On the existence and stability of electrostatic structures in non-Maxwellian electron-positron-ion plasmas

Electrostatic solitary waves in plasmas are the focus of many current studies of localized electrostatic disturbances in both laboratory and astrophysical plasmas. Here, an investigation of the nonlinear dynamics of plasma evolving in two dimensions, in the presence of excess superthermal background electrons and positrons, is undertaken. We investigate the effect of a magnetic field on weakly nonlinear ion acoustic waves. Deviation from the Maxwellian distribution is effectively modelled by the kappa model. A linear dispersion relation is derived, and a decrease in frequency and phase speed in both parallel and perpendicular modes can be seen, when the proportion of positrons to electrons increases. We show that ion acoustic solitary waves can be generated during the nonlinear evolution of a plasma fluid, and their nonlinear propagation is governed by a Zakharov-Kuznetsov (ZK) type equation. A multiple scales perturbation technique is used to derive the ZK equation. The solitary wave structures are dependent on the relation between the system parameters, specifically the superthermality of the system, the proportion of positron content, magnetic field strength, and the difference between electron and positron temperature. The parametric effect of these on electrostatic shock structures is investigated. In particular, we find that stronger superthermality leads to narrower excitations with smaller potential amplitudes. Increased positron concentration also suppresses both the amplitude and the width of solitary wave structures. However, the structures are only weakly affected by temperature differentials between electrons and positrons in our model. © 2013 AIP Publishing LLC.

Microstructural analysis of non-woven fabrics using scanning electron microscopy and image processing. Part 2:Application to hydroentangled fabrics

The image analysis techniques developed in Part 1 to study microstructural changes in non-woven fabrics are applied to measure the fibre orientation distribution and fibre length distribution of hydroentangled fabrics. The results are supported by strength and modulus measurements using samples from the same fabrics. It is shown that the techniques developed can successfully be used to assess the degree of entanglement of hydroentangled fabrics regardless of their thickness.

Pressure anisotropy effects on nonlinear electrostatic excitations in magnetized electron-positron-ion plasmas

The propagation of linear and nonlinear electrostatic waves is investigated in a magnetized anisotropic electron-positron-ion (e-p-i) plasma with superthermal electrons and positrons. A two-dimensional plasma geometry is assumed. The ions are assumed to be warm and anisotropic due to an external magnetic field. The anisotropic ion pressure is defined using the double adiabatic Chew-Golberger-Low (CGL) theory. In the linear regime, two normal modes are predicted, whose characteristics are investigated parametrically, focusing on the effect of superthermality of electrons and positrons, ion pressure anisotropy, positron concentration and magnetic field strength. A Zakharov-Kuznetsov (ZK) type equation is derived for the electrostatic potential (disturbance) via a reductive perturbation method. The parametric role of superthermality, positron content, ion pressure anisotropy and magnetic field strength on the characteristics of solitary wave structures is investigated. Following Allen and Rowlands [J. Plasma Phys. 53, 63 (1995)], we have shown that the pulse soliton solution of the ZK equation is unstable to oblique perturbations, and have analytically traced the dependence of the instability growth rate on superthermality and ion pressure anisotropy.

Non-equilibrium modeling of the FE XVII 3C/3D Line Ratio in an Intense X-ray Free-electron Laser Excited Plasma

Recent measurements using an X-ray Free Electron Laser (XFEL) and an Electron Beam Ion Trap at the Linac Coherent Light Source facility highlighted large discrepancies between the observed and theoretical values for the Fe XVII 3C/3D line intensity ratio. This result raised the question of whether the theoretical oscillator strengths may be significantly in error, due to insufficiencies in the atomic structure calculations. We present time-dependent spectral modeling of this experiment and show that non-equilibrium effects can dramatically reduce the predicted 3C/3D line intensity ratio, compared with that obtained by simply taking the ratio of oscillator strengths. Once these non-equilibrium effects are accounted for, the measured line intensity ratio can be used to determine a revised value for the 3C/3D oscillator strength ratio, giving a range from 3.0 to 3.5. We also provide a framework to narrow this range further, if more precise information about the pulse parameters can be determined. We discuss the implications of the new results for the use of Fe XVII spectral features as astrophysical diagnostics and investigate the importance of time-dependent effects in interpreting XFEL-excited plasmas.

