Polarization Characteristics of Porous Electrode Systems with Adsorbed Intermediates Participating in the Electrode Reaction

Current-potential relationships are derived for porous electrode systems following a homogeneous model and whenadsorbed intermediates participate in the electrode reaction. Limiting Tafel slopes were deduced and compared with thecorresponding behavior on planar electrode systems. The theoretical results showed doubling of Tafel slopes when theslow-step is a charge-transfer reaction and a nonlogarithmic current-voltage behavior when the slow-step is a chemical reaction.Comparison of the experimental results with theory for the case of oxygen reduction on carbon surfaces in alkalinemedia indicates that a slow chemical reaction following the initial charge-transfer reaction to be the likely rate-controllingstep. Theoretical relationships are utilized to determine the exchange current density and the surface coverage by the adsorbedintermediates during the course of oxygen reduction from alkaline solutions on "carbon." Tafel slope measurementson planar and porous electrodes for the same reaction are suggested as one of the diagnostic criteria for elucidatingthe mechanistic pathways of electrochemical reactions.

Polarization relaxation, dielectric dispersion, and solvation dynamics in dense dipolar liquid

A unified treatment of polarization relaxation, dielectric dispersion and solvation dynamics in a dense, dipolar liquid is presented. It is shown that the information of solvent polarization relaxation that is obtained by macroscopic dielectric dispersion experiments is not sufficient to understand dynamics of solvation of a newly created ion or dipole. In solvation, a significant contribution comes from intermediate wave vector processes which depend critically on the short range (nearest‐neighbor) spatial and orientational order that are present in a dense, dipolar liquid. An analytic expression is obtained for the time dependent solvation energy that depends, in addition to the translational and rotational diffusion coefficients of the liquid, on the ratio of solute–solvent molecular sizes and on the microscopic structure of the polar liquid. Mean spherical approximation (MSA) theory is used to obtain numerical results for polarization relaxation, for wave vector and frequency dependent dielectric function and for time dependent solvation energy. We find that in the absence of translational contribution, the solvation of an ion is, in general, nonexponential. In this case, the short time decay is dominated by the longitudinal relaxation time but the long time decay is dominated by much slower large wave vector processes involving nearest‐neighbor molecules. The presence of a significant translational contribution drastically alters the decay behavior. Now, the long‐time behavior is given by the longitudinal relaxation time constant and the short time dynamics is controlled by the large wave vector processes. Thus, although the continuum model itself is conceptually wrong, a continuum model like result is recovered in the presence of a sizeable translational contribution. The continuum model result is also recovered in the limit of large solute to solvent size ratio. In the opposite limit of small solute size, the decay is markedly nonexponential (if the translational contribution is not very large) and a complete breakdown of the continuum model takes place. The significance of these results is discussed.

An unusual C-H center dot center dot center dot O hydrogen bond mediated reversal of polypeptide chain direction in a synthetic peptide helix

An unusual C-terminal conformation has been detected in a synthetic decapeptide designed to analyze the stereochemistry of helix termination in polypeptides. The crystal structure of the decapeptide Boc-Leu-Aib-Val-Ala-Leu-Aib-Val-(D)Ala-(D)Leu-Aib-OMe reveals a helical segment spanning residues 1-7 and helix termination by formation of a Schellman motif, generated by (D)Ala(8) adopting the left-handed helical (alpha(L)) conformation. The extended conformation at (D)Leu(9) results in a compact folded structure, stabilized by a potentially strong C-H ... O hydrogen bond between Ala(4) (CH)-H-alpha and (D)Leu(9)CO. The parameters for C-H ... O interaction are Ala(4) (CH)-H-alpha .. O=C (D)Leu(9) distance 3.27 Angstrom C-alpha-H .. O angle 176 degrees, and O .. H-alpha distance 2.29 Angstrom. This structure suggests that insertion of contiguous D-residues may provide a handle for the generation of designed structures containing more than one helical segment folded in a compact manner. (C) 2000 Academic Press.

