Structure-potential relationship and nature of disorder in liquids and glassy solids

A method based on the minimal-spanning tree is extended to a collection of points in three dimensions. Two parameters, the average edge length and its standard deviation characterize the disorder. The structural phase diagram for a monatomic system of particles and the characteristic values for the uniform random distribution of points have been obtained. The method is applied to hard spheres and Lennard-Jones systems. These systems occupy distinct regions in the structural phase diagram. The structure of the Lennard-Jones system approaches that of the defective close-packed arrangements at low temperatures whereas in the liquid regime, it deviates from the close-packed configuration.

Structure–property relationship in superconducting cuprates

An examination of the structure and superconducting properties of the various families of cuprates suggests several interesting structural commonalities. Relations between some of the structural parameters of the cuprates and the superconducting transition temperature, T-c, provide useful insights. Variations of T-c on the hole concentration, the in-plane Cu-O and the apical Cu-O distances, as well as the Madelung potentials and bond valence sums are particularly noteworthy. The Cu-O charge-transfer energy appears to be fundamental in determining the properties of cuprates.

Levitation effect and its relationship with the underlying potential energy landscape

Positions of potential energy minima for spherical monatomic sorbates in zeolite NaY have been identified for different sizes of the sorbate. It is found that for small sorbates (sigma less than or equal to 4.96 Angstrom) there are only six adsorption sites per alpha-cage, which are located close to the inner surface of the alpha-cage. For larger sorbates, additional sites of comparable energies appear close to the 12-ring window which forms the bottleneck for intercage diffusion. Minimum energy paths between these sites have been computed. These suggest that the barriers for both intracage and intercage site-to-site migrations are comparable and decrease with increase in sorbate size. Earlier simulation studies on the diffusion of monatomic sorbates in zeolites indicated that there is a dramatic change in the nature of dependence of D on sorbate size around 4.96 Angstrom, for zeolite NaY. Therefore, the present results suggest that the dependence of D on sorbate size and the changes in the potential energy landscape are correlated. The sorbate-zeolite system is characterized by a flatter potential energy landscape when the sorbate size is large. (C) 1999 American Institute of Physics. [S0021-9606(99)51110-0].

Conformation and orientation of alkyl chains in the layered organic-inorganic hybrids: (CnH2n+1NH3)(2)PbI4 (n=12,16,18)

Layered organic inorganic hybrids based on perovskite-derived alkylammonium lead halides have been demonstrated as important new materials in the construction of molecular electronic devices. Typical of this class of materials are the single-perovskite slab lead iodides of the general formula (CnH2n+1NH3)(2)PbI4. While for small n, these compounds are amenable to single-crystal structure determination, the increasing degree of disorder in the long chain (n = 12,14...) compounds makes such an analysis difficult. In this study, we use powder X-ray diffraction, and vibrational and C-13 NMR spectroscopies to establish the conformation, orientation and organization of hydrocarbon chains in the series of layered alkylammonium lead iodides (CnH2n+1NH3)(2)PbI4 (n = 12,16,18). We find that the alkyl chains adopt a tilted bilayer arrangement, while the structure of the inorganic layer remains invariant with respect to the value of n. Conformation-sensitive methylene stretching modes in the infrared and Raman spectra, as well as the C-13 NMR spectra indicate that bonds in the methylene chain are in trans configuration. The skeletal modes of the alkyl chain in the Raman spectra establish that there is a high degree of all-trans conformational registry for the values of n studied here. From the orientation dependence of the infrared spectra of crystals of (CnH2n+1NH3)(2)PbI4 ( n = 12,16), we find that the molecular axis of the all-trans alkyl chains are tilted away from the interlayer normal by an angle of 55degrees. This value of this tilt angle is consistent with the dependence of the c lattice expansion as a function of n, as determined from powder X-ray diffraction.

Orientation dependent electrocatalysis using self-assembled molecular films

Surface orientation of self-assembled molecular films of 2,9,6,23-tetraamino cobalt phthalocyanine on gold and silver is shown to determine the nature and the products of the electrocatalytic reduction of oxygen.

The absolute orientation of a molecule in space: Extension of the 'CIP' system

A scheme for denoting the absolute spatial orientation of molecules and molecular fragments is presented; this is based on three angular deviations - one for each spatial dimension - with respect to a reference orientation, which is itself defined with the help of certain features of the Cahn-Ingold-Prelog stereochemical notation. The new scheme helps in reconstructing the three-dimensional characteristics of molecules from purely verbal descriptors, and may thus find application in various information storage and retrieval processes (e.,-. encrypting holograms, etc.).

Effect of lattice orientation on crack tip constraint in ductile single crystals

In this work, the effect of lattice orientation on the fields prevailing near a notch tip is investigated pertaining to various constraint levels in FCC single crystals. A modified boundary layer formulation is employed and numerical solutions under mode I, plane strain conditions are generated by assuming an elastic-perfectly plastic FCC single crystal. The analysis is carried out corresponding to different lattice orientations with respect to the notch line. It is found that the near-tip deformation field, especially the development of kink or slip shear bands is sensitive to the constraint level. The stress distribution and the size and shape of the plastic zone near the notch tip are also strongly influenced by the level of T-stress. The present results clearly establish that ductile single crystal fracture geometries would progressively lose crack tip constraint as the T-stress becomes more negative irrespective of lattice orientation. Also, the near-tip field for a range of constraint levels can be characterized by two-parameters such as K-T or J-Q as in isotropic plastic solids.

