Protonic conductivity of (NH4) 4Fe(CN)6·1.5H2O by complex admittance method

The protonic conductivity of ammonium ferrocyanide hydrate has been studied by the complex admittance method. The admittance plots show departures from ideal Debye behaviour. The values of ionic conductivity (sigma = 3.7 X 10(-5) (OMEGA-cm)-1) and diffusion coefficient (D = 3.8 X 10(-10) cm2/s) obtained at room temperature are consistent with the corresponding values estimated by an earlier NMR study.

Adiabatic eigenfunction-based approach for coherent excitation transfer: An almost analytical treatment of the Fenna-Matthews-Olson complex

We suggest a method of studying coherence in finite-level systems coupled to the environment and use it for the Hamiltonian that has been used to describe the light-harvesting pigment-protein complex. The method works with the adiabatic states and transforms the Hamiltonian to a form in which the terms responsible for decoherence and population relaxation are separated out. Decoherence is then accounted for nonperturbatively and population relaxation using a Markovian master equation. Almost analytical results can be obtained for the seven-level system, and the calculations are very simple for systems with more levels. We apply the treatment to the seven-level system, and the results are in excellent agreement with the exact numerical results of Nalbach et al. Nalbach, Braun, and Thorwart, Phys. Rev. E 84, 041926 (2011)]. Our approach is able to account for decoherence and population relaxation separately. It is found that decoherence causes only damping of oscillations and does not lead to transfer to the reaction center. Population relaxation is necessary for efficient transfer to the reaction center, in agreement with earlier findings. Our results show that the transformation to the adiabatic basis followed by a Redfield type of approach leads to results in good agreement with exact simulation.

Adiabatic Eigenfunction Based Approach to Coherent Transfer: Application to the Fenna-Matthews-Olson (FMO) Complex and the Role of Correlations in the Efficiency of Energy Transfer

We have recently suggested a method (Pallavi Bhattacharyya and K. L. Sebastian, Physical Review E 2013, 87, 062712) for the analysis of coherence in finite-level systems that are coupled to the surroundings and used it to study the process of energy transfer in the Fenna-Matthews-Olson (FMO) complex. The method makes use of adiabatic eigenstates of the Hamiltonian, with a subsequent transformation of the Hamiltonian into a form where the terms responsible for decoherence and population relaxation could be separated out at the lowest order. Thus one can account for decoherence nonperturbatively, and a Markovian type of master equation could be used for evaluating the population relaxation. In this paper, we apply this method to a two-level system as well as to a seven-level system. Comparisons with exact numerical results show that the method works quite well and is in good agreement with numerical calculations. The technique can be applied with ease to systems with larger numbers of levels as well. We also investigate how the presence of correlations among the bath degrees of freedom of the different bacteriochlorophyll a molecules of the FMO Complex affect the rate of energy transfer. Surprisingly, in the cases that we studied, our calculations suggest that the presence of anticorrelations, in contrast to correlations, make the excitation transfer more facile.

Ionic transport in (PEG)x LiBr systems

Ionic conductivity in (PEG)(x)LiBr systems is measured using the complex impedance method in the temperature range -20 degrees C to 100 degrees C. For x = 6 and 10, above a certain concentration dependent temperature T-c, a power law fit based on mode coupling theory is seen to better explain the data than the Vogel-Tamman-Fulcher (VTF) expression. Li-7 NMR linewidth measurements indicate two regions of motional narrowing, one attributable to segmental motion and the other to translational diffusion.

