962 resultados para Rotation de Faraday


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The α→γ→α→β transitions of para-dichlorobenzene have been studied by employing infrared and n.q.r. spectroscopy as well as differential scanning calorimetry. The γ phase is associated with considerably higher values of some of the intramolecular vibration frequencies. The α→γ transition shows athermal nucleation behaviour as in martensitic transitions. Intermolecular vibration bands around 46 and 85 cm–1 present in γ and α phases disappear in the β phase. The α→β transition seems to be associated with some orientational disorder.

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Mössbauer and electrical resistivity measurements on Eu1–xSrxFeO3(0.0 < x[less-than-or-eq] 0.4) show the presence of a time-averaged electron configuration of Fe in these solids at T > TN. Variable range hopping arising from Anderson localization seems to occur at T < TN indicating that the electron hopping time in this regime is likely to be greater than 10–7 s. Mössbauer studies on Nd1–xSrxCoO3 show that in the Anderson localization regime, the hopping time is greater than 10–7 s in this system as well.

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The hydrolysis reactions of organometallic ruthenium(II) piano-stool complexes of the type Ru-II(eta(6)-cymene)(L)Cl](0/+) (1-5, where L = kappa(1)- or kappa(2)-1,1-bis(diphenylphosphino)methane,1,1bis-(diphenylphosphino)methane oxide, kappa(1)-mercaptobenzothiazole) have been studied using density functional theory at the B3LYP level. In addition to considering a syn attack in an associative fashion, where the nucleophile approaches from the same side as the leaving group, we have explored alternative paths such as an anti attack in an associative manner, where the nucleophile attacks from the opposite side of the leaving group. During the anti attack, an intermediate is formed and there is a coordination mode change of the arene ring from eta(6) to eta(2) along with its rotation. When the intermediate goes to the product, the arene ring slips back from eta(2) to eta(6) coordination. This coordinated movement of the arene ring makes the associative anti attack an accessible pathway for the substitution process. Our calculations predict very similar activation barriers for both syn and anti attacks. In the dissociative path, the rate-determining step is the generation of a coordinatively unsaturated 16-electron ruthenium species. This turns out to be viable once solvent effects are included. The large size of the ancillary ligands on Ru makes the dissociative process as favorable as the associative process. Activation energy calculations reveal that although the dissociative path is favorable for kappa(1) complexes, both dissociative and associative processes can have significant contribution to the hydrolysis reaction in kappa(2) complexes. Once activated by hydrolysis, these complexes react with guanine and adenine bases of DNA. The thermodynamic stabilities of complexes formed with the nucleobases are also presented.

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We study the vaporization and precipitation dynamics of a nanosilica encapsulated water droplet by levitating it acoustically and heating it with a CO2 laser. For all concentrations, we observe three phases: solvent evaporation, surface agglomeration, and precipitation leading to bowl or ring shaped structures. At higher concentrations, ring reorientation and rotation are seen consistently. The surface temperature from an infrared camera is seen to be dependent on the final geometrical shape of the droplet and its rotation induced by the acoustic field of the levitator. With nonuniform particle distribution, these structures can experience rupture which modifies the droplet rotational speed. (C) 2010 American Institute of Physics. doi:10.1063/1.3493178]

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13 C resonances of carbonyl and methyl groups in amides are shifted down-field on interaction with alkali and alkaline earth metal salts. The magnitude of the shift depends on the ionic potential of the cation. Ions like Li+ bind to the amide carbonyl group both in neat amide solutions as well as in concentrated salt solutions in water.

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Time-dependent models of collisionless stellar systems with harmonic potentials allowing for an essentially exact analytic description have recently been described. These include oscillating spheres and spheroids. This paper extends the analysis to time-dependent elliptic discs. Although restricted to two space dimensions, the systems are richer in that their parameters form a 10-dimensional phase space (in contrast to six for the earlier models). Apart from total energy and angular momentum, two additional conserved quantities emerge naturally. These can be chosen as the areas of extremal sections of the ellipsoidal region of phase space occupied by the system (their product gives the conserved volume). The present paper describes the construction of these models. An application to a tidal encounter is given which allows one to go beyond the impulse approximation and demonstrates the effects of rotation of the perturbed system on energy and angular-momentum transfer. The angular-momentum transfer is shown to scale inversely as the cube of the encounter velocity for an initial configuration of the perturbed galaxy with zero quadrupole moment.

