Fast detection of the magnetic easy axis on steel sheet using the continuous rotational Barkhausen method

The magnetic behaviour of most commercial ferromagnetic steels is usually anisotropic presenting a magnetic easy axis. Changes in the direction of this axis can be related to mechanical changes and anomalies that occur in the fabrication process. The present work describes a method that uses a device with permanent magnets to create a precise rotational magnetic field. The device measures continuous Magnetic Barkhausen Noise signals related to the angle of magnetization, in order to determine the direction of the macroscopic magnetic easy axis. It also offers the possibility of obtaining real time parameters that quantify the magnetic anisotropy of the sample. (C) 2011 Elsevier Ltd. All rights reserved.

A Homonuclear Rotational Echo Double-Resonance Method for Measuring Site-Resolved Distance Distributions in I=1/2 Spin Pairs, Clusters, and Multispin Systems

Deutsche Forschungsgemeinschaft [SFB 858]

Morphogenesis in guinea grass pastures under rotational grazing strategies

This study was conducted in order to evaluate the morphogenetic and structural characteristics of guinea grass cv. Mombasa under three post-grazing heights (intense - 30 cm, lenient - 50 cm and variable - 50 in spring-summer and 30 cm in autumn-winter) when sward light interception reached 95% during regrowth. Post-grazing heights were allocated to experimental units (0.25 ha) in a completely randomized block design with three replications. Post-grazing heights affected only leaf elongation rate and the number of live leaves. Pastures managed with variable post-grazing height showed higher leaf elongation rate in the summer of 2007. This management strategy also resulted in a higher number of live leaves. During the spring of 2006, plants showed lower leaf elongation rate, leaf appearance rate and number of live leaves, and greater phyllochron and leaf lifespan. In contrast, during the summer of 2007, the leaf appearance rate, leaf elongation rate, number of live leaves, and final leaf length were greater while phyllochron, stem elongation rate, and leaf senescence rate were lower. The management of the guinea grass cv. Mombasa with intense or variable post-grazing height throughout the year seems to represent an interesting management target, in terms of leaf appearance rate and number of live leaves.

Tiller population density and tillering dynamics in marandu palisade grass subjected to strategies of rotational stocking management and nitrogen fertilization

The objective of this experiment was to evaluate tiller population density and the dynamics of the tillering process in marandu palisade grass subjected to strategies of rotational stocking management and nitrogen fertilization. Treatments corresponded to combinations between two targets of pre-grazing conditions (sward surface height of 25 and 35 cm) and two rates of nitrogen application (50 and 200 kg ha-1 year-1), and were allocated to experimental units according to a 2 x 2 factorial arrangement in a randomised complete block design, with four replications. The following response variables were studied: initial (TPDi), intermediate (TPDm) and final (TPDf) tiller population density as well as the rates of tiller appearance (TAR) and death (TDR) and the tiller population stability index (SI). TPDi was similar to all treatments, with differences in tiller population density becoming more pronounced as the experiment progressed, resulting in larger TPDf on swards managed at 25 cm pre-grazing height. Tiller death was larger on swards managed at 35 cm, with differences in tiller appearance being recorded only from February 2010 onwards. Stability of tiller population was higher on swards managed at 25 cm pre-grazing height. Overall, there was no effect of nitrogen on the studied variables, and the most adequate grazing strategy corresponded to the pre-grazing height of 25 cm, regardless of the nitrogen application rate used.

Variable rotational line broadening in the Be star Achernar

Aims. The main theoretical problem for the formation of a Keplerian disk around Be stars is how angular momentum is supplied from the star to the disk, even more so since Be stars probably rotate somewhat subcritically. For instance, nonradial pulsation may transport angular momentum to the stellar surface until (part of) this excess supports the disk-formation/replenishment. The nearby Be star Achernar is presently building a new disk and o ers an excellent opportunity to observe this process from relatively close-up. Methods. Spectra from various sources and epochs are scrutinized to identify the salient stellar parameters characterizing the disk life cycle as defined by H emission. The variable strength of the non-radial pulsation is confirmed, but does not a ect the other results. Results. For the first time it is demonstrated that the photospheric line width does vary in a Be star, by as much as v sin i . 35 km However, unlike assumptions in which a photospheric spin-up accumulates during the diskless phase and then is released into the disk as it is fed, the apparent photospheric spin-up is positively correlated with the appearance of H line emission. The photospheric line widths and circumstellar emission increase together, and the apparent stellar rotation declines to the value at quiescence after the H line emission becomes undetectable

Rotational diffusion membrane and fluorescence anisotropy.