Preparation, Structural, and Electrical Studies of Polyaniline/ZnFe2O4 Nanocomposites

Polyaniline/ZnFe2O4 nanocomposites were synthesized by a simple and inexpensive one-step in situ polymerization method in the presence of ZnFe2O4 nanoparticles. The structural, morphological, and electrical properties of the samples were characterized by wide angle X-ray diffraction (WAXD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). WAXD and SEM revealed the formation of polyaniline/ZnFe2O4 nanocomposites. Infrared spectroscopy indicated that there was some interaction between the ZnFe2O4 nanoparticles and polyaniline. The dc electrical conductivity measurements were carried in the temperature range of 80 to 300 K. With increase in the doping concentration of ZnFe2O4, the conductivity of the nanocomposites found to be decreasing from 5.15 to 0.92 Scm(-1) and the temperature dependent resistivity follows ln rho(T) similar to T-1/2 behavior. The nanocomposites (80 wt % of ZnFe2O4) show a more negative magnetoresistance compared with that of pure polyaniline (PANI). These results suggest that the interaction between the polymer matrix PANI and zinc nanoparticles take place in these nanocomposites. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 120: 2856-2862, 2011

Effect of Multiwall Carbon Nanotubes on Electrical and Structural Properties of Polyaniline

Polyaniline (PANI) and PANI/CNT (multiwall carbon nanotubes, CNT) composites were prepared using an oxidative chemical polymerization method with ammonium persulfate and dodecyl benzene sulfonic acid as the oxidizing agent and surfactant, respectively. Fourier-transform infrared spectroscopy spectra illustrate the presence of PANI in the composite and show that some interaction exists between PANI and CNT. Embedding of CNT in the PANI matrix is confirmed by scanning electron micrography. Conductivity of the PANI/CNT composites was higher than that of pure PANI, and the maximum conductivity obtained was 4.44 S/cm at 20 wt.% CNT.

Charge transport and magnetic properties of coaxial composite fibrils of polypyrrole/multiwall carbon nanotubes at low temperature

We report the low temperature electrical and magnetic properties of polypyrrole (PPy)/multiwall carbon nanotube (MWNT) coaxial composite fibrils synthesized by the electro-polymerization method. The iron-filled MWNTs were first grown by chemical vapor deposition of a mixture of liquid phase organic compound and ferrocene by the one step method. Then the PPy/MWNT fibrils were prepared by the electrochemical polymerization process. Electron microscopy studies reveal that PPy coating on the surface of nanotube is quite uniform throughout the length. The temperature dependent electrical resistivity and magnetization measurements were done from room temperature down to 5 and 10 K, respectively. The room temperature resistivity (rho) of PPy/MWNT composite fibril sample is similar to 3.8 Omega m with resistivity ratio R-5 K/R-300 K] of similar to 300, and the analysis of rho(T) in terms of reduced activation energy shows that resistivity lies in the insulating regime below 40 K. The resistivity varies according to three dimensional variable range hopping mechanism at low temperature. The magnetization versus applied field (M-H loop) data up to a field of 20 kOe are presented, displaying ferromagnetic behavior at all temperatures with enhanced coercivities similar to 680 and 1870 Oe at room temperature and 10 K, respectively. The observation of enhanced coercivity is due to significant dipolar interaction among encapsulated iron nanoparticles, and their shape anisotropy contribution as well.

Microscopic and dielectric studies of ZnO nanoparticles loaded in ortho-chloropolyaniline nanocomposites

We have studied the preparation of zinc oxide nanoparticles loaded in various weight percentages in ortho-chloropolyaniline by in situ polymerization method. The length of the O-chloropolyaniline tube is found to be 200 nm and diameter is about 150 nm wherein the embedded ZnO nanoparticles is of 13 nm as confirmed from scanning electron microscopy as well as transmission electron microscopy characterizations. The presence of the vibration band of the metal oxide and other characteristic bands confirms that the polymer nanocomposites are characterized by their Fourier transmission infrared spectroscopy. The X-ray diffraction pattern of nanocomposites reveals their polycrystalline nature. Electrical property of nanocomposites is a function of the filler as well as the matrix. Cole-Cole plots reveal the presence of well-defined semicircular arcs at high frequencies which are attributed to the bulk resistance of the material. Among all nanocomposites, 30 wt% shows the low relaxation time of 151 s, and hence it has high conductivity.

