Theory of polymer breaking under tension

We consider the breaking of a polymer molecule which is fixed at one end and is acted upon by a force at the other. The polymer is assumed to be a linear chain joined together by bonds which satisfy the Morse potential. The applied force is found to modify the Morse potential so that the minimum becomes metastable. Breaking is just the decay of this metastable bond, by causing it to go over the barrier. Increasing the force causes the potential to become more and more distorted and eventually leads to the disappearance of the barrier. The limiting force at which the barrier disappears is D(e)a/2,D-e with a the parameters characterizing the Morse potential. The rate of breaking is first calculated using multidimensional quantum transition state theory. We use the harmonic approximation to account for vibrations of all the units. It includes tunneling contributions to the rate, but is valid only above a certain critical temperature. It is possible to get an analytical expression for the rate of breaking. We have calculated the rate of breaking for a model, which mimics polyethylene. First we calculate the rate of breaking of a single bond, without worrying about the other bonds. Inclusion of other bonds under the harmonic approximation is found to lower this rate by at the most one order of magnitude. Quantum effects are found to increase the rate of breaking and are significant only at temperatures less than 150 K. At 300 K, the calculations predict a bond in polyethylene to have a lifetime of only seconds at a force which is only half the limiting force. Calculations were also done using the Lennard-Jones potential. The results for Lennard-Jones and Morse potentials were rather different, due to the different long-range behaviors of the two potentials. A calculation including friction was carried out, at the classical level, by assuming that each atom of the chain is coupled to its own collection of harmonic oscillators. Comparison of the results with the simulations of Oliveira and Taylor [J. Chem. Phys. 101, 10 118 (1994)] showed the rate to be two to three orders of magnitude higher. As a possible explanation of discrepancy, we consider the translational motion of the ends of the broken chains. Using a continuum approximation for the chain, we find that in the absence of friction, the rate of the process can be limited by the rate at which the two broken ends separate from one another and the lowering of the rate is at the most a factor of 2, for the parameters used in the simulation (for polyethylene). In the presence of friction, we find that the rate can be lowered by one to two orders of magnitude, making our results to be in reasonable agreement with the simulations.

The role of sustainable agriculture and renewable-resource management in reducing greenhouse-gas emissions and increasing sinks in China and India

This paper contains an analysis of the technical options in agriculture for reducing greenhouse-gas emissions and increasing sinks, arising from three distinct mechanisms: (i) increasing carbon sinks in soil organic matter and above-ground biomass; (ii) avoiding carbon emissions from farms by reducing direct and indirect energy use; and (iii) increasing renewable-energy production from biomass that either substitutes for consumption of fossil fuels or replaces inefficient burning of fuelwood or crop residues, and so avoids carbon emissions, together with use of biogas digesters and improved cookstoves. We then review best-practice sustainable agriculture and renewable-resource-management projects and initiatives in China and India, and analyse the annual net sinks being created by these projects, and the potential market value of the carbon sequestered. We conclude with a summary of the policy and institutional conditions and reforms required for adoption of best sustainability practice in the agricultural sector to achieve the desired reductions in emissions and increases in sinks. A review of 40 sustainable agriculture and renewable-resource-management projects in China and India under the three mechanisms estimated a carbon mitigation potential of 64.8 MtC yr(-1) from 5.5 Mha. The potential income for carbon mitigation is $324 million at $5 per tonne of carbon. The potential exists to increase this by orders of magnitude, and so contribute significantly to greenhouse-gas abatement. Most agricultural mitigation options also provide several ancillary benefits. However, there are many technical, financial, policy, legal and institutional barriers to overcome.

density matrix renormalization group study of polyacene

We study the nature of excited states of long polyacene oligomers within a Pariser-Parr-Pople (PPP) Hamiltonian using the Symmetrized Density Matrix Renormalization Group (SDMRG) technique. We find a crossover between the two-photon state and the lowest dipole allowed excited state as the system size is increased from tetracene to pentacene. The spin-gap is the smallest gap. We also study the equilibrium geome tries in the ground and excited states from bond orders and bond-bond correlation functions. We find that the Peierls instability in the ground state of polyacene is conditional both from energetics and structure factors computed froth correlation functions.

