of climate change projections from the Coupled Model Intercomparison Project Phase 5 (CMIP5) multi-model ensemble with the LARS-WG weather generator, which delivers an attractive option for the downscaling of large-scale climate projections from global climate models (GCMs) to local-scale climate scenarios for impact assessments. A subset of 18 GCMs from the CMIP5 ensemble and 2 Representative Concentration Pathways (RCPs), RCP4.5 and RCP8.5, were integrated with LARS-WG. For computationally demanding impact assessments, where it is not practical to explore all possible combinations of GCM × RCP, a climate sensitivity index could be used to select a subset of GCMs which preserves the range of uncertainty found in CMIP5. This would allow us to quantify uncertainty in predictions of impacts resulting from the CMIP5 ensemble by conducting fewer simulation experiments. In a case study, we describe the use of the Sirius wheat simulation model to design in silico wheat ideotypes that are optimised for future climates in Europe, sampling uncertainty in GCMs, emission scenarios, time periods and European locations with contrasting climates. Two contrasting GCMs were selected for the analysis, ‘hot’ HadGEM2-ES and ‘cool’ GISS-E2-R-CC. Despite large uncertainty in future climate projections, we were able to identify target traits for wheat improvement which may assist breeding for high-yielding wheat cultivars with increased yield stability