Estudos de acoplamento spin-órbita em dinâmica do sistema solar

Pós-graduação em Física - FEG

Experimental and Theoretical Study of the OH Vibrational Spectra and Overtone Chemistry of Gas-Phase Vinylacetic Acid

In this study we present the gas-phase vibrational spectrum of vinylacetic acid with a focus on the ν = 1−5 vibrational states of the OH stretching transitions. Cross sections for ν = 1, 2, 4 and 5 of the OH stretching vibrational transitions are derived on the basis of the vapor pressure data obtained for vinylacetic acid. Ab initio calculations are used to assist in the band assignments of the experimental spectra, and to determine the threshold for the decarboxylation of vinylacetic acid. When compared to the theoretical energy barrier to decarboxylation, it is found that the νOH = 4 transition with thermal excitation of low frequency modes or rotational motion and νOH = 5 transitions have sufficient energy for the reaction to proceed following overtone excitation.

Simulation of Freight Trains Equipped with Partially Filled Tank Containers and Related Resonance Phenomenon

To study the fluid motion-vehicle dynamics interaction, a model of four, liquid filled two-axle container freight wagons was set up. The railway vehicle has been modelled as a multi-body system (MBS). To include fluid sloshing, an equivalent mechanical model has been developed and incorporated. The influence of several factors has been studied in computer simulations, such as track defects, curve negotiation, train velocity, wheel wear, liquid and solid wagonload, and container baffles. SIMPACK has been used for MBS analysis, and ANSYS for liquid sloshing modelling and equivalent mechanical systems validation. Acceleration and braking manoeuvres of the freight train set the liquid cargo into motion. This longitudinal sloshing motion of the fluid cargo inside the tanks initiated a swinging motion of some components of the coupling gear. The coupling gear consists of UIC standard traction hooks and coupling screws that are located between buffers. One of the coupling screws is placed in the traction hook of the opposite wagon thus joining the two wagons, whereas the unused coupling screw rests on a hanger. Simulation results showed that, for certain combinations of type of liquid, filling level and container dimensions, the liquid cargo could provoke an undesirable, although not hazardous, release of the unused coupling screw from its hanger. The coupling screw's release was especially obtained when a period of acceleration was followed by an abrupt braking manoeuvre at 1 m/s2. It was shown that a resonance effect between the liquid's oscillation and the coupling screw's rotary motion could be the reason for the coupling screw's undesired release. Possible solutions to avoid the phenomenon are given.Acceleration and braking manoeuvres of the freight train set the liquid cargo into motion. This longitudinal sloshing motion of the fluid cargo inside the tanks initiated a swinging motion of some components of the coupling gear. The coupling gear consists of UIC standard traction hooks and coupling screws that are located between buffers. One of the coupling screws is placed in the traction hook of the opposite wagon thus joining the two wagons, whereas the unused coupling screw rests on a hanger. This paper reports on a study of the fluid motion-train vehicle dynamics interaction. In the study, a model of four, liquid-filled two-axle container freight wagons was developed. The railway vehicle has been modeled as a multi-body system (MBS). To include fluid sloshing, an equivalent mechanical model has been developed and incorporated. The influence of several factors has been studied in computer simulations, such as track defects, curve negotiation, train velocity, wheel wear, liquid and solid wagonload, and container baffles. A simulation program was used for MBS analysis, and a finite element analysis program was used for liquid sloshing modeling and equivalent mechanical systems validation. Acceleration and braking maneuvers of the freight train set the liquid cargo into motion. This longitudinal sloshing motion of the fluid cargo inside the tanks initiated a swinging motion of some components of the coupling gear. Simulation results showed that, for certain combinations of type of liquid, filling level and container dimensions, the liquid cargo could provoke an undesirable, although not hazardous, release of an unused coupling screw from its hanger. It was shown that a resonance effect between the liquid's oscillation and the coupling screw's rotary motion could be the reason for the coupling screw's undesired release. Solutions are suggested to avoid the resonance problem, and directions for future research are given.

