Competition of the connectivity with the local and the global order in polymer melts and crystals

The competition between the connectivity and the local or global order in model fully-flexible chain molecules is investigated by molecular-dynamics simulations. States with both missing (melts) and high (crystal) global order are considered. Local order is characterized within the first coordination shell (FCS) of a tagged monomer and found to be lower than in atomic systems in both melt and crystal. The role played by the bonds linking the tagged monomer to FCS monomers (radial bonds), and the bonds linking two FCS monomers (shell bonds) is investigated. The detailed analysis in terms of Steinhardt's orientation order parameters Q_l (l = 2 - 10) reveals that increasing the number of shell bonds decreases the FCS order in both melt and crystal. Differently, the FCS arrangements organize the radial bonds. Even if the molecular chains are fully flexible, the distribution of the angle formed by adjacent radial bonds exhibits sharp contributions at the characteristic angles {\theta} = 70{\deg}, 122{\deg}, 180{\deg}. The fractions of adjacent radial bonds with {\theta} = 122{\deg}, 180{\deg} are enhanced by the global order of the crystal, whereas the fraction with 70{\deg} < {\theta} < 110{\deg} is nearly unaffected by the crystallization. Kink defects, i.e. large lateral displacements of the chains, are evidenced in the crystalline state.Comment: J. Chem. Phys. in pres

A gradient index metamaterial

Metamaterials--artificially structured materials with tailored electromagnetic response--can be designed to have properties difficult to achieve with existing materials. Here we present a structured metamaterial, based on conducting split ring resonators (SRRs), which has an effective index-of-refraction with a constant spatial gradient. We experimentally confirm the gradient by measuring the deflection of a microwave beam by a planar slab of the composite metamaterial over a broad range of frequencies. The gradient index metamaterial represents an alternative approach to the development of gradient index lenses and similar optics that may be advantageous, especially at higher frequencies. In particular, the gradient index material we propose may be suited for terahertz applications, where the magnetic resonant response of SRRs has recently been demonstrated

Transport into the south polar vortex in early spring

Estimates of the mean circulation and diffusive transport of ozone and other species into the Antarctic polar vortex during the spring of 1987 are made using data from the Airborne Antarctic Ozone Experiment. Measurements of long-lived tracers of tropospheric origin remained relatively constant at the levels of the maximum rate of decline of ozone during September. At lower levels in the stratosphere some evidence exists to support intrusions of tropospheric or low latitude air. Given the distribution in latitude and height of these tracers measured from the ER-2 aircraft, it can be inferred that the Lagrangian or diabatic mean circulation was zero or downward over Antarctica during the period of the ozone decline. The observation of a decline in ozone therefore requires a photochemical sink for ozone. The magnitude of the required photochemical sink must be sufficient to offset the transport of ozone into the polar region and produce the observed decline. Quasi-isentropic mixing and downward motion are coupled and are difficult to estimate from a single tracer. The full suite of measured tracers and auxiliary information are brought together to provide an estimate of the rate at which air is cycled through the polar vortex during spring. Estimates of large scale transport of potential vorticity and ozone from previous years are generally consistent with the data from the airborne experiment in suggesting a relatively slow rate of mass flow through the polar vortex in the lower stratosphere during September

Predictive relation for the α-relaxation time of a coarse-grained polymer melt under steady shear

We examine the influence of steady shear on structural relaxation in a simulated coarse-grained unentangled polymer melt over a wide range of temperature and shear rates. Shear is found to progressively suppress the α-relaxation process observed in the intermediate scattering function, leading ultimately to a purely inertially dominated β-relaxation at high shear rates, a trend similar to increasing temperature. On the basis of a scaling argument emphasizing dynamic heterogeneity in cooled liquids and its alteration under material deformation, we deduce and validate a parameter-free scaling relation for both the structural relaxation time τα from the intermediate scattering function and the “stretching exponent” β quantifying the extent of dynamic heterogeneity over the entire range of temperatures and shear rates that we can simulate

Instantaneous Normal Mode Analysis of Supercooled Water

We use the instantaneous normal mode approach to provide a description of the local curvature of the potential energy surface of a model for water. We focus on the region of the phase diagram in which the dynamics may be described by the mode-coupling theory. We find, surprisingly, that the diffusion constant depends mainly on the fraction of directions in configuration space connecting different local minima, supporting the conjecture that the dynamics are controlled by the geometric properties of configuration space. Furthermore, we find an unexpected relation between the number of basins accessed in equilibrium and the connectivity between them.Comment: 5 pages, 4 figure