Ambiguity-free polarization measurements from mixture initial preparations

Starting from beam and target spin systems which are polarized in the usual way by applying external magnetic fields, measurements of appropriate final state tensor parameters, viz., {t0,1k, k=1,...,2j} of particle d with spin j in a reaction a+b→d+c1+c2+. . .are suggested to determine the reaction amplitudes in spin space free from any associated discrete ambiguity.

Direction dependence in supernova data: constraining isotropy

We revise and extend the extreme value statistic, introduced in Gupta et al., to study direction dependence in the high-redshift supernova data, arising either from departures, from the cosmological principle or due to direction-dependent statistical systematics in the data. We introduce a likelihood function that analytically marginalizes over the,Hubble constant and use it to extend our previous statistic. We also introduce a new statistic that is sensitive to direction dependence arising from living off-centre inside a large void as well as from previously mentioned reasons for anisotropy. We show that for large data sets, this statistic has a limiting form that can be computed analytically. We apply our statistics to the gold data sets from Riess et al., as in our previous work. Our revision and extension of the previous statistic show that the effect of marginalizing over the Hubble constant instead of using its best-fitting value on our results is only marginal. However, correction of errors in our previous work reduces the level of non-Gaussianity in the 2004 gold data that were found in our earlier work. The revised results for the 2007 gold data show that the data are consistent with isotropy and Gaussianity. Our second statistic confirms these results.

Top polarization as a probe of new physics

We investigate the effects of new physics scenarios containing a high mass vector resonance on top pair production at the LHC, using the polarization of the produced top. In particular we use kinematic distributions of the secondary lepton coming from top decay, which depends on top polarization, as it has been shown that the angular distribution of the decay lepton is insensitive to the anomalous tbW vertex and hence is a pure probe of new physics in top quark production. Spin sensitive variables involving the decay lepton are used to reconstruct the top polarization. Some sensitivity is found for the new couplings of the top.

Comment on “Southward magnetic field in the neutral sheet produced by wavy motions Propagating in the dawn‐dusk direction”

In a recent paper Nakagawa and Nishida [1989] have suggested that wavy motions of the neutral sheet can be generated by the Kelvin‐Helmholtz instability if the dawn‐dusk flow of only several tens of km/s is present. However, their mathematical analysis is based on the choice of particular magnetic field directions in the three regions consisting of north, south lobes and the neutral sheet. In an earlier paper Uberoi [1986] discussed the Kelvin‐Helmholtz instability of a similar structured plasma layer without any assumptions either on velocity field directions or on the magnetic field directions, thus pointing out the angle effect due to variation in magnetic field directions on the instability criterion. The relevance of these results to the problem of wavy motions of the neutral sheet are pointed out. In particular it is found that when the y‐component of the magnetic field in each lobe is taken into consideration the Kelvin‐Helmholtz instability can be exicted only when the dawn‐dusk flow is of several hundreds of km/s a order of ten higher than that arrived in the analysis by Nakagawa and Nishida [1989].

Photoconductivity in β-AgI

Excitation spectra and transient and steady-state photoconductivity have been studied in undoped and 0.8-mole% Cu-doped single-crystal β-AgI between 150 and 260°K. A single peak in the spectral response was found to occur in each case, at 2.88 eV for undoped and at 2.81 eV for copper-doped specimens at 260 K, the difference being due to a decrease in band gap. The anisotropy due to polarization of incident radiation parallel or perpendicular to the c direction, which is a measure of the energy difference between the Γ9 and Γ7 levels in the valence band, was found to be 0.010 eV. Transient-photoconductivity experiments showed that the hole lifetime was 6 μ sec at 300°K, an order of magnitude larger than the electron lifetime. The hole drift mobility was found to be 12±2 cm2/ V sec at 300°K and limited by traps at a depth of 0.51±0.01 eV with concentration (3-5)×109/cm3 and capture cross section 10-11 cm2. The study of photoconductivity decay versus temperature revealed the presence of shallow hole traps at 0.14±0.02 eV with concentration greater than 1016/cm3 and capture cross section 10-19 cm2. The steady-state photoconductivity was determined by the deep hole traps at 0.51 eV, and showed the presence of shallow electron traps at a depth of 0.28 eV. The trap distribution was found to be substantially the same in pure and copper-doped specimens, indicating the monovalent substitutional role of copper. The effects of iodine annealing, cadmium doping, and heating above the transition temperature were also studied. The possible nature of the traps is discussed.