Technical developments for computed tomography on the CENBG nanobeam line

The use of ion microbeams as probes for computedtomography has proven to be a powerful tool for the three-dimensional characterization of specimens a few tens of micrometers in size. Compared to other types of probes, the main advantage is that quantitative information about mass density and composition can be obtained directly, using specific reconstruction codes. At the Centre d’Etudes Nucléaires de Bordeaux Gradignan (CENBG), this technique was initially developed for applications in cellular biology. However, the observation of the cell ultrastructure requires a sub-micron resolution. The construction of the nanobeamline at the Applications Interdisciplinaires des Faisceaux d’Ions en Region Aquitaine (AIFIRA) irradiation facility has opened new perspectives for such applications. The implementation of computedtomography on the nanobeamline of CENBG has required a careful design of the analysis chamber, especially microscopes for precise sample visualization, and detectors for scanning transmission ion microscopy (STIM) and for particle induced X-ray emission (PIXE). The sample can be precisely positioned in the three directions X, Y, Z and a stepper motor coupled to a goniometer ensures the rotational motion. First images of 3D tomography were obtained on a reference sample containing microspheres of certified diameter, showing the good stability of the beam and the sample stage, and the precision of the motion.

Stability analysis of a free falling pararotor

The pararotor is a decelerator device based on the autorotation of a rotating wing. When it is dropped, it generates an aerodynamic force parallel to the main motion direction, acting as a decelerating force. In this paper, the rotational motion equations are shown for the vertical flight without any lateral wind component and some simplifying assumptions are introduced to obtain analytic solutions of the motion. First, the equilibrium state is obtained as a function of the main parameters. Then the equilibrium stability is analyzed. The motion stability depends on two nondimensional parameters, which contain geometric, inertia, and aerodynamic characteristics of the device. Based on these two parameters a stability diagram can be defined. Some stability regions with different types of stability trajectories (nodes, spirals, focuses) can be identified for spinning motion around axes close to the major, minor, and intermediate principal axes. It is found that the blades contribute to stability in a case of spin around the intermediate principal inertia axis, which is otherwise unstable. Subsequently, the equations for determining the angles of nutation and spin of the body are obtained, thus defining the orientation of the body for a stationary motion and the parameters on which that position depends.

A proposta (i)modesta de Berkeley. Um mundo sem matéria

Berkeley’s general tenet about immaterialism is presented and discussed. I examined apart the several theses that concur to the immaterialist theory. After that, the general argument is presented and discussed. In particular, I stress Berkeley’s assumption that a world without matter and a world with matter would be indistinguishable from the point of view of (i) the content of perceptions, (ii) natural science (viz. Newtonian mechanics). I stress that this assumption depends on a relative account of circular motion, generating the centrifugal forces, as Newton shows in his bucket experiment. In spite of the efforts by Leibniz and Huygens, such a relative account of rotational motion was never presented. So the thesis about the scientific and perceptual identity between worlds with and without matter remains a simple case of wishful thinking in need for a justification.

Evaluation of the sonically induced narrowing of nuclear magnetic resonance spectra of solids

