An analysis of the environmental energetics associated with the transition of the first South Atlantic hurricane

This study presents the first analysis of the energetics associated with a hybrid cyclone`s transition in the Southern Hemisphere, Hurricane Catarina ( March 2004). Catarina has earned a place in history as the first documented South Atlantic hurricane, but its unusual tropical transition is still poorly understood. Here we show that Catarina`s transition was preceded by marked environmental changes in the Lorenz energy cycle, with an abrupt shift from a baroclinic to a predominantly barotropic state. Such changes help to explain the unusual vortex`s growth until its transition was completed. Although the vortex`s energy flux is not explicitly calculated, a likely mechanism linking the environmental energetics with Catarina is the extraction of eddy kinetic energy from horizontal momentum and heat transfers within the through component of the blocking. The results advance the understanding of this rare event and suggest that the technique has a great potential to study transitioning systems in general.

Transition redshift: new kinematic constraints from supernovae

The transition redshift (deceleration/acceleration) is discussed by expanding the deceleration parameter to first order around its present value. A detailed study is carried out by considering two different parametrizations, q = q(0) + q(1)z and q = q(0) + q(1)z(1 + z)(-1), and the associated free parameters (q(0), q(1)) are constrained by three different supernovae (SNe) samples. A previous analysis by Riess et al. using the first expansion is slightly improved and confirmed in light of their recent data (Gold07 sample). However, by fitting the model with the Supernova Legacy Survey (SNLS) type Ia sample, we find that the best fit to the redshift transition is z(t) = 0.61, instead of z(t) = 0.46 as derived by the High-z Supernovae Search (HZSNS) team. This result based in the SNLS sample is also in good agreement with the sample of Davis et al., z(t) = 0.60(-0.11)(+0.28) (1 sigma). Such results are in line with some independent analyses and accommodate more easily the concordance flat model (Lambda CDM). For both parametrizations, the three SNe Ia samples considered favour recent acceleration and past deceleration with a high degree of statistical confidence level. All the kinematic results presented here depend neither on the validity of general relativity nor on the matter-energy contents of the Universe.

An accelerating cosmology without dark energy

The negative pressure accompanying gravitationally-induced particle creation can lead to a cold dark matter (CDM) dominated, accelerating Universe (Lima et al. 1996 [1]) without requiring the presence of dark energy or a cosmological constant. In a recent study, Lima et al. 2008 [2] (LSS) demonstrated that particle creation driven cosmological models are capable of accounting for the SNIa observations [3] of the recent transition from a decelerating to an accelerating Universe, without the need for Dark Energy. Here we consider a class of such models where the particle creation rate is assumed to be of the form Gamma = beta H + gamma H(0), where H is the Hubble parameter and H(0) is its present value. The evolution of such models is tested at low redshift by the latest SNe Ia data provided by the Union compilation [4] and at high redshift using the value of z(eq), the redshift of the epoch of matter - radiation equality, inferred from the WMAP constraints on the early Integrated Sachs-Wolfe (ISW) effect [5]. Since the contributions of baryons and radiation were ignored in the work of LSS, we include them in our study of this class of models. The parameters of these more realistic models with continuous creation of CDM are constrained at widely-separated epochs (z(eq) approximate to 3000 and z approximate to 0) in the evolution of the Universe. The comparison of the parameter values, {beta, gamma}, determined at these different epochs reveals a tension between the values favored by the high redshift CMB constraint on z(eq) from the ISW and those which follow from the low redshift SNIa data, posing a potential challenge to this class of models. While for beta = 0 this conflict is only at less than or similar to 2 sigma, it worsens as beta increases from zero.

Multivariate analysis of the energy cycle of the South American rainy season

The South American (SA) rainy season is studied in this paper through the application of a multivariate Empirical Orthogonal Function (EOF) analysis to a SA gridded precipitation analysis and to the components of Lorenz Energy Cycle (LEC) derived from the National Centers for Environmental Prediction (NCEP) reanalysis. The EOF analysis leads to the identification of patterns of the rainy season and the associated mechanisms in terms of their energetics. The first combined EOF represents the northwest-southeast dipole of the precipitation between South and Central America, the South American Monsoon System (SAMS). The second combined EOF represents a synoptic pattern associated with the SACZ (South Atlantic convergence zone) and the third EOF is in spatial quadrature to the second EOF. The phase relationship of the EOFs, as computed from the principal components (PCs), suggests a nonlinear transition from the SACZ to the fully developed SAMS mode by November and between both components describing the SACZ by September-October (the rainy season onset). According to the LEC, the first mode is dominated by the eddy generation term at its maximum, the second by both baroclinic and eddy generation terms and the third by barotropic instability previous to the connection to the second mode by September-October. The predominance of the different LEC components at each phase of the SAMS can be used as an indicator of the onset of the rainy season in terms of physical processes, while the existence of the outstanding spectral peaks in the time dependence of the EOFs at the intraseasonal time scale could be used for monitoring purposes. Copyright (C) 2009 Royal Meteorological Society

Nutrition in Transition: Dietary Patterns of Rural Amazonian Women During a Period of Economic Change