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This study is focused on the development and evaluation of ion mobility instrumentation with various atmospheric pressure ionization techniques and includes the following work. First, a high-resolution drift tube ion mobility spectrometer (IMS), coupled with a commercial triple quadrupole mass spectrometer (MS), was developed. This drift tube IMS is compatible with the front-end of commercial Sciex mass spectrometers (e.g., Sciex API-300, 365, and 3000) and also allows easy (only minor modifications are needed) installation between the original atmospheric pressure ion source and the triple quadrupole mass spectrometer. Performance haracteristics (e.g.,resolving power, detection limit, transmission efficiency of ions) of this IMS-MS instrument were evaluated. Development of the IMS-MS instrument also led to a study where a proposal was made that tetraalkylammonium ions can be used as chemical standards for ESI-IMS. Second, the same drift tube design was also used to build a standalone ion mobility spectrometer equipped with a Faraday plate detector. For this highresolution (resolving power about 100 shown) IMS device, a multi-ion source platform was built, which allows the use of a range of atmospheric pressure ionization methods, such as: corona discharge chemical ionization (CD-APCI), atmospheric pressure photoionization (APPI), and radioactive atmospheric pressure chemical ionization (R-APCI). The multi-ion source platform provides easy switching between ionization methods and both positive and negative ionization modes can be used. Third, a simple desorpion/ionization on silicon (DIOS) ion source set-up for use with the developed IMS and IMS-MS instruments was built and its operation demonstrated. Fourth, a prototype of a commercial aspiration-type ion mobility spectrometer was mounted in front of a commercial triple quadrupole mass spectrometer. The set-up, which is simple, easy to install, and requires no major modifications to the MS, provides the possibility of gathering fundamental information about aspiration mobility spectrometry.

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Working under the hypothesis that magnetic flux in the sun is generated at the bottom of the convection zone, Choudhuri and Gilman (1987; Astrophys. J. 316, 788) found that a magnetic flux tube symmetric around the rotation axis, when released at the bottom of the convection zone, gets deflected by the Coriolis force and tends to move parallel to the rotation axis as it rises in the convection zone. As a result, all the flux emerges at rather high latitudes and the flux observed at the typical sunspot latitudes remains unexplained. Choudhuri (1989; Solar Physics, in press) finds that non-axisymmetric perturbations too cannot subdue the Coriolis force. In this paper, we no longer treat the convection zone to be passive as in the previous papers, but we consider the role of turbulence in the convection zone in inhibiting the Coriolis force. The interaction of the flux tubes with the turbulence is treated in a phenomenological way as follows: (1) Large scale turbulence on the scale of giant cells can physically drag the tubes outwards, thus pulling the flux towards lower latitudes by dominating over the Coriolis force. (2) Small scale turbulence of the size of the tubes can exchange angular momentum with the tube, thus suppressing the growth of the Coriolis force and making the tubes emerge at lower latitudes. Numerical simulations show that the giant cells can drag the tubes and make them emerge at lower latitufes only if the velocities within the giant cells are unrealistically large of if the radii of the flux tubes are as small as 10 km. However, small scale turbulence can successfully suppress the growth of the Coriolis force if the tubes have radii smaller than about 300 km which may not be unreasonable. Such flux tubes can then emerge at low latitudes where sunspots are seen.

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A model for coalescence efficiency of two drops embedded in an eddy has been developed. Unlike the other models which consider only head-on collisions, the model considers the droplets to approach at an arbitrary angle. The drop pair is permitted to undergo rotation while they approach each other. For coalescence to occur, the drops are assumed to approach each other under a squeezing force acting over the life time of eddy but which can vary with time depending upon the angle of approach. The model accounts for the deformation of tip regions of the approaching drops and, describes the rupture of the intervening film, based on stability considerations while film drainage is continuing under the combined influence of the hydrodynamic and van der Waals forces. The coalescence efficiency is defined as the ratio of the range of angles resulting in coalescence to the total range of all possible approach angles. The model not only reconciles the contradictory predictions made by the earlier models based on similar framework but also brings out the important role of dispersed-phase viscosity. It further predicts that the dispersions involving pure phases can be stabilized at high rps values. Apart from explaining the hitherto unexplained experimental data of Konno et al. qualitatively, the model also offers an alternate explanation for the interesting observations of Shinnar.

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We report a comparative modified neglect of diatomic overlap (MNDO), Austin method one (AM1), and parametric method 3 (PM3) study of trans‐stilbene (tS) in its ground, excited (singlet and triplet), and ionic (positive and negative polarons and bipolarons) states. We have also calculated the barrier for ring rotation about the backbone single bond. Our results show that PM3 geometries are superior to MNDO and AM1, at least for tS. PM3 predicts, in contrast with MNDO, AM1 and even ab initio 3‐21G, a coplanar structure for tS, in accordance with recent experimental data. Singlet and triplet energies obtained from heats of formation are in surprisingly good agreement with experimental data.