The Nuclear Magnetic Resonance (NMR) spectra of liquids contain a wealth of quantitative information that may be derived, for instance, from chemical shifts and spin-spin couplings. The available information depends on the incoherent rapid molecular motion that causes complicating effects present in the solid state to average to zero. Whereas liquid state NMR spectra show narrow lines, the corresponding NMR spectra from the solid state are normally composed of exceedingly broad resonance lines due to highly restricted molecular motion. It is, therefore, difficult to obtain directly as detailed information from the spectra of solids as from those derived from the liquid state. Studies on a new technique (SINNMR, the sonically induced narrowing of the NMR spectra of solids) to remove line broadening effects in the NMR spectra of the solid state are reported within this thesis. SINNMR involves narrowing the NMR absorptions from solid particles by irradiating them with ultrasound when they are suspended in a support liquid. It is proposed that ultrasound induces incoherent motion of the suspended particles, producing motional characteristics of the particles similar to those of rather large molecules. The first report of apparently successful experiments involving SINNMR[1] emphasised both the irreproducibility of the technique and the uncertainty regarding its true origin. If SINNMR can be made reproducible and the effect definitively attributed to the sonically induced incoherent motional averaging of particles, the technique could offer a simple alternative to the now classical magic-angle spinning (MAS) NMR[2] and the recently reported dynamic angle spinning (DAS)[3] and double rotation (DOR)[4] techniques. Evidence is presented in this thesis to support the proposal that ultrasound may be used to narrow the NMR spectral resonances from solids by inducing incoherent motion of particles suspended in support liquids and, additionally, for some solids, by inducing rotational motion of molecular constituents in the lattices of solids. Successful SINNMR line narrowing using 20 kHz ultrasound is reported for a variety of samples: including trisodium orthophosphate, polytetrafluoroethylene and aluminium alloys. Investigations of SINNMR line narrowing in trisodium phosphate have revealed the relationship between ultrasonic power, particle size and support liquid density for the production of optimum SINNMR conditions. It is also proposed that the incoherent motion of particles induced by 20 kHz ultrasound can originate from interactions between acoustically induced cavitation microjets and particles.

NMR spectroscopy in the presence of ultrasound and other perturbations

The work described in this thesis has been concerned with exploring the potential uses of ultrasound in Nuclear Magnetic Resonance (NMR) spectroscopy, The NMR spectra of liquids provide detailed structural information that may be deduced from the chemical shifts and spin-spin coupling, that are evident in the narrow resonances, arising from some of the nuclear broadening interactions being reduced to zero. In the solid state, all of the nuclear broadening interactions are present and broad lines in the NMR spectrum are observed. Current techniques employed to reduce the line widths in solids are based on coherent averaging techniques such as MAS NMR1,2 which can remove first order interactions. Recently DOR3 and DAS4 have become available to remove higher order interactions. SINNMR (Sonically Induced Narrowing of the NMR spectra of solids) has been reported by Homer et al5 and developed by Homer and Howard6 to reduce the line widths of solids. The basis of their work is the proposal that a colloidal suspension of solid particles can be made to move like large molecules by using ultrasonic agitation. The advantage of the technique is that the particles move incoherently removing all of the nuclear interactions responsible for broad lines. This thesis describes work on the extension of SINNMR by showing that the line width of 27AI and 11B for the glass Na20/B203/AI203 can be reduced by placing solid particles in a colloidal suspension. Further line width reduction is possible by applying ultrasound, at 2 MHz, of sufficient intensity. It is proposed that a cavitation field is responsible for imparting sufficient rotational motion to the solid particles to partially average the nuclear interactions responsible for broad lines. Rapid stirring of the colloidal suspension generates turbulent flow, however, the motion is insufficient to narrow the line widths for 27AI in the glass. Investigations of sonochemical reactions for in situ rate measurements by NMR have been made. 8y using the Weissler reaction7, it has been shown that ultrasonic cavitation is possible up to 10MHz. Preliminary studies have been carried out into the rate of ultrasonic polymerisation of methylmethacrylate by NMR. Long range order in liquid crystals can imposed when they are aligned in the presence a magnetic field. The degree of alignment can be monitored by NMR using, for example a deuterated solute added to the liquid crystal8. Ultrasonic streaming can then be employed to deflect the directors of the liquid crystal from their equilibrium position, resulting in a change In the NMR spectrum. The angle of deflection has been found for the thermotropic liquid crystal (I35) to be ca, 35° and for the lyotropic (ZLI-1167) to be ca, 20°, Mechanical stirring can used to re- orientate the liquid crystal but was found to give a smaller deflection, In a separate study, that did not use ultrasound, it has been found that the signal to noise ratio of 13C NMR signals can be enhanced by rapidly stirring a Iiquid. Accelerating the diffusion of nuclei out of the coil region enables M0 to be re-established more rapidly than the normal relaxation process. This allows the pulse repetition rate to be reduced without saturating the spin system. The influence of varying the relaxation delay, acquisition time and inter-pulse delay have been studied and parameters optimised. By studying cholesterol the technique was found to be most effective for nuclei with long relaxation times, such as quaternary carbon sites. Key Worde: NMR, Ulf.rasciund, 1,.lqi.fi!:l cryllltalt!h SCll1C1otlemlstryl I!r1hano~d algnflllf

