Zonal-mean dynamics of extended recoveries from stratospheric sudden warmings

The recovery of the Arctic polar vortex following stratospheric sudden warmings is found to take upward of 3 months in a particular subset of cases, termed here polar-night jet oscillation (PJO) events. The anomalous zonal-mean circulation above the pole during this recovery is characterized by a persistently warm lower stratosphere, and above this a cold midstratosphere and anomalously high stratopause, which descends as the event unfolds. Composites of these events in the Canadian Middle Atmosphere Model show the persistence of the lower-stratospheric anomaly is a result of strongly suppressed wave driving and weak radiative cooling at these heights. The upper-stratospheric and lower-mesospheric anomalies are driven immediately following the warming by anomalous planetary-scale eddies, following which, anomalous parameterized nonorographic and orographic gravity waves play an important role. These details are found to be robust for PJO events (as opposed to sudden warmings in general) in that many details of individual PJO events match the composite mean. Azonal-mean quasigeostrophic model on the sphere is shown to reproduce the response to the thermal and mechanical forcings produced during a PJO event. The former is well approximated by Newtonian cooling. The response can thus be considered as a transient approach to the steady-state, downward control limit. In this context, the time scale of the lower-stratospheric anomaly is determined by the transient, radiative response to the extended absence of wave driving. The extent to which the dynamics of the wave-driven descent of the stratopause can be considered analogous to the descending phases of the quasi-biennial oscillation (QBO) is also discussed.

Thermodynamics/dynamics coupling in weakly compressible turbulent stratified fluids

In traditional and geophysical fluid dynamics, it is common to describe stratified turbulent fluid flows with low Mach number and small relative density variations by means of the incompressible Boussinesq approximation. Although such an approximation is often interpreted as decoupling the thermodynamics from the dynamics, this paper reviews recent results and derive new ones that show that the reality is actually more subtle and complex when diabatic effects and a nonlinear equation of state are retained. Such an analysis reveals indeed: (1) that the compressible work of expansion/contraction remains of comparable importance as the mechanical energy conversions in contrast to what is usually assumed; (2) in a Boussinesq fluid, compressible effects occur in the guise of changes in gravitational potential energy due to density changes. This makes it possible to construct a fully consistent description of the thermodynamics of incompressible fluids for an arbitrary nonlinear equation of state; (3) rigorous methods based on using the available potential energy and potential enthalpy budgets can be used to quantify the work of expansion/contraction B in steady and transient flows, which reveals that B is predominantly controlled by molecular diffusive effects, and act as a significant sink of kinetic energy.

Dipole polarizability and Rayleigh light scattering by the hydrated electron

Assuming the existence of a confined state of the electron in bulk water the polarizability of the hydrated electron is analyzed. Statistically uncorrelated supermolecular structures composed of seven water molecules (first solvation shell) with an extra electron were extracted from classical Monte Carlo simulation and used in quantum mechanical second-order Moller-Plesset calculations. It is found that the bound excess electron contributes with 274 a.u. to the total dipole polarizability of 345 a.u. for (H(2)O)(7)(-). From the calculated polarizabilities the Rayleigh elastic light scattering properties are inferred and found to considerably enhance activity and light depolarization. (C) 2009 Elsevier B.V. All rights reserved.

A Multitechnique Study of Structure and Dynamics of Polyfluorene Cast Films and the Influence on Their Photoluminescence

This article describes the microstructure and dynamics in the solid state of polyfluorene-based polymers, poly(9,)-dioctylfluorenyl-2,7-diyl) (PFO), a semicrystalline polymer, and poly [(9,9-dioctyl- 2,7-divinylene-fluorenylene)-alt-co-{2-methoxy-5-(2-ethyl-hexyloxy)- 1,4-phenylene vinylene}, a copolymer with mesomorphic phase properties. These Structures were determined by wide-angle X-ray scattering (WAXS) measurements, Assuming a packing model for the copolymer structure, where the planes of the phenyl rings are stacked and separated by an average distance of similar to 4.5 angstrom and laterally spaced by about similar to 16 angstrom, we followed the evolution of these distances as a function of temperature using WAXS and associated the changes observed to the polymer relaxation processes identified by dynamical mechanical thermal analysis. Specific molecular motions were studied by solid-state nuclear magnetic resonance. The onset of the side-chain motion at about 213 K (beta-relaxation) produced a small increase in the lateral spacing and in the stacking distance of the phenyl rings in them aggregated Structures, Besides, at about 383 K (alpha-relaxation) there occurs a significant increase in the amplitude of the torsion motion in the backbone, producing a greater increase in the stacking distance of the phenyl rings. Similar results were observed in the semicrystalline phase of PFO, but in this case the presence of the crystalline structure affects considerably the overall dynamics, which tends to be more hindered. Put together, Our data explain many features of the temperature dependence of the photoluminescence of these two polymers.