Structural properties of model membranes, such as lipid vesicles, may be investigated through the addition of fluorescent probes. After incorporation, the fluorescent molecules are excited with linearly polarized light and the fluorescence emission is depolarized due to translational as well as rotational diffusion during the lifetime of the excited state. The monitoring of emitted light is undertaken through the technique of time-resolved fluorescence: the intensity of the emitted light informs on fluorescence decay times, and the decay of the components of the emitted light yield rotational correlation times which inform on the fluidity of the medium. The fluorescent molecule DPH, of uniaxial symmetry, is rather hydrophobic and has collinear transition and emission moments. It has been used frequently as a probe for the monitoring of the fluidity of the lipid bilayer along the phase transition of the chains. The interpretation of experimental data requires models for localization of fluorescent molecules as well as for possible restrictions on their movement. In this study, we develop calculations for two models for uniaxial diffusion of fluorescent molecules, such as DPH, suggested in several articles in the literature. A zeroth order test model consists of a free randomly rotating dipole in a homogeneous solution, and serves as the basis for the study of the diffusion of models in anisotropic media. In the second model, we consider random rotations of emitting dipoles distributed within cones with their axes perpendicular to the vesicle spherical geometry. In the third model, the dipole rotates in the plane of the of bilayer spherical geometry, within a movement that might occur between the monolayers forming the bilayer. For each of the models analysed, two methods are used by us in order to analyse the rotational diffusion: (I) solution of the corresponding rotational diffusion equation for a single molecule, taking into account the boundary conditions imposed by the models, for the probability of the fluorescent molecule to be found with a given configuration at time t. Considering the distribution of molecules in the geometry proposed, we obtain the analytical expression for the fluorescence anisotropy, except for the cone geometry, for which the solution is obtained numerically; (II) numerical simulations of a restricted rotational random walk in the two geometries corresponding to the two models. The latter method may be very useful in the cases of low-symmetry geometries or of composed geometries.

Studies of pure rotational spectra of isolated molecules and molecular adducts using pulsed jet Fourier transform microwave (PJ-FTM) spectroscopy

This thesis focuses on studying molecular structure and internal dynamics by using pulsed jet Fourier transform microwave (PJ-FTMW) spectroscopy combined with theoretical calculations. Several kinds of interesting chemical problems are investigated by analyzing the MW spectra of the corresponding molecular systems. First, the general aspects of rotational spectroscopy are summarized, and then the basic theory on molecular rotation and experimental method are described briefly. ab initio and density function theory (DFT) calculations that used in this thesis to assist the assignment of rotational spectrum are also included. From chapter 3 to chapter 8, several molecular systems concerning different kind of general chemical problems are presented. In chapter 3, the conformation and internal motions of dimethyl sulfate are reported. The internal rotations of the two methyl groups split each rotational transition into several components line, allowing for the determination of accurate values of the V3 barrier height to internal rotation and of the orientation of the methyl groups with respect to the principal axis system. In chapter 4 and 5, the results concerning two kinds of carboxylic acid bi-molecules, formed via two strong hydrogen bonds, are presented. This kind of adduct is interesting also because a double proton transfer can easily take place, connecting either two equivalent or two non-equivalent molecular conformations. Chapter 6 concerns a medium strong hydrogen bonded molecular complex of alcohol with ether. The dimer of ethanol-dimethylether was chosen as the model system for this purpose. Chapter 7 focuses on weak halogen…H hydrogen bond interaction. The nature of O-H…F and C-H…Cl interaction has been discussed through analyzing the rotational spectra of CH3CHClF/H2O. In chapter 8, two molecular complexes concerning the halogen bond interaction are presented.