Bródy András gazdaságiciklus-elmélete (András Bródy's theory of economic cycles)

Bródy András kutatásainak egyik központi témaköre a gazdasági mozgás vizsgálata volt. Írásunkban Bródy elméletét kívánjuk röviden áttekinteni és összefoglalni. A termelés sokszektoros leírása egyben árelméletét (értékelméletét, méréselméletét) is keretbe foglalja. Ebben a keretben a gazdasági mozgás összetett ingadozása technológiai alapon elemezhető. Bródy megközelítésében a gazdasági ciklust nem külső megrázkódások magyarázzák, hanem a termelési rendszer belső arányai és kapcsolatai. A termelési struktúrát az árak és a volumenek egyformán alakítják, ezek között nincsen kitüntetett vagy domináns tényező. Az árak és a volumenek a köztük lévő duális kapcsolatban alakulnak ki. A gazdaság mozgásegyenleteit technológiai mérlegösszefüggések, valamint a piaci csere útján a gazdaságban újraelosztásra (újratermelésre) kerülő termékek felhasználása és az eszközlekötés változása írja le. Az így meghatározott mozgásegyenletek a gazdaság természetes mozgását ciklusmozgás alakjában írják le. A technológia vagy az értékviszonyok megváltozása (sokkok) a gazdaság ciklikus mozgásának megváltozásában tükröződik. Bródy munkáiban technológiai megalapozást nyer a történelemből ismert számos jellegzetes gazdasági ciklus. / === / Economic motion and dynamics are at the heart of Andras Brody's creative output. This paper attempts a bird's-eye view of his theory of economic cycles. Brody's multi-sector modelling of production has provided a framework for price theory (the theory of value and measurement). His theory of economic motion with cyclical characteristics is technology driven. It argues that the complex web of economic cycles is determined by the proportions and interrelationships of the system of production, not by arbitrary external shocks. The structure's behaviour are driven by prices and proportions, with the duality of prices and proportions as a dominant feature. These are features in common with the Leontief models, which Brody extended to economic cycles. Brody saw economic cycles as natural motions of economic systems with accumulated assets (time lags) and market exchange of goods (demand and supply adjustment). Changes in technology or valuations (shocks) are reflected in changing patterns of motion. His model of the economy is a fine instrument that enabled him to show how the technological parameters of its system determine the frequency and other characteristics of various economic cycles identified in economic history.

Reconstructability of 3-Dimensional Upper Ocean Circulation from SWOT Sea Surface Height Measurements

Utilizing the framework of effective surface quasi-geostrophic (eSQG) theory, we explored the potential of reconstructing the 3D upper ocean circulation structures, including the balanced vertical velocity (w) field, from high-resolution sea surface height (SSH) data of the planned SWOT satellite mission. Specifically, we utilized the 1/30°, submesoscale-resolving, OFES model output and subjected it through the SWOT simulator that generates the along-swath SSH data with expected measurement errors. Focusing on the Kuroshio Extension region in the North Pacific where regional Rossby numbers range from 0.22 to 0.32, we found that the eSQG dynamics constitutes an effective framework for reconstructing the 3D upper ocean circulation field. Using the modeled SSH data as input, the eSQG-reconstructed relative vorticity (ζ) and w fields are found to reach a correlation of 0.7–0.9 and 0.6–0.7, respectively, in the 1,000m upper ocean when compared to the original model output. Degradation due to the SWOT sampling and measurement errors in the input SSH data for the ζ and w reconstructions is found to be moderate, 5–25% for the 3D ζ field and 15-35% for the 3D w field. There exists a tendency for this degradation ratio to decrease in regions where the regional eddy variability (or Rossby number) increases.