KINEMATIC SYNTHESIS AND ANALYSIS OF THE RACK AND PINION MULTIPURPOSE MECHANISM

The general procedure for synthesizing the rack and pinion mechanism up to seven precision conditions is developed. To illustrate the method, the mechanism has been synthesized in closed form for three precision conditions of path generation, two positions of function generation, and a velocity condition at one of the precision points. This mechanism has a number of advantages over conventional four bar mechanisms. First, since the rack is always tangent to the pinion, the transmission angle is always 90 deg minus the pressure angle of the rack. Second, with both translation and rotation of the rock occurring, multiple outputs are available. Other advantages include the generation of monotonic functions for a wide variety of motion and nonmonotonic functions for a full range of motion as well as nonlinear amplified motions. In this work the mechanism is made to satisfy a number of amplified motions. In this work the mechanism is made to satisfy a number of practical design requirements such as completely rotatable input crank and others. By including the velocity specification, the designer has considerably more control of the output motion. The method of solution developed in this work uses the complex number method of mechanism synthesis. A numerical example is included

Kinematic Synthesis and Analysis of the Rack and Pinion Multi-Purpose Mechanism

The general procedure for synthesizing the rack and pinion mechanism up to seven precision conditions is developed. To illustrate the method, the mechanism has been synthesized in closed form for three precision conditions of path generation, two positions of function generation, and a velocity condition at one of the precision points. This mechanism has a number of advantages over conventional four bar mechanisms. First, since the rack is always tangent to the pinion, the transmission angle is always 90 deg minus the pressure angle of the rack. Second, with both translation and rotation of the rack occurring, multiple outputs are available. Other advantages include the generation of monotonic functions for a wide variety of motion and nonmonotonic functions for a full range of motion as well as nonlinear amplified motions. In this work the mechanism is made to satisfy a number of practical design requirements such as completely rotatable input crank and others. By including the velocity specification, the designer has considerably more control of the output motion. The method of solution developed in this work uses the complex number method of mechanism synthesis. A numerical example is included.

Finite volume evolution Galerkin method for hyperbolic conservation laws with spatially varying flux functions

We present a generalization of the finite volume evolution Galerkin scheme [M. Lukacova-Medvid'ova,J. Saibertov'a, G. Warnecke, Finite volume evolution Galerkin methods for nonlinear hyperbolic systems, J. Comp. Phys. (2002) 183 533-562; M. Luacova-Medvid'ova, K.W. Morton, G. Warnecke, Finite volume evolution Galerkin (FVEG) methods for hyperbolic problems, SIAM J. Sci. Comput. (2004) 26 1-30] for hyperbolic systems with spatially varying flux functions. Our goal is to develop a genuinely multi-dimensional numerical scheme for wave propagation problems in a heterogeneous media. We illustrate our methodology for acoustic waves in a heterogeneous medium but the results can be generalized to more complex systems. The finite volume evolution Galerkin (FVEG) method is a predictor-corrector method combining the finite volume corrector step with the evolutionary predictor step. In order to evolve fluxes along the cell interfaces we use multi-dimensional approximate evolution operator. The latter is constructed using the theory of bicharacteristics under the assumption of spatially dependent wave speeds. To approximate heterogeneous medium a staggered grid approach is used. Several numerical experiments for wave propagation with continuous as well as discontinuous wave speeds confirm the robustness and reliability of the new FVEG scheme.

A rapid and highly selective method for the estimation of pyro-,tri- and orthophosphates