Electron-impact excitation of Ar 2+

Context: Emission from Ar III is seen in planetary nebulae, in H II regions, and from laboratory plasmas. The analysis of such spectra requires accurate electron impact excitation data. Aims: The aim of this work is to improve the electron impact excitation data available for Ar2+, for application in studies of planetary nebulae and laboratory plasma spectra. The effects of the new data on diagnostic line ratios are also studied. Methods: Electron-impact excitation collision strengths have been calculated using the R-Matrix Intermediate-Coupling Frame-Transformation method and the R-Matrix Breit-Pauli method. Excitation cross sections are calculated between all levels of the configurations 3s^23p^4, 3s3p^5, 3p^6, 3p^53d, and 3s^23p^3nl (3d ≤ nl ≤ 5s). Maxwellian effective collision strengths are generated from the collision strength data. Results: Good agreement is found in the collision strengths calculated using the two R-Matrix methods. The collision strengths are compared with literature values for transitions within the 3s^23p4 configuration. The new data has a small effect on Te values obtained from the I(λ7135 Å+ λ7751 Å)/ I(λ5192 Å) line ratio, and a larger effect on the Ne values obtained from the I(λ7135 Å)/I(λ9 μm) line ratio. The final effective collision strength data is archived online.

NMR studies of the exchange reactions of CH3CN.BX3 with excess CH3CN /|nJoseph Fogelman. -- 260 St. Catharines, Ont. : [s. n.],

Exchange reactions between molecular complexes and excess acid or base are well known and have been extensively surveyed in the literature(l). Since the exchange mechanism will, in some way involve the breaking of the labile donor-acceptor bond, it follows that a discussion of the factors relating to bonding in molecular complexes will be relevant. In general, a strong Lewis base and a strong Lewis acid form a stable adduct provided that certain stereochemical requirements are met. A strong Lewis base has the following characteristics (1),(2) (i) high electron density at the donor site. (ii) a non-bonded electron pair which has a low ionization potential (iii) electron donating substituents at the donor atom site. (iv) facile approach of the site of the Lewis base to the acceptor site as dictated by the steric hindrance of the substituents. Examples of typical Lewis bases are ethers, nitriles, ketones, alcohols, amines and phosphines. For a strong Lewis acid, the following properties are important:( i) low electron density at the acceptor site. (ii) electron withdrawing substituents. (iii) substituents which do not interfere with the close approach of the Lewis base. (iv) availability of a vacant orbital capable of accepting the lone electron pair of the donor atom. Examples of Lewis acids are the group III and IV halides such (M=B, AI, Ga, In) and MX4 - (M=Si, Ge, Sn, Pb). The relative bond strengths of molecular complexes have been investigated by:- (i) (ii) (iii) (iv) (v] (vi) dipole moment measurements (3). shifts of the carbonyl peaks in the IIIR. (4) ,(5), (6) .. NMR chemical shift data (4),(7),(8),(9). D.V. and visible spectrophotometric shifts (10),(11). equilibrium constant data (12), (13). heats of dissociation and heats of reactions (l~), (16), (17), (18), (19). Many experiments have bben carried out on boron trihalides in order to determine their relative acid strengths. Using pyridine, nitrobenzene, acetonitrile and trimethylamine as reference Lewis bases, it was found that the acid strength varied in order:RBx3 > BC1 3 >BF 3 • For the acetonitrile-boron trihalide and trimethylamine boron trihalide complexes in nitrobenzene, an-NMR study (7) showed that the shift to lower field was. greatest for the BB~3 adduct ~n~ smallest for the BF 3 which is in agreement with the acid strengths. If electronegativities of the substituents were the only important effect, and since c~ Br ,one would expect the electron density at the boron nucleus to vary as BF3strength would vary as BF~BC1)BBr3: However, for the boron trihalides, the trend is in the opposite direction as determined experimentally. Considerable back-bonding (20), (21) between the halogen and the boron atoms has been proposed as the predominating factor, i.e. ~rt- back-bond between a lone electron pair on the halogen and the vacant orbital on the boron site. The degree of back-bonding varies inversely as the bo~on halogen distance and one would therefore expect the B-F bond to exhibit greater back-bonding character than the B-Cl or B-Br bonds. Since back-bonding transfers electron density from substituent to the boron atom site, this process would be expected to weaken the Lewis acid strength. This explains the Lewis acid strength increasing in the order BF 3 BC1 3 BBr 3 . When the acetonitrile boron trihalide complex is formed, the boron atom undergoes ~_cbange of hybridization from sp2 to sp3. From a linear relationship between the heat of formation of ethyl acetate adducts and the shift in the carbonyl I.R. stretch, Drago (22) et al have proposed that the angular di~tortion of the X-B-X bonds from sp2 (12 ) to sp3 (10 hybridization is proportional to the amount of charge transferred, i.e. to the nature of the base, and they have rejected the earlier concept of reorganization energy in explaining the formation of the adduct bond (19).