Combined Crystallographic and Solution Molecular Dynamics Study of Allosteric Effects in Ester and Ketone p-tert-Butylcalix[4]arene Derivatives and Their Complexes with Acetonitrile, Cd(II), and Pb(II)

We describe here a procedure to bridge the gap in the field of calixarene physicochemistry between solid-state atomic-resolution structural information and the liquid-state low-resolution thermodynamics and spectroscopic data. We use MD simulations to study the kinetics and energetics involved in the complexation of lower rim calix[4]arene derivatives (L), containing bidentate ester (1) and ketone (2) pendant groups, with acetonitrile molecule (MeCN) and Cd2+ and Pb2+ ions (M2+) in acetonitrile solution. On one hand, we found that the prior inclusion of MeCN into the calix to form a L(MeCN) adduct has only a weak effect in preorganizing the hydrophilic cavity toward metal ion binding. On the other hand, the strong ion-hydrophilic cavity interaction produces a wide open calix which enhances the binding of one MeCN molecule (allosteric effect) to stabilize the whole (M2+)1(MeCN) bifunctional complex. We reach two major conclusions: (i) the MD results for the (M2+)1(MeCN) binding are in close agreement with the ""endo"", fully encapsulated, metal complex found by X-ray diffraction and in vacuo MD calculations, and (ii) the MD structure for the more flexible 2 ligand, however, differs from the also endo solid-state molecule. In fact, it shows strong solvation effects at the calixarene lower bore by competing MeCN molecules that share the metal coordination sphere with the four C=O oxygens of an ""exo"" (M2+)2(MeCN) complex.

The effects of anticalcification treatments and hydration on the molecular dynamics of bovine pericardium collagen as revealed by (13)C solid-state NMR

This article describes a solid-state NMR (SSNMR) investigation of the influence of hydration and chemical cross-linking on the molecular dynamics of the constituents of the bovine pericardium (BP) tissues and its relation to the mechanical properties of the tissue. Samples of natural phenetylamine-diepoxide (DE)- and glutaraldehyde (GL)-fixed BP were investigated by (13)C cross-polarization SSNMR to probe the dynamics of the collagen, and the results were correlated to the mechanical properties of the tissues, probed by dynamical mechanical analysis. For samples of natural BP, the NMR results show that the higher the hydration level the more pronounced the molecular dynamics of the collagen backbone and sidechains, decreasing the tissue`s elastic modulus. In contrast, in DE- and GL-treated samples, the collagen molecules are more rigid, and the hydration seems to be less effective in increasing the collagen molecular dynamics and reducing the mechanical strength of the samples. This is mostly attributed to the presence of cross-links between the collagen plates, which renders the collagen mobility less dependent on the water absorption in chemically treated samples. Copyright (C) 2010 John Wiley & Sons, Ltd.

Picosecond Dynamics of Proton Transfer of a 7-Hydroxyflavylium Salt in Aqueous-Organic Solvent Mixtures

The intermediacy of the geminate base proton pair (A*center dot center dot center dot H(+)) in excited-state proton-transfer (ESPT) reactions (two-step mechanism) has been investigated employing the synthetic flavylium salt 7-hydroxy-4-methyl-flavylium chloride (HMF). In aqueous solution, the ESPT mechanism involves solely the excited acid AH* and base A* forms of HMF as indicated by the fluorescence spectra and double-exponential fluorescence decays (two species, two decay times). However, upon addition of either 1,4-dioxane or 1,2-propylene glycol, the decays become triple-exponential with a term consistent with the presence of the geminate base proton pair A*center dot center dot center dot H(+). The geminate pair becomes detectable because of the increase in the recombination rate constant, k(rec), of (A*center dot center dot center dot H(+)) with increasing the mole fraction of added organic cosolvent. Because the two-step ESPT mechanism splits the intrinsic prototropic reaction rates (deprotonation of AH(+)*, k(d), and recombination, k(rec) of A*center dot center dot center dot H(+)) from the diffusion controlled rates (dissociation, k(diss) and formation, k(diff)[H(+)], of A*center dot center dot center dot H+), the experimental detection of the geminate pair provides a wealth of information on the proton-transfer reaction (k(d) and k(rec)) as well as on proton diffusion/migration (k(diss) and k(diff)).

