I. Phosphorescence and the true lifetime of triplet states in fluid solutions. II. Why is condensed oxygen blue?

I. PHOSPHORESCENCE AND THE TRUE LIFETIME OF TRIPLET STATES IN FLUID SOLUTIONS

Phosphorescence has been observed in a highly purified fluid solution of naphthalene in 3-methylpentane (3-MP). The phosphorescence lifetime of C₁₀H₈ in 3-MP at -45 °C was found to be 0.49 ± 0.07 sec, while that of C₁₀D₈ under identical conditions is 0.64 ± 0.07 sec. At this temperature 3-MP has the same viscosity (0.65 centipoise) as that of benzene at room temperature. It is believed that even these long lifetimes are dominated by impurity quenching mechanisms. Therefore it seems that the radiationless decay times of the lowest triplet states of simple aromatic hydrocarbons in liquid solutions are sensibly the same as those in the solid phase. A slight dependence of the phosphorescence lifetime on solvent viscosity was observed in the temperature region, -60° to -18°C. This has been attributed to the diffusion-controlled quenching of the triplet state by residual impurity, perhaps oxygen. Bimolecular depopulation of the triplet state was found to be of major importance over a large part of the triplet decay.

The lifetime of triplet C₁₀H₈ at room temperature was also measured in highly purified benzene by means of both phosphorescence and triplet-triplet absorption. The lifetime was estimated to be at least ten times shorter than that in 3-MP. This is believed to be due not only to residual impurities in the solvent but also to small amounts of impurities produced through unavoidable irradiation by the excitation source. In agreement with this idea, lifetime shortening caused by intense flashes of light is readily observed. This latter result suggests that experiments employing flash lamp techniques are not suitable for these kinds of studies.

The theory of radiationless transitions, based on Robinson's theory, is briefly outlined. A simple theoretical model which is derived from Fano's autoionization gives identical result.

Il. WHY IS CONDENSED OXYGEN BLUE?

The blue color of oxygen is mostly derived from double transitions. This paper presents a theoretical calculation of the intensity of the double transition (a ¹Δ_g) (a ¹Δ_g)←(X ³Σ_g^-) (X ³Σ_g^-), using a model based on a pair of oxygen molecules at a fixed separation of 3.81 Å. The intensity enhancement is assumed to be derived from the mixing (a ¹Δ_g) (a ¹Δ_g) _~~~ (X ³Σ_g^-) (X ³Σ_u^-) and (a ¹Δ_g) (¹Δ_u) _~~~ (X ³Σ_g^-) (X ³Σ_g^-). Matrix elements for these interactions are calculated using a π-electron approximation for the pair system. Good molecular wavefunctions are used for all but the perturbing (B ³Σ_u^-) state, which is approximated in terms of ground state orbitals. The largest contribution to the matrix elements arises from large intramolecular terms multiplied by intermolecular overlap integrals. The strength of interaction depends not only on the intermolecular separation of the two oxygen molecules, but also as expected on the relative orientation. Matrix elements are calculated for different orientations, and the angular dependence is fit to an analytical expression. The theory therefore not only predicts an intensity dependence on density but also one on phase at constant density. Agreement between theory and available experimental results is satisfactory considering the nature of the approximation, and indicates the essential validity of the overall approach to this interesting intensity enhancement problem.

Experimental studies of weak superconductivity

Experimental investigations were made of the nature of weak superconductivity in a structure having well-defined, controllable characteristics and geometry. Controlled experiments were made possible by using a thin-film structure which was entirely metallic and consisted of a superconducting film with a localized section that was weak in the sense that its transition temperature was depressed relative to the rest of the film. The depression of transition temperature was brought about by underlaying the superconductor with a normal metal.

The DC and AC electrical characteristics of this structure were studied. It was found that this structure exhibited a non-zero, time-average supercurrent at finite voltage to at least .2 mV, and generated an oscillating electric potential at a frequency given by the Josephson relation. The DC V-I characteristic and the amplitude of the AC oscillation were found to be consistent with a two- fluid (normal current-supercurrent) model of weak super-conductivity based on e thermodynamically irreversible process of repetitive phase-slip, and featuring a periodic time dependence in the amplitude of the superconducting order parameter.