Chiral symmetry analysis and rigid rotational invariance for the lattice dynamics of single-wall carbon nanotubes

We provide a detailed expression of the vibrational potential for the lattice dynamics of single-wall carbon nanotubes (SWCNT's) satisfying the requirements of the exact rigid translational as well as rotational symmetries, which is a nontrivial generalization of the valence force model for the planar graphene sheet. With the model, the low-frequency behavior of the dispersion of the acoustic modes as well as the flexure mode can be precisely calculated. Based upon a comprehensive chiral symmetry analysis, the calculated mode frequencies (including all the Raman- and infrared-active modes), velocities of acoustic modes, and the polarization vectors are systematically fitted in terms of the chiral angle and radius, where the restrictions of various symmetry operations of SWCNT's are fulfilled.

On the motion of points constrained and resisted, and on the motion of a rigid body : the second part a new edition of a Treatise on dynamics.

Mode of access: Internet.

Self-consistent microscopic treatment of the effects of self-motion of the probe on ionic and dipolar solvation dynamics

A simple but self-consistent microscopic theory for the time dependent solvation energy of both ions and dipoles is presented which includes, for the first time, the details of the self-motion of the probe on its own solvation dynamics. The theory leads to several interesting predictions. The most important of them is that, for dipolar solvation, both the rotational and the translational motions of the dipolar solute probe can significantly accelerate the rate of solvation. In addition, the rotational self-motion of the solute can also give rise to an additional mechanism of nonexponentiality in solvation time correlation functions in otherwise slow liquids. A comparison between the present theoretical predictions and the recent experimental studies of Maroncelli et al. on solvation dynamics of aniline in l-propanol seems to indicate that the said experiments have missed the initial solvent response up to about 45 ps. After mapping the experimental results on the redefined time scale, the theoretical results can explain the experimental results for solvation of aniline in 1-propanol very well. For ionic solvation, the translational motion is significant for light solutes only. For example, for Li+ in water, translational motion speeds up the solvation by about 20%. The present theory demonstrates that in dipolar solvation the partial quenching of the self-motion due to the presence of specific solute-solvent interactions (such as H-bonding) may lead to a much slower solvation than that when the self-motion is present. This point has been discussed. In addition, we present the theoretical results for solvation of aniline in propylene carbonate, Here, the solvation is predicted to be complete within 15-20 ps.

Effect of orientational motion of mobile chromophores on the dynamics of Forster energy transfer in polymers

Brownian dynamics (BD) simulations have been carried out to explore the effects of the orientational motion of the donor-acceptor (D-A) chromophore pair on the Forster energy transfer between the D-A pair embedded in a polymer chain in solution. It is found that the usually employed orientational averaging (that is, replacing the orientational factor, kappa, by kappa (2) = 2/3) may lead to an error in the estimation of the rate of the reaction by about 20%. In the limit of slow orientational relaxation, the preaveraging of the orientational factor leads to an overestimation of the rate, while in the opposite limit of very fast orientational relaxation, the usual scheme underestimates the rate. The latter results from an interesting interplay between reaction and diffusion. On the other hand, when one of the chromophores is fixed, the preaveraged rate is found to be fairly reliable if the rotational relaxation of the chromophore is sufficiently fast. The present study also reveals a power law dependence of the FRET rate on the chain length (rate proportional to N- alpha, with alpha approximate to 2.6).