Stabilizing a pulsed field emission from an array of carbon nanotubes

In this paper, we propose a new design configuration for a carbon nanotube (CNT) array based pulsed field emission device to stabilize the field emission current. In the new design, we consider a pointed height distribution of the carbon nanotube array under a diode configuration with two side gates maintained at a negative potential to obtain a highly intense beam of electrons localized at the center of the array. The randomly oriented CNTs are assumed to be grown on a metallic substrate in the form of a thin film. A model of field emission from an array of CNTs under diode configuration was proposed and validated by experiments. Despite high output, the current in such a thin film device often decays drastically. The present paper is focused on understanding this problem. The random orientation of the CNTs and the electromechanical interaction are modeled to explain the self-assembly. The degraded state of the CNTs and the electromechanical force are employed to update the orientation of the CNTs. Pulsed field emission current at the device scale is finally obtained by using the Fowler-Nordheim equation by considering a dynamic electric field across the cathode and the anode and integration of current densities over the computational cell surfaces on the anode side. Furthermore we compare the subsequent performance of the pointed array with the conventionally used random and uniform arrays and show that the proposed design outperforms the conventional designs by several orders of magnitude. Based on the developed model, numerical simulations aimed at understanding the effects of various geometric parameters and their statistical features on the device current history are reported.

Bounds on fourth generation induced lepton flavour violating double insertions in supersymmetry

We derive bounds on leptonic double mass insertions of the type delta(l)(i4)delta(l)(4j) in four generational MSSM, using the present limits on l(i) -> l(j) + gamma. Two main features distinguish the rates of these processes in MSSM4 from MSSM3: (a) tan beta is restricted to be very small less than or similar to 3 and (b) the large masses for the fourth generation leptons. In spite of small tan beta, there is an enhancement in amplitudes with LLRR (4 delta(ll)(i4)delta(rr)(4j)) type insertions which pick up the mass of the fourth generation lepton, m(tau'). We find these bounds to be at least two orders of magnitude more stringent than those in MSSM3. (C) 2011 Elsevier B.V. All rights reserved.

Generalized asymptotic expansions for the wavenumbers in infinite flexible in vacuo orthotropic cylindrical shells

Analytical expressions are found for the wavenumbers and resonance frequencies in flexible, orthotropic shells using the asymptotic methods. These expressions are valid for arbitrary circumferential orders n. The Donnell-Mushtari shell theory is used to model the dynamics of the cylindrical shell. Initially, an in vacuo cylindrical isotropic shell is considered and expressions for all the wavenumbers (bending, near-field bending, longitudinal and torsional) are found. Subsequently, defining a suitable orthotropy parameter epsilon, the problem of wave propagation in an orthotropic shell is posed as a perturbation on the corresponding problem for an isotropic shell. Asymptotic expressions for the wavenumbers in the in vacuo orthotropic shell are then obtained by treating epsilon as an expansion parameter. In both cases (isotropy and orthotropy), a frequency-scaling parameter (eta) and Poisson's ratio (nu) are used to find elegant expansions in the different frequency regimes. The asymptotic expansions are compared with numerical solutions in each of the cases and the match is found to be good. The main contribution of this work lies in the extension of the existing literature by developing closed-form expressions for wavenumbers with arbitrary circumferential orders n in the case of both, isotropic and orthotropic shells. Finally, we present natural frequency expressions in finite shells (isotropic and orthotropic) for the axisymmetric mode and compare them with numerical and ANSYS results. Here also, the comparison is found to be good. (C) 2011 Elsevier Ltd. All rights reserved.

A Simulation Based Study and Analysis of Double Gate Tunnel FET Performance for Low Stand-By Power Applications

The conventional metal oxide semiconductor field effect transistor (MOSFET)may not be suitable for future low standby power (LSTP) applications due to its high off-state current as the sub-threshold swing is theoretically limited to 60mV/decade. Tunnel field effect transistor (TFET) based on gate controlled band to band tunneling has attracted attention for such applications due to its extremely small sub-threshold swing (much less than 60mV/decade). This paper takes a simulation approach to gain some insight into its electrostatics and the carrier transport mechanism. Using 2D device simulations, a thorough study and analysis of the electrical parameters of the planar double gate TFET is performed. Due to excellent sub-threshold characteristics and a reverse biased structure, it offers orders of magnitude less leakage current compared to the conventional MOSFET. In this work, it is shown that the device can be scaled down to channel lengths as small as 30 nm without affecting its performance. Also, it is observed that the bulk region of the device plays a major role in determining the sub-threshold characteristics of the device and considerable improvement in performance (in terms of ION/IOFF ratio) can be achieved if the thickness of the device is reduced. An ION/IOFF ratio of 2x1012 and a minimum point sub-threshold swing of 22mV/decade is obtained.