Scanning Electron Microscopy Studies on Tear and Wear Failure of Short Kevlar Fiber-Thermoplastic- Polyurethane Composite

Tear and wear properties of short kevlar fiber, thermoplastic polcurethane (TPU) composite with respect to fiber loading-and fiber onentation has been studied and the fracture surfaces were examined under scanning electron microscope (SEM). Tear strength first decreased up to 20 phr fiber loading and then gradually increased with increasing fiber loading. Anisotropy in tear strength was evident beyond a fiber loading of 20 phr. Tear fracture surface of unfilled TPU showed sinusoidal folding characteristics of high strength matrix. At low fiber loading the tear failure was mainly due to fibermatrix failure whereas at higher fiber loading the failure occurred by fiber breakage. Abrasion loss shows a continuous rise with increasing fiber loading, the loss in the transverse orientation of fibers being higher than that in the longitudinal orientation. The abraded surface showed lone cracks and ridges parallel to the direction of abrasion indicating an abrasive wear mechanism. In the presence of fber the abrasion loss was mainly due to fiber low.

Phenylethynylarene Based Donor-Acceptor Systems: Design, Synthesis and Photophysical Studies

This thesis Entitled phenylethynylarene based Donor-Acceptor systems:Desigh,Synthesis and Photophysical studies. A strategy for the design of donor-acceptor dyads, wherein decay of the charge separated (CS) state to low lying local triplet levels could possibly be prevented, is proposed. In order to examine this strategy, a linked donor-acceptor dyad BPEPPT with bis(phenylethYlly/)pyrene (BPEP) as the light absorber and acceptor and phenothiazine (PT) as donor was designed and photoinduced electron transfer in the dyad investigated. Absorption spectra of the dyad can be obtained by adding contributions due 10 the BPEP and PT moieties indicating that the constituents do not interact in the ground stale. Fluorescence of the BPEP moiety was efficiently quenched by the PT donor and this was attributed to electron lransfer from PT to BPEP. Picosecond transient absorption studies suggested formation of a charge separated state directly from the singlet excited state of BPEP. Nanosecond flash photolysis experiments gave long-ived transient absorptions assignable to PT radical cation and BPEP radical anion. These assignments were confirmed by oxygen quenching studies and secondary electron transfer experiments. Based on the available data, energy level diagram for BPEP-PT was constructed. The long lifetime of the charge separated state was attributed to the inverted region effects. The CS state did not undergo decay to low lying BPEP triplet indicating the success of our strategy

Synthesis, characterization and physiochemical information, along with antimicrobial studies of some metal complexes derived from an ON donor semicarbazone ligand

Eight new transition metal complexes of benzaldehyde-N(4)–phenylsemicarbazone have been synthesized and characterized by elemental analyses, molar conductance, electronic and infrared spectral studies. In all the complexes, the semicarbazone is coordinated as neutral bidentate ligand. 1H NMR spectrum of [Zn(HL)2(OAc)2] shows that there is no enolisation of the ligand in the complex. The magnetic susceptibility measurements indicate that Cr(III), Mn(II), Fe(III), Co(II) and Cu(II) complexes are paramagnetic and Ni(II) is diamagnetic. The EPR spectrum of [Mn(HL)2(OAc)2] in DMF solution at 77K shows hyperfine sextet with low intensity forbidden lines lying between each of the two main hyperfine lines. The g values calculated for the [Cu(HL)2SO4] complex in frozen DMF, indicate the presence of unpaired electron in the dx2−y2 orbital. The metal ligand bonding parameters evaluated showed strong in-plane bonding and in-plane bonding. The ligand and complexes were screened for their possible antimicrobial activities.