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Suomen maatalousmaihin kertynyttä fosforia hyödynnetään tehottomasti, ja samalla muokkauskerroksen suuri fosforimäärä on alttiina huuhtoutumiselle. Arbuskelimykorritsaa (AM) hyödyntämällä on mahdollista tehostaa viljelykasvin fosforinottoa ja kasvua, ja siten vähentää fosforin huuhtoutumista. Tämän tutkielman tavoitteena oli selvittää mykorritsan vaikutus kasvin kasvuun ja fosforinottoon karjanlantalannoituksella mineraalilannoitukseen verrattuna sekä näiden lannoitusten pitkäaikaisvaikutusta AM-sieniyhteisöihin. Jotta lannoituskäytäntöjen vaikutus mykorritsaan voitiin suhteuttaa muihin maan laatutekijöihin, näiden käytäntöjen vaikutus myös satomääriin sekä muihin maan laatumittareihin arvioitiin. Pitkäaikainen kenttäkoe perustettiin kolmelle paikkakunnalle Pohjois-Ruotsissa vuosina 1965–66. Kuusivuotinen viljelykierto koostui joko viisivuotisesta nurmesta ja ohrasta tai ohramonokulttuurista. Lannoituskäsittelyt 32-vuoden ajan olivat suositusten mukainen (NPK) ja edelliseen nähden kaksinkertainen (2NPK) mineraalilannoitus sekä karjanlantalannoitus (KL), jonka ravinnemäärä vastasi NPK -käsittelyä. Kolmen lannoituskäsittelyn vaikutusta mykorritsan tehokkuuteen kasvin kasvun ja fosforiravitsemuksen näkökulmasta tutkittiin astiakokeissa. Mykorritsasieniyhteisöjen toiminnallisten erojen selvittämiseksi tehtiin takaisin- ja ristiinsiirrostuskoe. (5 v-%) steriloitua maanäytettä NPK- ja KL -käsittelyistä siirrostettiin käsittelemättömiin maanäytteisiin, jotka olivat samoista lannoituskäsittelyistä. Mykorritsan positiivinen vaikutus kasvin kasvuun ja fosforiravitsemukseen oli suurin kun käytettiin karjanlantaa. NPK ja 2NPK -käsittelyiden välillä ei havaittu eroja. Takaisin- ja ristiinsiirrostuskokeessa ei ollut tilastollisesti merkitseviä eroja. Nurmi- ja ohrasadot olivat suurimmat kun mineraalilannoitetta annettiin suosituksiin nähden kaksinkertainen määrä. Satomäärät olivat yhtä suuret tai suuremmat kun käytettiin karjanlantaa NPK –lannoituksen sijaan. Karjanlantakäsittely lisäsi maaperän kokonaishiili- ja kokonaistyppipitoisuutta verrattuna NPK -käsittelyyn, joka sisälsi saman määrän ravinteita. Samalla huuhtoutumiselle altis liukoisen fosforin pitoisuus säilyi alhaisella tasolla. Karjanlanta edisti mykorritsan toimintaedellytyksiä, ja siksi mykorritsasta saatua hyötyä fosforinotossa ja kasvuvaikutuksena mineraalilannoitteisiin verrattuna, mutta se ei vaikuttanut mykorritsasieniyhteisön toiminnallisiin ominaisuuksiin. Karjanlantalannoitus paransi mitattuja maan ominaisuuksia kokonaisuudessaan, eikä se vähentänyt satoja.

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The problem of estimating the three-dimensional rotational parameters of a rigid body from its monocular image data has been considered using the method of moment invariants. Second- and third-order moment invariants are used to construct the feature vector for the scale and orientation independent identification of the camera view axis direction in the body-fixed reference frame. The camera rotation angle about the view axis is derived from second-order central moments. The relative attitude of the rigid body is then expressed in terms of quaternion parameters to model the outputs of a video sensor in attitude control simulations. Experimental results and simulation outputs are presented using the mathematical model of a spacecraft.

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Both semiempirical and ab initio calculations are reported for conformational studies of a series of alpha-substituted acetones CH3COCH2XCH3 where X = CH2, O or S and of phenacyl sulfide PhCOCH2SCH3. For conformational studies in the lowest triplet state of these molecules, the MINDO/3 method was employed in the unrestricted Hartree-Fock frame. Results reveal that rotation around a bond alpha to the carbonyl group is more favourable than that around the beta bond. The preferred conformations in the lowest triplet state are nearly the same as in the ground state.

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Context. Turbulent fluxes of angular momentum and heat due to rotationally affected convection play a key role in determining differential rotation of stars. Aims. We compute turbulent angular momentum and heat transport as functions of the rotation rate from stratified convection. We compare results from spherical and Cartesian models in the same parameter regime in order to study whether restricted geometry introduces artefacts into the results. Methods. We employ direct numerical simulations of turbulent convection in spherical and Cartesian geometries. In order to alleviate the computational cost in the spherical runs and to reach as high spatial resolution as possible, we model only parts of the latitude and longitude. The rotational influence, measured by the Coriolis number or inverse Rossby number, is varied from zero to roughly seven, which is the regime that is likely to be realised in the solar convection zone. Cartesian simulations are performed in overlapping parameter regimes. Results. For slow rotation we find that the radial and latitudinal turbulent angular momentum fluxes are directed inward and equatorward, respectively. In the rapid rotation regime the radial flux changes sign in accordance with earlier numerical results, but in contradiction with theory. The latitudinal flux remains mostly equatorward and develops a maximum close to the equator. In Cartesian simulations this peak can be explained by the strong 'banana cells'. Their effect in the spherical case does not appear to be as large. The latitudinal heat flux is mostly equatorward for slow rotation but changes sign for rapid rotation. Longitudinal heat flux is always in the retrograde direction. The rotation profiles vary from anti-solar (slow equator) for slow and intermediate rotation to solar-like (fast equator) for rapid rotation. The solar-like profiles are dominated by the Taylor-Proudman balance.

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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.