The intramolecular charge transfer in a donor-pi-acceptor dianion probed by resonance Raman spectroscopy and quantum chemical calculations

The dideprotonation of 4-(4-nitrophenylazo)resorcinol generates an anionic species with substantial electronic pi delocalization. As compared to the parent neutral species, the anionic first excited electronic transition, characterized as an intramolecular charge transfer (ICT) from the CO(-) groups to the NO(2) moiety, shows a drastic red shift of ca. 200 nm in the lambda(max) in the UV-vis spectrum, leading to one of the lowest ICT energies observed (lambda(max) = 630 nm in dimethyl sulfoxide (DMSO)) in this class of push-pull molecular systems. Concomitantly, a threefold increase in the molar absorptivity (epsilon(max)) in comparison to the neutral species is observed. The resonance Raman enhancement profiles reveal that in the neutral species the chromophore involves several modes, as nu(C-N), nu(N=N), nu(C=C) and nu(s)(NO(2)), whereas in the dianion, there is a selective enhancement of the NO(2) vibrational modes. The quantum chemical calculations of the electronic transitions and vibrational wavenumbers led to a consistent analysis of the enhancement patterns observed in the resonance Raman spectra. Copyright (C) 2009 John Wiley & Sons, Ltd.

Residual-based test for Nonlinear Cointegration with application in PPPs

Nested by linear cointegration first provided in Granger (1981), the definition of nonlinear cointegration is presented in this paper. Sequentially, a nonlinear cointegrated economic system is introduced. What we mainly study is testing no nonlinear cointegration against nonlinear cointegration by residual-based test, which is ready for detecting stochastic trend in nonlinear autoregression models. We construct cointegrating regression along with smooth transition components from smooth transition autoregression model. Some properties are analyzed and discussed during the estimation procedure for cointegrating regression, including description of transition variable. Autoregression of order one is considered as the model of estimated residuals for residual-based test, from which the teststatistic is obtained. Critical values and asymptotic distribution of the test statistic that we request for different cointegrating regressions with different sample sizes are derived based on Monte Carlo simulation. The proposed theoretical methods and models are illustrated by an empirical example, comparing the results with linear cointegration application in Hamilton (1994). It is concluded that there exists nonlinear cointegration in our system in the final results.

Outdoor performance of forest seedlings pre-cultivated under artificial lights : effects of the light spectra used for pre-cultivation on the future establishment and development

Forest nurseries are essential for producing good quality seedlings, thus being a key element in the reforestation process. With increasing climate change awareness, nursery managers are looking for new tools that can help reduce the effects of their operations on the environment. The ZEPHYR project, funded by the European Commission under the Seventh Framework Programme (FP7), has the objective of finding new alternatives for nurseries by developing innovative zero-impact technologies for forest plant production. Due to their direct relationship to the energy consumption of the nurseries, one of the main elements addressed are the grow lights used for the pre-cultivation. New LED luminaires with a light spectrum tailored to the seedlings’ needs are being studied and compared against the traditional fluorescent lamps. Seedlings of Picea abies and Pinus sylvestris were grown under five different light spectra (one fluorescent and 4 LED) during 5 weeks with a photoperiod of 16 hours at 100 μmol∙m-2∙s-1 and 60% humidity. In order to evaluate if these seedlings were able cope with real field stress conditions, a forest field trial was also designed. The terrain chosen was a typical planting site in mid-Sweden after clear-cutting. Two vegetation periods after the outplanting, the seedlings that were pre-cultivated under the LED lamps have performed at least as well as those that were grown under fluorescent lights. These results show that there is a good  potential for lightning substitution in forestry nurseries.

Forecast comparison with nonlinear methods for brazilian industrial production

Este trabalho avalia as previsões de três métodos não lineares — Markov Switching Autoregressive Model, Logistic Smooth Transition Autoregressive Model e Autometrics com Dummy Saturation — para a produção industrial mensal brasileira e testa se elas são mais precisas que aquelas de preditores naive, como o modelo autorregressivo de ordem p e o mecanismo de double differencing. Os resultados mostram que a saturação com dummies de degrau e o Logistic Smooth Transition Autoregressive Model podem ser superiores ao mecanismo de double differencing, mas o modelo linear autoregressivo é mais preciso que todos os outros métodos analisados.