Synthesis and spectral investigations of vanadium(IV/V) complexes derived from an ONS donor thiosemicarbazone ligand

Four oxovanadium and one dioxovanadium complex with 2-hydroxyacetophenone N(4)- phenylthiosemicarbazone (H2L) which are represented as [VOLphen]·2H2O (1), [VOLbipy] (2), [VOLdmbipy] (3), [VOL]2 (4) and [VO2HL]·CH3OH (5) have been synthesized and characterized by elemental analyses, electronic, infrared and EPR spectral techniques. In all the complexes 1–4 the ligand coordinates through phenolic oxygen, azomethine nitrogen and thiolate sulfur. But in complex [VO2HL]·CH3OH, coordination takes place in thione form instead of thiolate sulfur. All the complexes except [VO2HL]·CH3OH are EPR active due to the presence of an unpaired electron. In frozen DMF at 77 K, all the oxovanadium(IV) complexes show axial anisotropy with two sets of eight line patterns

Ground and Excited State Electron Transfer Reaction Between a few Anthracene Appended Tertiary Amines and Suitable Electron Acceptors

the thesis entitled “Ground and Excited State Electron Transfer Reaction Between a few Anthracene Appended Tertiary Amines and Suitable Electron Acceptors” portrays our attempts to explore the solvent, concentration and temperature effect of the reaction between a few (anthracen-9- yl)methanamines with electron acceptors like DMAD, DBA and DBE. We have also studied the effect of solvent and percentage fluorescence quenching in the photoinduced electron transfer reactions of these ‘donor-spacer-acceptor’ systems. Finally we look in to the intramolecular electron transfer reactions of a few tertiary amine appended dibenzobarrelenes and bisdibenzobarrelenes

Theoretical Design and Synthesis of Donor-Acceptor Conjugated Polymers for Photovoltaic and NLO Applications

Polymers with conjugated π-electron backbone display unusual electronic properties such as low energy optical transition, low ionization potentials, and high electron affinities. The properties that make these materials attractive include a wide range of electrical conductivity, mechanical flexibility and thermal stability. Some of the potential applications of these conjugated polymers are in sensors, solar cells, field effect transistors, field emission and electrochromic displays, supercapacitors and energy storage. With recent advances in the stability of conjugated polymer materials, and improved control of properties, a growing number of applications are currently being explored. Some of the important applications of conducting polymers include: they are used in electrostatic materials, conducting adhesives, shielding against electromagnetic interference (EMI), artificial nerves, aircraft structures, diodes, and transistors.

Estimates of electronic coupling for excess electron transfer in DNA

Electronic coupling Vda is one of the key parameters that determine the rate of charge transfer through DNA. While there have been several computational studies of Vda for hole transfer, estimates of electronic couplings for excess electron transfer (ET) in DNA remain unavailable. In the paper, an efficient strategy is established for calculating the ET matrix elements between base pairs in a π stack. Two approaches are considered. First, we employ the diabatic-state (DS) method in which donor and acceptor are represented with radical anions of the canonical base pairs adenine-thymine (AT) and guanine-cytosine (GC). In this approach, similar values of Vda are obtained with the standard 6-31 G* and extended 6-31++ G* basis sets. Second, the electronic couplings are derived from lowest unoccupied molecular orbitals (LUMOs) of neutral systems by using the generalized Mulliken-Hush or fragment charge methods. Because the radical-anion states of AT and GC are well reproduced by LUMOs of the neutral base pairs calculated without diffuse functions, the estimated values of Vda are in good agreement with the couplings obtained for radical-anion states using the DS method. However, when the calculation of a neutral stack is carried out with diffuse functions, LUMOs of the system exhibit the dipole-bound character and cannot be used for estimating electronic couplings. Our calculations suggest that the ET matrix elements Vda for models containing intrastrand thymine and cytosine bases are essentially larger than the couplings in complexes with interstrand pyrimidine bases. The matrix elements for excess electron transfer are found to be considerably smaller than the corresponding values for hole transfer and to be very responsive to structural changes in a DNA stack