A fast algorithm for finding frequent episodes in event streams

Frequent episode discovery is a popular framework for mining data available as a long sequence of events. An episode is essentially a short ordered sequence of event types and the frequency of an episode is some suitable measure of how often the episode occurs in the data sequence. Recently,we proposed a new frequency measure for episodes based on the notion of non-overlapped occurrences of episodes in the event sequence, and showed that, such a definition, in addition to yielding computationally efficient algorithms, has some important theoretical properties in connecting frequent episode discovery with HMM learning. This paper presents some new algorithms for frequent episode discovery under this non-overlapped occurrences-based frequency definition. The algorithms presented here are better (by a factor of N, where N denotes the size of episodes being discovered) in terms of both time and space complexities when compared to existing methods for frequent episode discovery. We show through some simulation experiments, that our algorithms are very efficient. The new algorithms presented here have arguably the least possible orders of spaceand time complexities for the task of frequent episode discovery.

On Pushing Multilingual Query Operators into Relational Engines

To effectively support today’s global economy, database systems need to manage data in multiple languages simultaneously. While current database systems do support the storage and management of multilingual data, they are not capable of querying across different natural languages. To address this lacuna, we have recently proposed two cross-lingual functionalities, LexEQUAL[13] and SemEQUAL[14], for matching multilingual names and concepts, respectively. In this paper, we investigate the native implementation of these multilingual functionalities as first-class operators on relational engines. Specifically, we propose a new multilingual storage datatype, and an associated algebra of the multilingual operators on this datatype. These components have been successfully implemented in the PostgreSQL database system, including integration of the algebra with the query optimizer and inclusion of a metric index in the access layer. Our experiments demonstrate that the performance of the native implementation is up to two orders-of-magnitude faster than the corresponding outsidethe- server implementation. Further, these multilingual additions do not adversely impact the existing functionality and performance. To the best of our knowledge, our prototype represents the first practical implementation of a crosslingual database query engine.

Utilizing an ionic liquid for synthesizing a soft matter polymer ``gel'' electrolyte for high rate capability lithium-ion batteries

A cross-linked polymer ``gel'' electrolyte obtained from free radical polymerization of a vinyl monomer (acrylonitrile; AN) in a room temperature ionic liquid electrolyte (N,N-methyl butyl pyrrolidinium-bis (trifluoromethanesulphonyl)imide-lithium bis(trifluoromethanesulphonyl) imide;LiTFSI-[Py(1,4)-TFSI]) for application in high rate capability rechargeable lithium-ion batteries is discussed here. This is a novel alternative compared to the often employed approach of using a molecular liquid as the medium for performing the polymerization reaction. The polymer ``gel'' electrolytes (AN:Py(1,4)-TFSI = 0.16-0.18, w/w) showed remarkable compliable mechanical strength and higher thermal stability compared to LiTFSI-[Py(1,4)-TFSI]. Despite two orders increase in magnitude of viscosity of polymer ``gels'', the room temperature ionic conductivity of the ``gels'' (1.1 x 10(-3)-1.7 x 10(-3) Omega(-1) cm(-1)) were nearly identical to that of the ionic liquid (1.8 x 10(-3) Omega(-1) cm(-1)). The present ``gel'' electrolytes did not exhibit any ageing effects on ionic conductivity similar to the conventional polymer gel electrolytes (e.g. high molecular weight polymer + salt + high dielectric constant molecular solvent). The disorder (ionic liquid) to a relative order (cross-linked polymer electrolyte) transformation does not at all influence the concentration of conducting species. The polymer framework is still able to provide efficient pathways for fast ion transport. Unlike the ionic liquid which is impossible to assemble without a conventional separator in a cell, the polymer ``gel'' electrolyte could be conveniently assembled without a separator in a Li vertical bar lithium iron phosphate (LiFePO(4)) cell. Compared to the ionic liquid, the ``gel'' electrolyte showed exceptional cyclability and rate capability (current density: 35-760 mA g(-1) with LiFePO(4) electronically wired with carbon (amorphous or multiwalled nanotube [MWCNT]).