Forecast comparison with nonlinear methods for Brazilian industrial production

This work assesses the forecasts of three nonlinear methods | Markov Switching Autoregressive Model, Logistic Smooth Transition Auto-regressive Model, and Auto-metrics with Dummy Saturation | for the Brazilian monthly industrial production and tests if they are more accurate than those of naive predictors such as the autoregressive model of order p and the double di erencing device. The results show that the step dummy saturation and the logistic smooth transition autoregressive can be superior to the double di erencing device, but the linear autoregressive model is more accurate than all the other methods analyzed.

Comparison between two methods for cardiac output measurement in propofol-anesthetized dogs: thermodilution and Doppler

ObjectiveTo compare cardiac output (CO) measured by Doppler echocardiography and thermodilution techniques in spontaneously breathing dogs during continuous infusion of propofol. To do so, CO was obtained using the thermodilution method (CO(TD)) and Doppler evaluation of pulmonary flow (CO(DP)) and aortic flow (CO(DA)).Study designProspective cohort study.AnimalsEight adult dogs weighing 8.3 +/- 2.0 kg.MethodsPropofol was used for induction (7.5 +/- 1.9 mg kg-1 IV) followed by a continuous rate infusion at 0.7 mg kg-1 minute-1. The animals were positioned in left lateral recumbency on an echocardiography table that allowed for positioning of the transducer at the 3rd and 5th intercostal spaces of the left hemithorax for Doppler evaluation of pulmonary and aortic valves, respectively. CO(DP) and CO(DA) were calculated from pulmonary and aortic velocity spectra, respectively. A pulmonary artery catheter was inserted via the jugular vein and positioned inside the lumen of the pulmonary artery in order to evaluate CO(TD). The first measurement of CO(TD), CO(DP) and CO(DA) was performed 30 minutes after beginning continuous infusion (T0) and then at 15-minute intervals (T15, T30, T45 and T60). Numeric data were submitted to two-way anova for repeated measurements, Pearson's correlation coefficient and Bland & Altman analysis. Data are presented as mean +/- SD.ResultsAt T0, CO(TD) was lower than CO(DA). CO(DA) was higher than CO(TD) and CO(DP) at T30, T45 and T60. The difference between the CO(TD) and CO(DP), when all data were included, was -0.04 +/- 0.22 L minute-1 and Pearson's correlation coefficient (r) was 0.86. The difference between the CO(TD) and CO(DA) was -0.87 +/- 0.54 L minute-1 and r = 0.69. For CO(TD) and CO(DP), the difference was -0.82 +/- 0.59 L minute-1 and r = 0.61.ConclusionDoppler evaluation of pulmonary flow was a clinically acceptable method for assessing the CO in propofol-anesthetized dogs.

Assessment of a high-order finite difference upwind scheme for the simulation of convection-diffusion problems

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

Levenberg-Marquardt application to two-phase nonlinear parameter estimation for finned-tube coil evaporators

A procedure for calculation of refrigerant mass flow rate is implemented in the distributed numerical model to simulate the flow in finned-tube coil dry-expansion evaporators, usually found in refrigeration and air-conditioning systems. Two-phase refrigerant flow inside the tubes is assumed to be one-dimensional, unsteady, and homogeneous. In themodel the effects of refrigerant pressure drop and the moisture condensation from the air flowing over the external surface of the tubes are considered. The results obtained are the distributions of refrigerant velocity, temperature and void fraction, tube-wall temperature, air temperature, and absolute humidity. The finite volume method is used to discretize the governing equations. Additionally, given the operation conditions and the geometric parameters, the model allows the calculation of the refrigerant mass flow rate. The value of mass flow rate is computed using the process of parameter estimation with the minimization method of Levenberg-Marquardt minimization. In order to validate the developed model, the obtained results using HFC-134a as a refrigerant are compared with available data from the literature.

Force and displacement transmissibility of a nonlinear isolator with high-static-low-dynamic-stiffness

Engineers often face the challenge of reducing the level of vibrations experienced by a given payload or those transmitted to the support structure to which a vibrating source is attached. In order to increase the range over which vibrations are isolated, soft mounts are often used in practice. The drawback of this approach is the static displacement may be too large for reasons of available space for example. Ideally, a vibration isolator should have a high-static stiffness, to withstand static loads without too large a displacement, and at the same time, a low dynamic stiffness so that the natural frequency of the system is as low as possible which will result in an increased isolation region. These two effects are mutually exclusive in linear isolators but can be overcome if properly configured nonlinear isolators are used. This paper is concerned with the characterisation of such a nonlinear isolator comprising three springs, two of which are configured to reduce the dynamic stiffness of the isolator. The dynamic behaviour of the isolator supporting a lumped mass is investigated using force and displacement transmissibility, which are derived by modelling the dynamic system as a single-degree-of-freedom system. This results in the system dynamics being approximately described by the Duffing equation. For a linear isolator, the dynamics of the system are the same regardless if the source of the excitation is a harmonic force acting on the payload (force transmissibility) or a harmonic motion of the base (displacement transmissibility) on which the payload is mounted. In this paper these two expressions are compared for the nonlinear isolator and it is shown that they differ. A particular feature of the displacement transmissibility is that the response is unbounded at the nonlinear resonance frequency unless the damping in the isolator is greater than some threshold value, which is not the case for force transmissibility. An explanation for this is offered in the paper. (C) 2011 Elsevier Ltd. All rights reserved.