Understanding electron heat flux signatures in the solar wind

Suprathermal electrons (E > 80 eV) carry heat flux away from the Sun. Processes controlling the heat flux are not well understood. To gain insight into these processes, we model heat flux as a linear dependence on two independent parameters: electron number flux and electron pitch angle anisotropy. Pitch angle anisotropy is further modeled as a linear dependence on two solar wind components: magnetic field strength and plasma density. These components show no correlation with number flux, reinforcing its independence from pitch angle anisotropy. Multiple linear regression applied to 2 years of Wind data shows good correspondence between modeled and observed heat flux and anisotropy. The results suggest that the interplay of solar wind parameters and electron number flux results in distinctive heat flux dropouts at heliospheric features like plasma sheets but that these parameters continuously modify heat flux. This is inconsistent with magnetic disconnection as the primary cause of heat flux dropouts. Analysis of fast and slow solar wind regimes separately shows that electron number flux and pitch angle anisotropy are equally correlated with heat flux in slow wind but that number flux is the dominant correlative in fast wind. Also, magnetic field strength correlates better with pitch angle anisotropy in slow wind than in fast wind. The energy dependence of the model fits suggests different scattering processes in fast and slow wind.

Structural and equilibrium studies on mixed ligand complexes of Co(II), Ni(II), Cu(II) and Zn(II) with N-(2-benzimidazolyl)methyliminodiacetic acid and typical N,N donor ligands

Mixed ligand complexes: [Co(L)(bipy)] (.) 3H(2)O (1), [Ni(L)(phen)] (.) H2O (2), [Cu(L)(phen)] (.) 3H(2)O (3) and [Zn(L)(bipy)] (.) 3H(2)O (4), where L2- = two -COOH deprotonated dianion of N-(2-benzimidazolyl)methyliminodiacetic acid (H(2)bzimida, hereafter, H,L), bipy = 2,2' bipyridine and phen = 1,10-phenanthroline have been isolated and characterized by elemental analysis, spectral and magnetic measurements and thermal studies. Single crystal X-ray diffraction studies show octahedral geometry for 1, 2 and 4 and square pyramidal geometry for 3. Equilibrium studies in aqueous solution (ionic strength I = 10(-1) mol dm(-3) (NaNO3), at 25 +/- 1 degrees C) using different molar proportions of M(II):H2L:B, where M = Co, Ni, Cu and Zn and B = phen, bipy and en (ethylene diamine), however, provides evidence of formation of mononuclear and binuclear binary and mixed ligand complexes: M(L), M(H-1L)(-), M(B)(2+), M(L)(B), M(H-1L)(B)(-), M-2(H-1L)(OH), (B)M(H-1L)M(B)(+), where H-1L3- represents two -COOH and the benzimidazole NI-H deprotonated quadridentate (O-, N, O-, N), or, quinquedentate (O-, N, O-, N, N-) function of the coordinated ligand H,L. Binuclear mixed ligand complex formation equilibria: M(L)(B) + M(B)(2+) = (B)M(H-1L)M(B)(+) + H+ is favoured with higher pi-acidity of the B ligands. For Co(II), Ni(II) and Cu(II), these equilibria are accompanied by blue shift of the electronic absorption maxima of M(II) ions, as a negatively charged bridging benzimidazolate moiety provides stronger ligand field than a neutral one. Solution stability of the mixed ligand complexes are in the expected order: Co(II) < Ni(II) < Cu(II) > Zn(II). The Delta logK(M) values are less negetive than their statistical values, indicating favoured formation of the mixed ligand complexes over the binary ones. (c) 2005 Elsevier B.V. All rights reserved.