The observed linewidth of the AC oscillation could be accounted for by incorporating Johnson noise in the two-fluid model.

Experimentally it was found that the behavior of a short (length on the order of the coherence distance) weak superconductor could be characterized by its critical current and normal-state resistance, and an empirical expression was obtained for the time dependence of the super-current and voltage.

It was found that the results could not be explained on the basis of the theory of the Josephson junction.

Efeitos macrovasculares, microvasculares e interação leucócito-endotélio, na endotoxemia experimental após o uso de Dobutamina com e sem ressuscitação volêmica

Na sepse, o mecanismo desencadeador de morte é a disfunção múltipla de órgãos e sistemas. Com isso a microcirculação é considerada o motor na patogênese da sepse. A perfusão microcirculatória representa um dos principais objetivos para melhorar as taxas de sobrevida. Uma vez reconhecida a síndrome séptica, o protocolo clínico estabelece o uso de fluidoterapia com salina, de forma vigorosa na primeira hora e seguida de suporte inotrópico com Dobutamina. A partir daí foi levantada a hipótese das drogas β-agonistas serem relevantes na recuperação da microcirculação, antes mesmo de seu conhecido papel na recuperação do choque cardiogênico. Assim, estudar o papel da Dobutamina, um β-agonista, na resposta adrenérgica em situação de sepse se faz necessário e urgente e o entendimento de sua ação, associada à reposição volêmica, foi objeto deste estudo. Foram usados no presente estudo, 78 hamsters, induzida a endotoxemia com LPS (2mg/kg/de massa de peso corporal) e divididos em 9 grupos: controle (n=10), endotóxico(n=10), endotóxico tratados com Dobutamina na dose de 5 e 15 μg /kg/min (n=10), Isoproterenol(n=10), ressuscitação volêmica (n=10) e ressuscitação volêmica associada à Dobutamina 5 (n=10) e 15 μg/kg/min (n=4) e Isoproterenol (n=4). Foram comparados os resultados de recuperação da densidade capilar funcional ao longo do tempo entre os grupos, e obteve-se resultado estatisticamente significativo no grupo em que se usa Dobutamina de 5μg/kg/min associada à ressuscitação volêmica p< 0,05. Em conclusão este estudo mostra que o papel da ressuscitação volêmica é crucial na resposta da microcirculação para melhorar a densidade capilar funcional, que a velocidade da hemácia capilar tem relação direta com a melhora na perfusão tecidual e que a associação de recuperação volêmica com solução salina e Dobutamina na dose de 5 μg /kg /min melhora significativamente sua resposta e melhora a perfusão.

Fluid-structure interaction simulation of an inflatable aerodynamic tension-cone decelerator

Inflatable aerodynamic decelerators have potential advantages for planetary re-entry in robotic and human exploration missions. In this paper, we focus on an inflatable tension cone design that has potential advantages over other geometries. A computational fluid-structure interaction model of a tension cone is employed to investigate the behavior of the inflatable aeroshell at supersonic speeds for conditions matching recent experimental results. A parametric study is carried out to investigate the deflections of the tension cone as a function of inflation pressure of the torus at a Mach of 2.5. Comparison of the behavior of the structure, amplitude of deformations, and determined loads are reported. © 2010 by the American Institute of Aeronautics and Astronautics, Inc.