Processing and fiber content effects on the machinability of compression moulded random direction short GFRP composites

The random direction short Glass Fiber Reinforced Plastics (GFRP) have been prepared by two compression moulding processes, namely the Preform and Sheet Moulding Compound (SMC) processes. Cutting force analysis and surface characterization are conducted on the random direction short GFRPs with varying fiber contents (25 similar to 40%). Edge trimming experiments are preformed using carbide inserts with varing the depth of cut and cutting speed. Machining characteristics of the Preform and SMC processed random direction short GFRPs are evaluated in terms of cutting forces, surface quality, and tool wear. It is found that composite primary processing and fiber contents are major contributing factors influencing the cutting force magnitudes and surface textures. The SMC composites show better surface finish over the Preform composites due to less delamination and fiber pullouts. Moreover, matrix damage and fiber protrusions at the machined edge are reduced by increasing fiber content in the random direction short GFRP composites.

On measurement of top polarization as a probe of t(t)over-bar production mechanisms at the LHC

In this note we demonstrate the use of top polarization in the study of t (t) over bar resonances at the LHC, in the possible case where the dynamics implies a non-zero top polarization. As a probe of top polarization we construct an asymmetry in the decay-lepton azimuthal angle distribution (corresponding to the sign of cos phi(l)) in the laboratory. The asymmetry is non-vanishing even for a symmetric collider like the LHC, where a positive z axis is not uniquely defined. The angular distribution of the leptons has the advantage of being a faithful top-spin analyzer, unaffected by possible anomalous tbW couplings, to linear order. We study, for purposes of demonstration, the case of a Z' as might exist in the little Higgs models. We identify kinematic cuts which ensure that our asymmetry reflects the polarization in sign and magnitude. We investigate possibilities at the LHC with two energy options: root s = 14TeV and root s = 7TeV, as well as at the Tevatron. At the LHC the model predicts net top quark polarization of the order of a few per cent for M-Z' similar or equal to 1200GeV, being as high as 10% for a smaller mass of the Z' of 700GeV and for the largest allowed coupling in the model, the values being higher for the 7TeV option. These polarizations translate to a deviation from the standard-model value of azimuthal asymmetry of up to about 4% (7%) for 14 (7) TeV LHC, whereas for the Tevatron, values as high as 12% are attained. For the 14TeV LHC with an integrated luminosity of 10 fb(-1), these numbers translate into a 3 sigma sensitivity over a large part of the range 500 less than or similar to M-Z' less than or similar to 1500GeV.

Minimal three-component SU(2) gadget for polarization optics

Two identities involving quarter-wave plates and half-wave plates are established. These are used to improve on an earlier gadget involving four wave plates leading to a new gadget involving just three plates, a half-wave plate and two quarter-wave plates, which can realize all SU(2) polarization transformations. This gadget is shown to involve the minimum number of quarter-wave and half-wave plates. The analysis leads to a decomposition theorem for SU (2) matrices in terms of factors which are symmetric fourth and eighth roots of the identity.

Influence of Inclination Angle and Machining Direction on Friction and Transfer Layer Formation