A rapid, highly selective and simple method has been developed for the quantitative determination of pyro-, tri- and orthophosphates. The method is based on the formation of a solid complex of bis(ethylenediamine)cobalt(III) species with pyrophosphate at pH 4.2-4.3, with triphosphate at pH 2.0-2.1 and with orthophosphate at pH 8.2-8.6. The proposed method for pyro- and triphosphates differs from the available method, which is based on the formation of an adduct with tris(ethylenediamine)cobalt(III) species. The complexes have the composition [Co(en)(2)HP2O7]4H(2)O and [Co(en)(2)H2P3O10]2H(2)O, respectively. The precipitation is instantaneous and quantitative under the recommended optimum conditions giving 99.5% gravimetric yield in both cases. There is no interferences from orthophosphate, trimetaphosphate and pyrophosphate species in the triphosphate estimation up to 5% of each component. The efficacy of the method has been established by determining pyrophosphate and triphosphate contents in various matrices. In the case of orthophosphate, the proposed method differs from the available methods such as ammonium phosphomolybdate, vanadophosphomolybdate and quinoline phosphomolybdate, which are based on the formation of a precipitate, followed by either titrimetry or gravimetry. The precipitation is instantaneous and the method is simple. Under the recommended pH and other reaction conditions, gravimetric yields of 99.6-100% are obtainable. The method is applicable to orthophosphoric acid and a variety of phosphate salts.

Metal chelates in vinyl polymerization: Bulk polymerization of acrylonitrile initiated by Cu(II)-imine complexes

This article deals with the kinetics and mechanism of acrylonitrile (AN) polymerization initiated by Cu(II)-4-anilino 3-pentene 2-one[Cu(II)ANIPO], Cu(II)-4-p-toluedeno 3-pentene 2-one [Cu(II)TPO], and Cu(II)-4-p-nitroanilino 3-pentene 2-one [Cu(II)NAPO] in bulk at 60°C. The polymerization is free radical in nature. The exponent of initiator(I) is 0.5. The initiation step is a complex formation between the chelate and monomer and subsequent decomposition of the intermediate complex giving rise to free radical and Cu(I). This is substantiated by ultraviolet (UV) and electron spin resonance (ESR) studies. The activation energies and kinetic and chain transfer constants have also been evaluated.

Low PAPR Square STBCs from Complex Partial-Orthogonal Designs (CPODs)

Space-time codes from complex orthogonal designs (CODs) with no zero entries offer low Peak to Average Power Ratio (PAPR) and avoid the problem of switching off antennas. But square CODs for 2(a) antennas with a + 1. complex variables, with no zero entries were discovered only for a <= 3 and if a + 1 = 2(k), for k >= 4. In this paper, a method of obtaining no zero entry (NZE) square designs, called Complex Partial-Orthogonal Designs (CPODs), for 2(a+1) antennas whenever a certain type of NZE code exists for 2(a) antennas is presented. Then, starting from a so constructed NZE CPOD for n = 2(a+1) antennas, a construction procedure is given to obtain NZE CPODs for 2n antennas, successively. Compared to the CODs, CPODs have slightly more ML decoding complexity for rectangular QAM constellations and the same ML decoding complexity for other complex constellations. Using the recently constructed NZE CODs for 8 antennas our method leads to NZE CPODs for 16 antennas. The class of CPODs do not offer full-diversity for all complex constellations. For the NZE CPODs presented in the paper, conditions on the signal sets which will guarantee full-diversity are identified. Simulation results show that bit error performance of our codes is same as that of the CODs under average power constraint and superior to CODs under peak power constraint.

Metal Chelates in Vinyl Polymerization: Kinetics and Mechanism of Acrylonitrile Polymerization Initiated by Cu(I1) Imine Complexes

The free radical polymerization of acrylonitrile (AN) initiated by Cu(I1) 4-anilino 3-pentene 2-one [Cu(II) ANIPO] Cu(II), 4-p-toluedeno 3-pentene 2-one [Cu(II) TPO], and Cu(I1) 4-p-nitroanilino 3-pentene 2-one [Cu(II) NAPO] was studied in benzene at 50 and 60°C and in carbon tetrachloride (CCld), dimethyl sulfoxide (DMSO), and methanol (MeOH) at 60°C. Although the polymerization proceeded in a heterogeneous phase, it followed the kinetics of a homogeneous process. The monomer exponents were 22 at two different temperatures and in different solvents. The square-root dependence of R, on initiator concentration and higher monomer exponents accounted for a 1:2 complex formation between the chelate and monomer. The complex formatign was shown by ultraviolet (UV) study. The activation energies, kinetics, and chain transfer constants were also evaluated.