An experimental and numerical study of an oscillating transonic shock wave in a duct

A combined experimental and numerical study of a transonic shock wave in a parallel walled duct subject to downstream pressure perturbations has been conducted. Experiments and simulations have been carried out with a shock strength of M∞ = 1.4 for pressure perturbation frequencies in the range 16-90 Hz. The dynamics of unsteady shock motion and the interaction structure between the unsteady transonic shock wave and the turbulent tunnel floor boundary layer have been investigated. It is found that the (experimentally measured) dynamics of shock motion are generally well predicted by the computational scheme, especially at relatively low (≈ 40 Hz) frequencies. However, at higher frequencies (≈ 90 Hz), some subtle differences between the shock dynamics measured in experiments and those predicted by Computational Fluid Dynamics (CFD) exist. There is evidence from experiments that variations in shock / boundary layer interaction (SBLI) structure caused by shock motion are responsible for a change in the nature of shock dynamics between low and high frequency. In contrast, numerical results at low and high frequencies do not differ significantly and this suggests that the numerical method is not fully capturing the physics of the unsteady flow. Possible reasons for this are considered and a number of areas where CFD is unable to replicate experimental observations are identified. Significantly, CFD predicts changes in SBLI structure due to shock motion that are much too large and this may explain why none of the subtle effects on shock dynamics seen in experiments occur in CFD. Further work developing numerical methods that demonstrate a more realistic sensitivity of SBLI structure to unsteady shock motion is required. Copyright © 2010 by P.J.K. Bruce.

CFD-DEM simulation of propagation of sound waves in fluid particles fluidised medium

In this work, speed of sound in 2 phase mixture has been explored using CFD-DEM (Computational Fluid Dynamcis - Discrete Element Modelling). In this method volume averaged Navier Stokes, continuity and energy equations are solved for fluid. Particles are simulated as individual entities; their behaviour is captured by Newton's laws of motion and classical contact mechanics. Particle-fluid interaction is captured using drag laws given in literature.The speed of sound in a medium depends on physical properties. It has been found experimentally that speed of sound drops significantly in 2 phase mixture of fluidised particles because of its increased density relative to gas while maintaining its compressibility. Due to the high rate of heat transfer within 2 phase medium as given in Roy et al. (1990), it has been assumed that the fluidised gas-particle medium is isothermal.The similar phenomenon has been tried to be captured using CFD-DEM numerical simulation. The disturbance is introduced and fundamental frequency in the medium is noted to measure the speed of sound for e.g. organ pipe. It has been found that speed of sound is in agreement with the relationship given in Roy et al. (1990). Their assumption that the system is isothermal also appears to be valid.

Experimental evidence of flutter and divergence instabilities induced by dry friction

Flutter and divergence instabilities have been advocated to be possible in elastic structures with Coulomb friction, but no direct experimental evidence has ever been provided. Moreover, the same types of instability can be induced by tangential follower forces, but these are commonly thought to be of extremely difficult, if not impossible, practical realization. Therefore, a clear experimental basis for flutter and divergence induced by friction or follower-loading is still lacking. This is provided for the first time in the present article, showing how a follower force of tangential type can be realized via Coulomb friction and how this, in full agreement with the theory, can induce a blowing-up vibrational motion of increasing amplitude (flutter) or an exponentially growing motion (divergence). In addition, our results show the limits of a treatment based on the linearized equations, so that nonlinearities yield the initial blowing-up vibration of flutter to reach eventually a steady state. The presented results give full evidence to potential problems in the design of mechanical systems subject to friction, open a new perspective in the realization of follower-loading systems and of innovative structures exhibiting 'unusual' dynamical behaviors. © 2011 Elsevier Ltd.

Synchronization of modulated traveling baroclinic waves in a periodically forced, rotating fluid annulus.

Frequency entrainment and nonlinear synchronization are commonly observed between simple oscillatory systems, but their occurrence and behavior in continuum fluid systems are much less well understood. Motivated by possible applications to geophysical fluid systems, such as in atmospheric circulation and climate dynamics, we have carried out an experimental study of the interaction of fully developed baroclinic instability in a differentially heated, rotating fluid annulus with an externally imposed periodic modulation of the thermal boundary conditions. In quasiperiodic and chaotic amplitude-modulated traveling wave regimes, the results demonstrate a strong interaction between the natural periodic modulation of the wave amplitude and the externally imposed forcing. This leads to partial or complete phase synchronization. Synchronization effects were observed even with very weak amplitudes of forcing, and were found with both 1:1 and 1:2 frequency ratios between forcing and natural oscillations.