In the present investigation, unidirectional grinding marks were created on a set of steel plates. Sliding experiments were then conducted with the prepared steel plates using Al-Mg alloy pins and an inclined pin-on-plate sliding tester. The goals of the experiments were to ascertain the influence of inclination angle and grinding mark direction on friction and transfer layer formation during sliding contact. The inclination angle of the plate was held at 0.2 deg, 0.6 deg, 1 deg, 1.4 deg, 1.8 deg, 2.2 deg, and 2.6 deg in the tests. The pins were slid both perpendicular and parallel to the grinding marks direction. The experiments were conducted under both dry and lubricated conditions on each plate in an ambient environment. Results showed that the coefficient of friction and the formation of transfer layer depend on the grinding marks direction and inclination angle of the hard surfaces. For a given inclination angle, under both dry and lubricated conditions, the coefficient of friction and transfer layer formation were found to be greater when the pins slid perpendicular to the unidirectional grinding marks than when the pins slid parallel to the grinding marks. In addition, a stick-slip phenomenon was observed under lubricated conditions at the highest inclination angle for sliding perpendicular to the grinding marks direction. This phenomenon could be attributed to the extent of plane strain conditions taking place at the asperity level during sliding. DOI: 10.1115/1.4002604]

Polarization Changes of Radiation through Stimulated Raman Scattering

We study change in the polarization of electromagnetic waves due to the stimulated Raman scattering in a plasma. In this process an electromagnetic wave undergoes coherent scattering off an electron plasma wave. It is found that some of the observed polarization properties such as the rapid temporal variations, sense reversal, rotation of the plane of polarization, and change of nature of polarization in the case of pulsars and quasars could be accounted for through stimulated Raman scattering.

Top-spin analysis of new scalar and tensor interactions in e(+)e(-) collisions with beam polarization

We utilize top polarization in the process e(+)e(-) -> t (t) over bar at the International Linear Collider ( ILC) with transverse beam polarization to probe interactions of the scalar and tensor type beyond the standard model and to disentangle their individual contributions. Ninety percent confidence level limits on the interactions with realistic integrated luminosity are presented and are found to improve by an order of magnitude compared to the case when the spin of the top quark is not measured. Sensitivities of the order of a few times 10(-3) TeV-2 for real and imaginary parts of both scalar and tensor couplings at root s = 500 and 800 GeV with an integrated luminosity of 500 fb(-1) and completely polarized beams are shown to be possible. A powerful model-independent framework for inclusive measurements is employed to describe the spin-momentum correlations, and their C, P, and T properties are presented in a technical appendix.

Geometry and quadratic nonlinearity of charge transfer complexes in solution using depolarized hyper-Rayleigh scattering

We report large quadratic nonlinearity in a series of 1:1 molecular complexes between methyl substituted benzene donors and quinone acceptors in solution. The first hyperpolarizability, beta(HRS), which is very small for the individual components, becomes large by intermolecular charge transfer (CT) interaction between the donor and the acceptor in the complex. In addition, we have investigated the geometry of these CT complexes in solution using polarization resolved hyper-Rayleigh scattering (HRS). Using linearly (electric field vector along X direction) and circularly polarized incident light, respectively, we have measured two macroscopic depolarization ratios D = I-2 omega,I-X,I-X/I-2 omega,I-Z,I-X and D' = I-2 omega,I-X,I-C/I-2 omega,I-Z,I-C in the laboratory fixed XYZ frame by detecting the second harmonic scattered light in a polarization resolved fashion. The experimentally obtained first hyperpolarizability, beta(HRS), and the value of macroscopic depolarization ratios, D and D', are then matched with the theoretically deduced values from single and double configuration interaction calculations performed using the Zerner's intermediate neglect of differential overlap self-consistent reaction field technique. In solution, since several geometries are possible, we have carried out calculations by rotating the acceptor moiety around three different axes keeping the donor molecule fixed at an optimized geometry. These rotations give us the theoretical beta(HRS), D and D' values as a function of the geometry of the complex. The calculated beta(HRS), D, and D' values that closely match with the experimental values, give the dominant equilibrium geometry in solution. All the CT complexes between methyl benzenes and chloranil or 1,2-dichloro-4,5-dicyano-p-benzoquinone investigated here are found to have a slipped parallel stacking of the donors and the acceptors. Furthermore, the geometries are staggered and in some pairs, a twist angle as high as 30 degrees is observed. Thus, we have demonstrated in this paper that the polarization resolved HRS technique along with theoretical calculations can unravel the geometry of CT complexes in solution. (C) 2011 American Institute of Physics. doi:10.1063/1.3514922]