A density matrix renormalization group method study of optical properties of porphines and metalloporphines

The symmetrized density matrix renormalization group method is used to study linear and nonlinear optical properties of free base porphine and metalloporphine. Long-range interacting model, namely, Pariser-Parr-Pople model is employed to capture the quantum many-body effect in these systems. The nonlinear optical coefficients are computed within the correction vector method. The computed singlet and triplet low-lying excited state energies and their charge densities are in excellent agreement with experimental as well as many other theoretical results. The rearrangement of the charge density at carbon and nitrogen sites, on excitation, is discussed. From our bond order calculation, we conclude that porphine is well described by the 18-annulenic structure in the ground state and the molecule expands upon excitation. We have modeled the regular metalloporphine by taking an effective electric field due to the metal ion and computed the excitation spectrum. Metalloporphines have D(4h) symmetry and hence have more degenerate excited states. The ground state of metalloporphines shows 20-annulenic structure, as the charge on the metal ion increases. The linear polarizability seems to increase with the charge initially and then saturates. The same trend is observed in third order polarizability coefficients. (C) 2012 American Institute of Physics. [doi: 10.1063/1.3671946]

Real-time density matrix renormalization group dynamics of spin and charge transport in push-pull polyenes and related systems

In this paper we investigate the effect of terminal substituents on the dynamics of spin and charge transport in donor-acceptor substituted polyenes [D-(CH)(x)-A] chains, also known as push-pull polyenes. We employ a long-range correlated model Hamiltonian for the D-(CH)(x)-A system, and time-dependent density matrix renormalization group technique for time propagating the wave packet obtained by injecting a hole at a terminal site, in the ground state of the system. Our studies reveal that the end groups do not affect spin and charge velocities in any significant way, but change the amount of charge transported. We have compared these push-pull systems with donor-acceptor substituted polymethine imine (PMI), D-(CHN)(x)-A, systems in which besides electron affinities, the nature of p(z) orbitals in conjugation also alternate from site to site. We note that spin and charge dynamics in the PMIs are very different from that observed in the case of push-pull polyenes, and within the time scale of our studies, transport of spin and charge leads to the formation of a ``quasi-static'' state.

Tracking and Erosion of Silicone Rubber Nanocomposites under DC Voltages of both Polarities

In order to improve the tracking and erosion performance of outdoor polymeric silicone rubber (SR) insulators used in HV power transmission lines, micron sized inorganic fillers are usually added to the base SR matrix. In addition, insulators used in high voltage dc transmission lines are designed to have increased creepage distance to mitigate the tracking and erosion problems. ASTM D2303 standard gives a procedure for finding the tracking and erosion resistance of outdoor polymeric insulator weathershed material samples under laboratory conditions for ac voltages. In this paper, inclined plane (IP) tracking and erosion tests similar to ASTM D2303 were conducted under both positive and negative dc voltages for silicone rubber samples filled with micron and nano sized particles to understand the phenomena occurring during such tests. Micron sized Alumina Trihydrate (ATH) and nano sized alumina fillers were added to silicone rubber matrix to improve the resistance to tracking and erosion. The leakage current during the tests and the eroded mass at the end of the tests were monitored. Scanning Electron Microscopy (SEM) and Energy dispersive Xray (EDX) studies were conducted to understand the filler dispersion and the changes in surface morphology in both nanocomposite and microcomposite samples. The results suggest that nanocomposites performed better than microcomposites even for a small filler loading (4%) for both positive and negative dc stresses. It was also seen that the tracking and erosion performance of silicone rubber is better under negative dc as compared to positive dc voltage. EDX studies showed migration of different ions onto the surface of the sample during the IP test under positive dc which has led to an inferior performance as compared to the performance under negative dc.

Structure and properties of zinc alloy based metal matrix composites

Zinc-aluminium cast alloys (ZA alloys) exhibit good castability and mechanical properties but these alloys lack creep resistance and high temperature stability. One solution to improve these properties is to reinforce with ceramic particles or fibres, to result in MMCs. MMCs can be produced using casting technique involving infiltration. A systematic investigation was taken and this paper discusses the salient findings of the study on the ZA-27 alloy based MMCs produced through squeeze casting. (Reinforcing fibers: SAFFIL (chopped alumina) or mullite.)