Non-Covalent Interaction: Revealed by Rotational Spectroscopy

The pulsed jet Fourier transform microwave spectroscopy have been applied to several molecular complexes involving H2O, freons, methane, carboxylic acids, and rare gas. The obtained results showcase the suitability of this technique for studying the intermolecular interactions. The rotational spectra of three water adducts of halogenated organic molecules, i.e. chlorotrifluoroethylene, isoflurane and alfa,alfa,alfa,-trifluoroanisole, have been investigated. It has been found that, the halogenation of the partner molecules definitely changes the way in which water will link to the partner molecule. Quadrupole hyperfine structures and/or the tunneling splittings have been observed in the rotational spectra of difluoromethane-dichloromethane, chlorotrifluorometane-fluoromethane, difluoromethane-formaldehyde and trifluoromethane-benzene. These features have been useful to describe their intermolecular interactions (weak hydrogen bonds or halogen bonds), and to size the potential energy surfaces of their internal motions. The rotational spectrum of pyridine-methane pointed out that methane prefers to locate above the ring and link to pyridine through a C-H•••π weak hydrogen bond, rather than the C-H•••n interaction. This behavior, typical of complexes of pyridine with rare gases, suggests classifying CH4, in relation to its ability to form molecular complexes with aromatic molecules, as a pseudo rare gas. The conformational equilibria of three bi-molecules of carboxylic acids, acrylic acid-trifluoroacetic acid, difluoroacetic acid-formic acid and acrylic acid-fluoroacetic acid have been studied. The increase of the hydrogen bond length upon H→D isotopic substitution (Ubbelohde effect) has been deduced from the elongation of the carboxylic carbons C•••C distance. The van der Waals complex tetrahydrofuran-krypton shows that the systematic doubling of the rotational lines has been attributed to the residual pseudo-rotation of tetrahydrofuran in the complex, based on the values of the Coriolis coupling constants, and on the type (mu_b) of the interstate transitions.

Contribution of Non-Covalent Interactions and Electronic Effects on the Conformational Landscape and Tautomeric Equilibria of Molecules and Molecular Complexes: Structural and Dynamical Data from Rotational Spectroscopy

This thesis concerns the study of complex conformational surfaces and tautomeric equilibria of molecules and molecular complexes by quantum chemical methods and rotational spectroscopy techniques. In particular, the focus of this research is on the effects of substitution and noncovalent interactions in determining the energies and geometries of different conformers, tautomers or molecular complexes. The Free-Jet Absorption Millimeter Wave spectroscopy and the Pulsed-Jet Fourier Transform Microwave spectroscopy have been applied to perform these studies and the obtained results showcase the suitability of these techniques for the study of conformational surfaces and intermolecular interactions. The series of investigations of selected medium-size molecules and complexes have shown how different instrumental setups can be used to obtain a variety of results on molecular properties. The systems studied, include molecules of biological interest such as anethole and molecules of astrophysical interest such as N-methylaminoethanol. Moreover halogenation effects have been investigated on halogen substituted tautomeric systems (5-chlorohydroxypyridine and 6-chlorohydroxypyridine), where it has shown that the position of the inserted halogen atom affects the prototropic equilibrium. As for fluorination effects, interesting results have been achieved investigating some small complexes where a molecule of water is used as a probe to reveal the changes on the electrostatic potential of different fluorinated compounds: 2-fluoropyridine, 3-fluoropyridine and penta-fluoropyridine. While in the case of the molecular complex between water and 2-fluoropyridine and 3-fluoropyridine the geometry of the complex with one water molecule is analogous to that of pyridine with the water molecule linked to the pyridine nitrogen, the case of pentafluoropyridine reveals the effect of perfluorination and the water oxygen points towards the positive center of the pyridine ring. Additional molecular adducts with a molecule of water have been analyzed (benzylamine-water and acrylic acid-water) in order to reveal the stabilizing driving forces that characterize these complexes.

Structures of Cage, Prism, and Book Isomers of Water Hexamer from Broadband Rotational Spectroscopy

Theory predicts the water hexamer to be the smallest water cluster with a three-dimensional hydrogen-bonding network as its minimum energy structure. There are several possible low-energy isomers, and calculations with different methods and basis sets assign them different relative stabilities. Previous experimental work has provided evidence for the cage, book, and cyclic isomers, but no experiment has identified multiple coexisting structures. Here, we report that broadband rotational spectroscopy in a pulsed supersonic expansion unambiguously identifies all three isomers; we determined their oxygen framework structures by means of oxygen-18–substituted water (H218O). Relative isomer populations at different expansion conditions establish that the cage isomer is the minimum energy structure. Rotational spectra consistent with predicted heptamer and nonamer structures have also been identified.