Lorentz-violating dilatations in momentum space and some extensions on nonlinear actions of Lorentz-algebra-preserving systems

We work on some general extensions of the formalism for theories which preserve the relativity of inertial frames with a nonlinear action of the Lorentz transformations on momentum space. Relativistic particle models invariant under the corresponding deformed symmetries are presented with particular emphasis on deformed dilatation transformations. The algebraic transformations relating the deformed symmetries with the usual (undeformed) ones are provided in order to preserve the Lorentz algebra. Two distinct cases are considered: a deformed dilatation transformation with a spacelike preferred direction and a very special relativity embedding with a lightlike preferred direction. In both analysis we consider the possibility of introducing quantum deformations of the corresponding symmetries such that the spacetime coordinates can be reconstructed and the particular form of the real space-momentum commutator remains covariant. Eventually feasible experiments, for which the nonlinear Lorentz dilatation effects here pointed out may be detectable, are suggested.

Nonlinear Schrodinger equation with power-law confining potential

Critical limits of a stationary nonlinear three-dimensional Schrodinger equation with confining power-law potentials (similar to r(alpha)) are obtained using spherical symmetry. When the nonlinearity is given by an attractive two-body interaction (negative cubic term), it is shown how the maximum number of particles N-c in the trap increases as alpha decreases. With a negative cubic and positive quintic terms we study a first order phase transition, that occurs if the strength g(3) of the quintic term is less than a critical value g(3c). At the phase transition, the behavior of g(3c) with respect to alpha is given by g(3c)similar to 0.0036+0.0251/alpha+0.0088/alpha(2).

General soliton matrices in the Riemann-Hilbert problem for integrable nonlinear equations

We derive the soliton matrices corresponding to an arbitrary number of higher-order normal zeros for the matrix Riemann-Hilbert problem of arbitrary matrix dimension, thus giving the complete solution to the problem of higher-order solitons. Our soliton matrices explicitly give all higher-order multisoliton solutions to the nonlinear partial differential equations integrable through the matrix Riemann-Hilbert problem. We have applied these general results to the three-wave interaction system, and derived new classes of higher-order soliton and two-soliton solutions, in complement to those from our previous publication [Stud. Appl. Math. 110, 297 (2003)], where only the elementary higher-order zeros were considered. The higher-order solitons corresponding to nonelementary zeros generically describe the simultaneous breakup of a pumping wave (u(3)) into the other two components (u(1) and u(2)) and merger of u(1) and u(2) waves into the pumping u(3) wave. The two-soliton solutions corresponding to two simple zeros generically describe the breakup of the pumping u(3) wave into the u(1) and u(2) components, and the reverse process. In the nongeneric cases, these two-soliton solutions could describe the elastic interaction of the u(1) and u(2) waves, thus reproducing previous results obtained by Zakharov and Manakov [Zh. Eksp. Teor. Fiz. 69, 1654 (1975)] and Kaup [Stud. Appl. Math. 55, 9 (1976)]. (C) 2003 American Institute of Physics.

Studying nonlinear effects on the early stage of phase ordering using a decomposition method

Nonlinear effects on the early stage of phase ordering are studied using Adomian's decomposition method for the Ginzburg-Landau equation for a nonconserved order parameter. While the long-time regime and the linear behavior at short times of the theory are well understood, the onset of nonlinearities at short times and the breaking of the linear theory at different length scales are less understood. In the Adomians decomposition method, the solution is systematically calculated in the form of a polynomial expansion for the order parameter, with a time dependence given as a series expansion. The method is very accurate for short times, which allows to incorporate the short-time dynamics of the nonlinear terms in a analytical and controllable way. (c) 2005 Elsevier B.V. All rights reserved.

Nonlinear Gravitational Waves: Their Form and Effects

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

Kinetic energy sum spectra in nonmesonic weak decay of hypernuclei

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)