Control Design Applied to a Micro Electro Mechanical System: MEMS Comb drive

This paper presents the linear optimal control technique for reducing the chaotic movement of the micro-electro-mechanical Comb Drive system to a small periodic orbit. We analyze the non-linear dynamics in a micro-electro-mechanical Comb Drive and demonstrated that this model has a chaotic behavior. Chaos control problems consist of attempts to stabilize a chaotic system to an equilibrium point, a periodic orbit, or more general, about a given reference trajectory. This technique is applied in analyzes the nonlinear dynamics in an MEMS Comb drive. The simulation results show the identification by linear optimal control is very effective.

A note about the appearance of non-hyperbolic solutions in a mechanical pendulum system

The investigation of the behavior of a nonlinear system consists in the analysis of different stages of its motion, where the complexity varies with the proximity of a resonance region. Near this region the stability domain of the system undergoes sudden changes due basically to competition and interaction between periodic and saddle solutions inside the phase portrait, leading to the occurrence of the most different phenomena. Depending of the domain of the chosen control parameter, these events can reveal interesting geometric features of the system so that the phase portrait is not capable to express all them, since the projection of these solutions on the two-dimensional surface can hide some aspects of these events. In this work we will investigate the numerical solutions of a particular pendulum system close to a secondary resonance region, where we vary the control parameter in a restrict domain in order to draw a preliminary identification about what happens with this system. This domain includes the appearance of non-hyperbolic solutions where the basin of attraction in the center of the phase portrait diminishes considerably, almost disappearing, and afterwards its size increases with the direction of motion inverted. This phenomenon delimits a boundary between low and high frequency of the external excitation.

On Nonlinear Dynamics and an Optimal Control Design to a Longitudinal Flight

In this work, we analyzed a bifurcational behavior of a longitudinal flight nonlinear dynamics, taking as an example the F-8 aircraft Crusader. We deal with an analysis of high angles of attack in order to stabilize the oscillations; those were close to the critical angle of the aircraft, in the flight conditions, established. We proposed a linear optimal control design applied to the considered nonlinear aircraft model below angle of stall, taking into account regions of Hopf and saddled noddle bifurcations.

On an Active Control for a Structurally Nonlinear Mechanical System, Taking Into Account an Energy Pumping

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

A reducing of a chaotic movement to a periodic orbit, of a micro-electro-mechanical system, by using an optimal linear control design

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Swarm Control Designs applied to a Mechanical Oscillator

This paper presented the particle swarm optimization approach for nonlinear system identification and for reducing the oscillatory movement of the nonlinear systems to periodic orbits. We analyzes the non-linear dynamics in an oscillator mechanical and demonstrated that this model has a chaotic behavior. Chaos control problems consist of attempts to stabilize a chaotic system to an equilibrium point, a periodic orbit, or more general, about a given reference trajectory. This approaches is applied in analyzes the nonlinear dynamics in an oscillator mechanical. The simulation results show the identification by particle swarm optimization is very effective.

Temporal dynamics of two species of Chaetophoraceae (Chlorophyta) in tropical streams of São Paulo State, Southeastern Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Chaotic vibrations of a nonideal electro-mechanical system

Nonideal systems are those in which one takes account of the influence of the oscillatory system on the energy supply with a limited power (Kononenko, 1969). In this paper, a particular nonideal system is investigated, consisting of a pendulum whose support point is vibrated along a horizontal guide by a two bar linkage driven by a DC motor, considered to be a limited power supply. Under these conditions, the oscillations of the pendulum are analyzed through the variation of a control parameter. The voltage supply of the motor is considered to be a reliable control parameter. Each simulation starts from zero speed and reaches a steady-state condition when the motor oscillates around a medium speed. Near the fundamental resonance region, the system presents some interesting nonlinear phenomena, including multi-periodic, quasiperiodic, and chaotic motion. The loss of stability of the system occurs through a saddle-node bifurcation, where there is a collision of a stable orbit with an unstable one, which is approximately located close to the value of the pendulum's angular displacement given by alpha (C)= pi /2. The aims of this study are to better understand nonideal systems using numerical simulation, to identify the bifurcations that occur in the system, and to report the existence of a chaotic attractor near the fundamental resonance. (C) 2001 Elsevier B.V. Ltd. All rights reserved.