Added mass and wave radiation damping for flow-induced rotational vibrations of skinplates of hydraulic gates

One observed vibration mode for Tainter gate skinplates involves the bending of the skinplate about a horizontal nodal line. This vibration mode can be approximated as a streamwise rotational vibration about the horizontal nodal line. Such a streamwise rotational vibration of a Tainter gate skinplate must push away water from the portion of the skinplate rotating into the reservoir and draw water toward the gate over that portion of the skinplate receding from the reservoir. The induced pressure is termed the push-and-draw pressure. In the present paper, this push-and-draw pressure is analyzed using the potential theory developed for dissipative wave radiation problems. In the initial analysis, the usual circular-arc skinplate is replaced by a vertical, flat, rigid weir plate so that theoretical calculations can be undertaken. The theoretical push-and-draw pressure is used in the derivation of the non-dimensional equation of motion of the flow-induced rotational vibrations. Non-dimensionalization of the equation of motion permits the identification of the dimensionless equivalent added mass and the wave radiation damping coefficients. Free vibration tests of a vertical, flat, rigid weir plate model, both in air and in water, were performed to measure the equivalent added mass and the wave radiation damping coefficients. Experimental results compared favorably with the theoretical predictions, thus validating the theoretical analysis of the equivalent added mass and wave radiation damping coefficients as a prediction tool for flow-induced vibrations. Subsequently, the equation of motion of an inclined circular-arc skinplate was developed by incorporating a pressure correction coefficient, which permits empirical adaptation of the results from the hydrodynamic pressure analysis of the vertical, flat, rigid weir plate. Results from in-water free vibration tests on a 1/31-scale skinplate model of the Folsom Dam Tainter gate are used to demonstrate the utility of the equivalent added mass coefficient.

Broadband Fourier transform rotational spectroscopy for structure determination: The water heptamer

Over the recent years chirped-pulse, Fourier-transform microwave (CP-FTMW) spectrometers have chan- ged the scope of rotational spectroscopy. The broad frequency and large dynamic range make possible structural determinations in molecular systems of increasingly larger size from measurements of heavy atom (13C, 15N, 18O) isotopes recorded in natural abundance in the same spectrum as that of the parent isotopic species. The design of a broadband spectrometer operating in the 2–8 GHz frequency range with further improvements in sensitivity is presented. The current CP-FTMW spectrometer performance is benchmarked in the analyses of the rotational spectrum of the water heptamer, (H2O)7, in both 2– 8 GHz and 6–18 GHz frequency ranges. Two isomers of the water heptamer have been observed in a pulsed supersonic molecular expansion. High level ab initio structural searches were performed to pro- vide plausible low-energy candidates which were directly compared with accurate structures provided from broadband rotational spectra. The full substitution structure of the most stable species has been obtained through the analysis of all possible singly-substituted isotopologues (H218O and HDO), and a least-squares rm(1) geometry of the oxygen framework determined from 16 different isotopic species compares with the calculated O–O equilibrium distances at the 0.01 Å level.

Broadband Fourier transform rotational spectroscopy for structure determination: The water heptamer

Over the recent years chirped-pulse, Fourier-transform microwave (CP-FTMW) spectrometers have changed the scope of rotational spectroscopy. The broad frequency and large dynamic range make possible structural determinations in molecular systems of increasingly larger size from measurements of heavy atom (C-13, N-15, O-18) isotopes recorded in natural abundance in the same spectrum as that of the parent isotopic species. The design of a broadband spectrometer operating in the 2-8 GHz frequency range with further improvements in sensitivity is presented. The current CP-FTMW spectrometer performance is benchmarked in the analyses of the rotational spectrum of the water heptamer, (H2O)(7), in both 2-8 GHz and 6-18 GHz frequency ranges. Two isomers of the water heptamer have been observed in a pulsed supersonic molecular expansion. High level ab initio structural searches were performed to provide plausible low-energy candidates which were directly compared with accurate structures provided from broadband rotational spectra. The full substitution structure of the most stable species has been obtained through the analysis of all possible singly-substituted isotopologues ((H2O)-O-18 and HDO), and a least-squares r(m)((1)) geometry of the oxygen framework determined from 16 different isotopic species compares with the calculated O-O equilibrium distances at the 0.01 angstrom level. (C) 2013 Elsevier B.V. All rights reserved.