Synthesis and Characterization of Carbon Nanotube-Polymer Multilayer Structures

We develop lightweight, multilayer materials composed of alternating layers of poly dimethyl siloxane (PDMS) polymer and vertically aligned carbon nanotube (CNT) arrays, and characterize their mechanical response in compression. The CNT arrays used In the assembly are synthesized with graded mechanical properties along their thickness, and their use enables the creation of multilayer structures with low density (0.12-0.28 g/cm(3)). We test the mechanical response of structures composed of different numbers of CNT layers partially embedded in PDMS polymer, under quasi-static and dynamic loading. The resulting materials exhibit a hierarchical, fibrous structure with unique mechanical properties: They can sustain large compressive deformations (up to similar to 0.8 strain) with a nearly complete recovery and present strain localization in selected sections of the materials. Energy absorption, as determined by the hysteresis observed In stress-strain curves, is found to be at least 3 orders of magnitude larger than that of natural and synthetic cellular materials of comparable density. Conductive bucky paper Is Included within the polymer interlayers. This allows the measurement of resistance variation as a function of applied stress, showing strong correlation with the observed strain localization In compression.

Large reduction of leakage current by graded-layer La doping in (Ba0.5, Sr0.5)TiO3 thin films

A large reduction in the leakage current behavior in (Ba, Sr)TiO3 (BST) thin films was observed by graded-layer donor doping. The graded doping was achieved by introducing La-doped BST layers in the grown BST films. The films showed a large decrease (about six orders of magnitude) in the leakage current in comparison to undoped films at an electric field of 100 kV/cm. The large decrease in leakage current was attributed to the formation of highly resistive layers, originating from compensating defect chemistry involved for La-doped films grown in oxidizing environment. Temperature-dependent leakage-current behavior was studied to investigate the conduction mechanism and explanations of the results were sought from Poole–Frenkel conduction mechanism.

Enhancement of photoluminescence intensity by photoinduced interdiffusion in nanolayered a-Se/As2S3 films

Optical parameters of chalcogenide glass multilayers with 12–15 nm modulation lengths prepared by thermal evaporation can be changed by laser irradiation. Photoluminescence (PL) studies were carried out on such nonirradiated and irradiated multilayered samples of a-Se/As2S3 (sublayer thickness of a-Se is 4–5 nm for one set of samples and 1–2 nm for the other set. However As2S3 sublayer thickness is 11–12 nm for both sets of samples.) PL intensity can be increased by several orders of magnitude by reducing the Se well layer (lower band gap) thickness and can be further increased by irradiating the samples with appropriate wavelengths in the range of the absorption edge. The broadening of luminescence bands takes place either with a decrease in Se layer thickness or with irradiation. The former is due to the change in interface roughness and defects because of the enhanced structural disorder while the latter is due to photoinduced interdiffusion. The photoinduced interdiffusion creates defects at the interface between Se and As2S3 by forming an As–Se–S solid solution. From the deconvoluted PL spectrum, it is shown that the peak PL intensity, full width half maximum, and the PL quantum efficiency of particular defects giving rise to PL, can be tuned by changing the sublayer thickness or by interdiffusion.

Laser‐Induced Turbulence

In a recent experiment on laser beam transmission through an absorbing gas, the critical Reynold's number for the flow, induced by the heating of the gas, to become turbulent was found to be less than 30, which is many orders of magnitude smaller than that for pure shear flow in pipes. It is shown here that a Rayleigh number is the more appropriate criterion to characterize the stability of flow in this situation, and its value estimated in two limiting cases is found to bracket the expected critical Rayleigh number for vertical concentric cylinders.

Improved ferroelectric and leakage properties in symmetric BiFeO3/SrTiO3 superlattice

Symmetric BiFeO3/SrTiO3 superlattices were fabricated by pulsed laser deposition on SrTiO3 (100) substrates. Frequency independent and near saturated P-E hysteresis was observed in the case of a superlattice (periodicity of ∼ 11 nm) as compared to leaky hysteresis observed in epitaxial BiFeO3. Room temperature leakage current density of the superlattice was almost two orders of magnitude lower than that of BiFeO3. Observed leakage current behavior in case of both BiFeO3 and superlattice indicates the dominance of space charge limited conduction. Improvement in ferroelectric property was discussed in connection to enhanced epitaxial strain, reduced leakage current, and electrostatic interaction between BiFeO3 and SrTiO3.