Photocurrent Enhancement by Spontaneous Formation of a p n Junction in Calcium Doped Bismuth Vanadate Photoelectrodes

The application of bismuth vanadate BiVO4 photoelectrodes for solar water splitting is hindered by the poor carrier transport. To overcome this, multiple donor doping strategies e.g. dual doping, gradient doping have been explored. Here, we show for the first time the successful introduction of calcium Ca as an acceptor type dopant into BiVO4 photoelectrodes. Interestingly, instead of generating cathodic photocurrents, the Ca doped BiVO4 photoelectrodes show anodic photocurrents with an enhanced carrier separation efficiency. Hard X ray photoelectron spectroscopy HAXPES shows that this enhancement is caused by out diffusion of Ca during the deposition process, which spontaneously creates a p n junction within the BiVO4 layer. Overall, a significant two fold improvement of the AM1.5 photocurrent is obtained upon Ca doping. This study highlights the importance of controlled doping beyond simply modifying carrier concentration and may enable new device architectures in photoelectrode material

An Extended Variational Principle for the SK Spin-Glass Model

The recent proof by F. Guerra that the Parisi ansatz provides a lower bound on the free energy of the SK spin-glass model could have been taken as offering some support to the validity of the purported solution. In this work we present a broader variational principle, in which the lower bound, as well as the actual value, are obtained through an optimization procedure for which ultrametic/hierarchal structures form only a subset of the variational class. The validity of Parisi's ansatz for the SK model is still in question. The new variational principle may be of help in critical review of the issue.Comment: 4 pages, Revtex

Thermodynamics, Structure, and Dynamics of Water Confined between Hydrophobic Plates

We perform molecular dynamics simulations of 512 water-like molecules that interact via the TIP5P potential and are confined between two smooth hydrophobic plates that are separated by 1.10 nm. We find that the anomalous thermodynamic properties of water are shifted to lower temperatures relative to the bulk by $\approx 40$ K. The dynamics and structure of the confined water resemble bulk water at higher temperatures, consistent with the shift of thermodynamic anomalies to lower temperature. Due to this $T$ shift, our confined water simulations (down to $T = 220$ K) do not reach sufficiently low temperature to observe a liquid-liquid phase transition found for bulk water at $T\approx 215$ K using the TIP5P potential. We find that the different crystalline structures that can form for two different separations of the plates, 0.7 nm and 1.10 nm, have no counterparts in the bulk system, and discuss the relevance to experiments on confined water.Comment: 31 pages, 14 figure

Combined soft and hard X ray ambient pressure photoelectron spectroscopy studies of semiconductor electrolyte interfaces

The development of solar fuel generating materials would greatly benefit from a molecular level understanding of the semiconductor/electrolyte interface and changes in the interface induced by an applied potential and illumination by solar light. Ambient pressure photoelectron spectroscopy techniques with both soft and hard X-rays, AP-XPS and AP-HAXPES respectively, have the potential to markedly contribute to this understanding. In this paper we initially provide two examples of current challenges in solar fuels material development that AP-XPS and AP-HAXPES can directly address. This will be followed by a brief description of the distinguishing and complementary characteristics of soft and hard X-ray AP-XPS and AP-HAXPES and best approaches to achieving monolayer sensitivity in solid/aqueous electrolyte studies. In particular we focus on the detection of surface adsorbed hydroxyl groups in the presence of aqueous hydroxide anions in the electrolyte, a common situation when investigating photoanodes for solar fuel generating applications. The paper concludes by providing an example of a combined AP-XPS and AP-HAXPES study of a semiconductor/aqueous electrolyte interface currently used in water splitting devices specifically the BiVO4/aqueous potassium phosphate electrolyte interface

Componential coding in the condition monitoring of electrical machines Part 2: application to a conventional machine and a novel machine

This paper (Part 2) presents the practical application of componential coding, the principles of which were described in the accompanying Part 1 paper. Four major issues are addressed, including optimization of the neural network, assessment of the anomaly detection results, development of diagnostic approaches (based on the reconstruction error) and also benchmarking of componential coding with other techniques (including waveform measures, Fourier-based signal reconstruction and principal component analysis). This is achieved by applying componential coding to the data monitored from both a conventional induction motor and from a novel transverse flux motor. The results reveal that machine condition monitoring using componential coding is not only capable of detecting and then diagnosing anomalies but it also outperforms other conventional techniques in that it is able to separate very small and localized anomalies