On an Integrated Transfer Matrix method for multiply connected mufflers

The commercial automotive mufflers are generally of a complicated shape with multiply connected parts and complex acoustic elements. The analysis of such complex mufflers has always been a great challenge. In this paper, an Integrated Transfer Matrix method has been developed to analyze complex mufflers. Integrated transfer matrix relates the state variables across the entire cross-section of the muffler shell, as one moves along the axis of the muffler, and can be partitioned appropriately in order to relate the state variables of different tubes constituting the cross-section. The paper presents a generalized one-dimensional (1-D) approach, using the transfer matrices of simple acoustic elements, which are available from the literature. The present approach is robust and flexible owing to its capability to construct an overall matrix of the muffler with the transfer matrices of individual acoustic elements and boundary conditions, which can then be used to evaluate the transmission loss, insertion loss, etc. Results from the present approach have been validated through comparisons with the available experimental and three-dimensional finite element method (FEM) based results. The results show good agreement with both measurements and FEM analysis up to the cut-off frequency. (C) 2011 Elsevier Ltd. All rights reserved.

High emission currents and low threshold fields in multi-wall carbon nanotube-polymer composites in the vertical configuration

In this work, we present field emission characteristics of multi-wall carbon nanotube (MWCNT)-polystyrene composites at various weight fractions along the cross-section of sample. Scanning electron microscope images in cross-sectional view reveal that MWCNTs are homogeneously distributed across the thickness and the density of protruding tubes can be scaled with weight fraction of the composite film. Field emission from composites has been observed to vary considerably with density of MWCNTs in the polymer matrix. High current density of 100 mA/cm(2) was achieved at a field of 2.2 V/lm for 0.15 weight fraction. The field emission is observed to follow the Fowler-Nordheim tunneling mechanism, however, electrostatic screening is observed to play a role in limiting the current density at higher weight fractions. (C) 2012 American Institute of Physics. [doi:10.1063/1.3685754]

3-D acoustic analysis of elliptical chamber mufflers having an end-inlet and a side-outlet: An impedance matrix approach

The acoustical behavior of an elliptical chamber muffler having an end-inlet and side-outlet port is analyzed semi-analytically. A uniform piston source is assumed to model the 3-D acoustic field in the elliptical chamber cavity. Towards this end, we consider the modal expansion of acoustic pressure field in the elliptical cavity in terms of angular and radial Mathieu functions, subjected to rigid wall condition, whereupon under the assumption of a point source, Green's function is obtained. On integrating this function over piston area of the side or end port and dividing it by piston area, one obtains the acoustic field, whence one can find the impedance matrix parameters characterizing the 2-port system. The acoustic performance of these configurations is evaluated in terms of transmission loss (TL). The analytical results thus obtained are compared with 3-D HA carried on a commercial software for certain muffler configurations. These show excellent agreement, thereby validating the 3-D semi-analytical piston driven model. The influence of the chamber length as well as the angular and axial location of the end and side ports on TL performance is also discussed, thus providing useful guidelines to the muffler designer. (c) 2011 Elsevier B.V. All rights reserved.

Chitosan-polyvinyl alcohol-sulfonated polyethersulfone mixed-matrix membranes as methanol-barrier electrolytes for DMFCs

Chitosan (CS)-polyvinyl alcohol (PVA) cross-linked with sulfosuccinic acid (SSA) and modified with sulfonated polyethersulfone (SPES) mixed-matrix membranes are reported for their application in direct methanol fuel cells (DMFCs). Polyethersulfone (PES) is sulfonated by chlorosulfonic acid and factors affecting the sulfonation reaction, such as time and temperature, are studied. The ion-exchange capacity, degree of sulfonation, sorption, and proton conductivity for the mixed-matrix membranes are investigated. The mixed-matrix membranes are also characterised for their mechanical and thermal properties. The methanol-crossover flux across the mixed-matrix membranes is studied by measuring the mass balance of methanol using the density meter. The methanol cross-over for these membranes is found to be about 33% lower in relation to Nafion-117 membrane. The DMFC employing CS-PVA-SPES mixed-matrix membrane with an optimum content of 25 wt % SPES delivers a peak power-density of 5.5 mW cm-2 at a load current-density of 25 mA cm-2 while operating at 70 degrees C. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Density matrix renormalization group algorithm for Bethe lattices of spin-1/2 or spin-1 sites with Heisenberg antiferromagnetic exchange