Microstructural Studies of Ferroelectric Bi2VO5.5 Thin Films With LaNiO3 Electrodes

Thin films of Bi2VO5.5 (BVO), a vanadium analog of the n = I member of the Aurivillius family, have been prepared by pulsed laser deposition. The BVO films grow along the [001] direction on LaNiO3(LNO) and YBa2Cu3O7 (YBCO) electrode buffer layers on LaA- IO3(LAO) substrates as obtained from X-ray diffraction studies. The microstructure of the films and of the interfaces within the film and between the film and the substrate were characterized using transmission electron microscopy. The in-plane epitaxial relationship of the rhombohedral LNO on perovskite LAO was [100] LNO // [100] LAO and [001] LNO // [001] LAO. High resolution lattice images showed a sharp interface between LNO and LAO. However, the LNO film is twinned with a preferred orientation along the growth direction. The BVO layer is single crystalline on both LNO/LAO and YBCO/LAO with the caxis parallel to the growth direction except for a thin layer of about 400 Å at the interface which is polycrystalline.

Network Rhythms Influence the Relationship between Spike-Triggered Local Field Potential and Functional Connectivity

Characterizing the functional connectivity between neurons is key for understanding brain function. We recorded spikes and local field potentials (LFPs) from multielectrode arrays implanted in monkey visual cortex to test the hypotheses that spikes generated outward-traveling LFP waves and the strength of functional connectivity depended on stimulus contrast, as described recently. These hypotheses were proposed based on the observation that the latency of the peak negativity of the spike-triggered LFP average (STA) increased with distance between the spike and LFP electrodes, and the magnitude of the STA negativity and the distance over which it was observed decreased with increasing stimulus contrast. Detailed analysis of the shape of the STA, however, revealed contributions from two distinct sources-a transient negativity in the LFP locked to the spike (similar to 0 ms) that attenuated rapidly with distance, and a low-frequency rhythm with peak negativity similar to 25 ms after the spike that attenuated slowly with distance. The overall negative peak of the LFP, which combined both these components, shifted from similar to 0 to similar to 25 ms going from electrodes near the spike to electrodes far from the spike, giving an impression of a traveling wave, although the shift was fully explained by changing contributions from the two fixed components. The low-frequency rhythm was attenuated during stimulus presentations, decreasing the overall magnitude of the STA. These results highlight the importance of accounting for the network activity while using STAs to determine functional connectivity.

An Empirical Evaluation of Novelty-SAPPhIRE Relationship

The research shown in this paper is to check whether a framework for designing: GEMS of SAPPhIRE as req-sol, developed earlier, can support in the designing of novel concepts. This is done by asking the questions: (a) Is there a relationship between the constructs of the framework and novelty? (b) If there is a relationship, what is the degree of this relationship? A hypothesis — an increase in the size and variety of ideas used while designing should enhance the variety of concepts produced, leading to an increase in the novelty of the concept space — is developed to explain the relationship between novelty and the constructs. Eight existing observational studies of designing sessions, each involving an individual designer solving a conceptual design problem by following a think aloud protocol are used for the analysis. The hypothesis is verified empirically using the observational studies. Results also show a strong correlation between novelty and the constructs of the framework; correlation value decreases as the abstraction level of the constructs reduces, signifying the importance of using constructs at higher abstraction levels especially for novelty.

Beta-structure of polypeptides in non-aqueous solutions. II. Side-chain orientation

The specific side-chain orientations of the phenyl group in the polypeptides poly-S-benzyl-L-cysteine, poly-S-carbobenzoxy-L-cysteine and poly-O-carbobenzoxy-L-serine in the beta-structure have been studied by spectral measurements in solutions. All the three polypeptides exhibit aromatic CD bands, indicating the asymmetric placement of the side-chain phenyl rings when the polypeptide backbone takes up the antiparallel beta-structure. Supporting evidence for this is derived from n.m.r. spectra of the polypeptides, which show upfield shift of the phenyl protons due to the stacking of the aromatic rings. Molecular model building studies reveal the stacking of alternate phenyl groups along the polypeptide chain.

Relationship Between Physical Structure and Tribology of Single Soot Particles Generated by Burning Ethylene

Ethylene gas is burnt and the soot generated is sampled thermophoretically at different heights along the flame axis starting from a region close to the root of the flame. The morphology and crystallinity of the particle are recorded using high resolution transmission electron microscopes. The hardness of a single particle is measured using a nanoindenter. The frictional resistance and material removal of a particle are measured using an atomic force microscope. The particles present in the mid-flame region are found to have a crystalline shell. The ones at the flame root are found to be highly disordered and the ones at the flame tip and above have randomly distributed pockets of short range order. The physical state of a particle is found to relate, but not very strongly, with the mechanical and tribological properties of the particles.

Subcontracting Relationship of Indian SMEs with a Global TNC: Do SMEs Gain and How?

TNCs having their production bases in developing countries provide increasing opportunity for local SMEs to have subcontracting relationships with these TNCs.Even though some theoretical and a few empirical studies throw light on the nature of assistance provided by TNCs to local SMEs through subcontracting relationships,none of the studies so far analysed the diversity of assistance that subcontracting SMEs of India would be able to obtain from a TNC using quantitative measurement.This paper probes the extent of linkages and diversity of assistance that Indian subcontracting SMEs would be able to obtain from a TNC customer based on primary data from SME subcontractors of a major TNC automobile manufacturer. Statistical analysis of direct assistance revealed that SMEs receive more of product and purchase process assistance. The extent of assistance for their process related,marketing, human resource and financial requirements is low whereas the assistance for their organisational know-how requirements is moderate. The major indirect benefits these SMEs could achieve are knowledge transfer, business volume, superior work culture, reputation and quality improvement.