A density matrix renormalization group (DMRG) algorithm is presented for the Bethe lattice with connectivity Z = 3 and antiferromagnetic exchange between nearest-neighbor spins s = 1/2 or 1 sites in successive generations g. The algorithm is accurate for s = 1 sites. The ground states are magnetic with spin S(g) = 2(g)s, staggered magnetization that persists for large g > 20, and short-range spin correlation functions that decrease exponentially. A finite energy gap to S > S(g) leads to a magnetization plateau in the extended lattice. Closely similar DMRG results for s = 1/2 and 1 are interpreted in terms of an analytical three-site model.

A novel ``pro-sensitizer'' based sensing of enzymes using Tb(III) luminescence in a hydrogel matrix

Chemically synthesized ``pro-sensitizers'' release the sensitizer in the presence of lipase or beta-glucosidase, triggering a significant luminescence response from a lanthanide based hydrogel.

Ag@AgI, Core@Shell Structure in Agarose Matrix as Hybrid: Synthesis, Characterization, and Antimicrobial Activity

A novel in situ core@shell structure consisting of nanoparticles of Ag (Ag Nps) and AgI in agarose matrix (Ag@ AgI/agarose) has been synthesized as a hybrid, in order to have an efficient antibacterial agent for repetitive usage with no toxicity. The synthesized core@shell structure is very well characterized by XRD, UV-visible, photoluminescence, and TEM. A detailed antibacterial studies including repetitive cycles are carried out on Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus) bacteria in saline water, both in dark and on exposure to visible light. The hybrid could be recycled for the antibacterial activity and is nontoxic toward human cervical cancer cells (HeLa cells). The water insoluble Ag@AgI in agarose matrix forms a good coating on quartz, having good mechanical strength. EPR and TEM studies are carried out on the Ag@AgI/agarose and the bacteria, respectively, to elucidate a possible mechanism for killing of the bacteria.

On the microstructure-tensile property correlations in bulk metallic glass matrix composites with crystalline dendrites

Bulk metallic glass (BMG) matrix composites with crystalline dendrites as reinforcements exhibit a wide variance in their microstructures (and thus mechanical properties), which in turn can be attributed to the processing route employed, which affects the size and distribution of the dendrites. A critical investigation on the microstructure and tensile properties of Zr/Ti-based BMG composites of the same composition, but produced by different routes, was conducted so as to identify ``structure-property'' connections in these materials. This was accomplished by employing four different processing methods-arc melting, suction casting, semi-solid forging and induction melting on a water-cooled copper boat-on composites with two different dendrite volume fractions, V-d. The change in processing parameters only affects microstructural length scales such as the interdendritic spacing, lambda, and dendrite size, delta, whereas compositions of the matrix and dendrite are unaffected. Broadly, the composite's properties are insensitive to the microstructural length scales when V-d is high (similar to 75%), whereas they become process dependent for relatively lower V-d (similar to 55%). Larger delta in arc-melted and forged specimens result in higher ductility (7-9%) and lower hardening rates, whereas smaller dendrites increase the hardening rate. A bimodal distribution of dendrites offers excellent ductility at a marginal cost of yield strength. Finer lambda result in marked improvements in both ductility and yield strength, due to the confinement of shear band nucleation sites in smaller volumes of the glassy phase. Forging in the semi-solid state imparts such a microstructure. (c) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Charge transport in functionalized multi-wall carbon nanotube-Nafion composite

The charge transport in sulfonated multi-wall carbon nanotube (sMWNT)-Nafion composite is reported. The scanning electron microscope images of the composite, at 1 and 10 wt % of sMWNT, show that the nanotubes are well dispersed in polymer matrix, with conductivity values of 0.005 and 3.2 S/cm, respectively; and the percolation threshold is nearly 0.42 wt. %. The exponent (∼0.25) of the temperature dependence of conductivity in both samples indicates Mott's variable range hopping (VRH) transport. The conductance in 1 wt. % sample increases by three orders of magnitude at high electric-fields, consistent with VRH model. The negative magnetoresistance in 10 wt. % sample is attributed to the forward interference scattering mechanism in VRH transport. The ac conductance in 1 wt. % sample is expressed by σ(ω)∝ωs, and the temperature dependence of s follows the correlated barrier hopping model.