Objectives: The goal of this study was to understand the relationship between economic change (wage labor, retirement, and the Bolsa Familia program) and dietary patterns in the rural Amazon and to determine the extent to which these changes followed the pattern of the nutrition transition. Methods: The study was longitudinal. The weighed-inventory method and economic interviews were used to collect data on dietary intake and household economics in a sample of 30 and 52 women in 2002 and 2009, respectively. Twenty of the women participated in both years and make-up the longitudinal sub-sample. Comparative statistics were used to identify changes in dietary patterns over time and multiple linear regressions were used to explore the relationship between economics, subsistence strategies, and diet. Results: There was a significant decline in kcal (P < 0.01) and carbohydrate (P < 0.01) but no change in protein intake over time in both the larger and smaller, longitudinal subsample. The percent of energy, carbohydrate, protein, and fat purchased increased in the larger and longitudinal samples (P <= 0.02) and there was an increase in refined carbohydrate and processed, fatty-meat consumption over time. The abandonment of manioc gardens was associated with increased dependence on purchased food (P = 0.03) while receipt of the Bolsa Familia was associated with increased protein intake and adequacy (P = 0.02). Conclusions: The dietary changes observed are only in partial agreement with predictions of the nutrition transition literature. The relationship between the economic and diet changes was shaped by the local context which should be considered when implementing CCT programs, like the Bolsa Familia. Am. J. Hum. Biol. 23:458-469, 2011. (C) 2011 Wiley-Liss, Inc.

A scenario for torus T(2) destruction via a global bifurcation

We show a scenario of a two-frequeney torus breakdown, in which a global bifurcation occurs due to the collision of a quasi-periodic torus T(2) with saddle points, creating a heteroclinic saddle connection. We analyze the geometry of this torus-saddle collision by showing the local dynamics and the invariant manifolds (global dynamics) of the saddle points. Moreover, we present detailed evidences of a heteroclinic saddle-focus orbit responsible for the type-if intermittency induced by this global bifurcation. We also characterize this transition to chaos by measuring the Lyapunov exponents and the scaling laws. (C) 2007 Elsevier Ltd. All rights reserved.

Transition metal atoms encapsulated in adamantane molecules

We performed a first principles total energy investigation on the structural, electronic, and magnetic properties of 3d-transition metal-encapsulated adamantane molecules (TM@C(10)H(16). with TM = Cr, Mn, Fe, Co, and Ni). We find that the C-C interactions are strong enough to maintain the molecular rigidity upon TM incorporation, although outward relaxations and formation energies are large. We built a microscopic model that explains the electronic structure of those molecules. (C) 2011 Elsevier B.V. All rights reserved.

Trends on 3d transition metal impurities in diamond

We carried out a first principles investigation on the electronic properties and chemical trends of 3d transition metal related impurities in diamond. In terms of formation energy, the interstitial site is considerably more unfavorable than the substitutional or divacancy ones. Going from Ti to Ni, the 3d-related energy levels in the gap become deeper toward the valence band in all three sites. However, in the divacancy one, those levels cross with the divacancy-related ones, such that the electronic property of the center depends on the character of the highest occupied level. (C) 2009 Elsevier B.A. All rights reserved.

Energy States of Phosphorous Donor in Silicon in Fields up to 18 T

The evolution of the energy states of the phosphorous donor in silicon with magnetic field has been the subject of previous experimental and theoretical studies to fields of 10 T. We now present experimental optical absorption data to 18 T in combination with theoretical data to the same field. We observe features that are not revealed in the earlier work, including additional interactions and anti-crossings between the different final states. For example, according to the theory, for the ""1s -> 2p (+)"" transition, there are anti-crossings at about 5, 10, 14, 16, and 18 T. In the experiments, we resolve at least the 5, 10, and 14 T anti-crossings, and our data at 16 and 18 T are consistent with the calculations.

Triple Structural Transition below Room Temperature in the Antifilarial Drug Diethylcarbamazine Citrate

A very unusual triple structural transition pattern below room temperature was observed for the antifilarial drug diethylcarbamazine citrate. Besides the first thermal, crystallographic, and vibrational investigations of this first-line drug used in clinical treatment for lymphatic filariasis, a noteworthy behavior with three structural transformations as a function of temperature was demonstrated by differential scanning calorimetry, Raman spectroscopy, and single-crystal X-ray diffractometry. Our X-ray data on single crystals allow for a complete featuring and understanding of all transitions, since the four structures associated with the three solid-solid phase transformations were accurately determined. Two of three structural transitions show an order-disorder mechanism and temperature hysteresis with exothermic peaks at 224 K (T(1)`) and 213 K (T(2)`) upon cooling and endothermic ones at 248 K (T(1)) and 226 K (T(2)) upon heating. The other transition occurs at 108 K (T(3)) and it is temperature-rate sensitive. Molecular displacements onto the (010) plane and conformational changes of the diethylcarbamazine backbone as a consequence of the C-H center dot center dot center dot N hydrogen bonding formation/cleavage between drug molecules explain the mechanism of the transitions at T(1)`/T(2). However, such changes are observed only on alternate columns of the drug intercalated by citrate chains, which leads to a doubling of the lattice period along the a axis of the 235 K structure with respect to the 150 and 293 K structures. At T(2)`/T(1), these structural alterations occur in all columns of the drug. At T(3), there is a rotation on the axis of the N-C bond between the carbamoyl moiety and an ethyl group of one crystallographically independent diethylcarbamazine molecule besides molecular shifts and other conformational alterations. The impact of this study is based on the fascinating finding in which the versatile capability of structural adaptation dependent on the thermal history was observed for a relatively simple organic salt, diethylcarbamazine citrate.

Solvatochromic Shift of the pi -> pi* Transition in All-Trans, Cis-13, Cis-11, Cis-9, and Cis-7 Retinal Isomers Induced by Water and Methanol

The solvatochromic shift of the lowest singlet it pi -> pi* electronic transition in the all-trans, cis-13, cis-11, cis-9, and cis-7 retinal isomers were computed under the influence of water, methanol, and benzene solvents. Excitation energies were calculated in gas phase and in solution. The calculations in solution were performed considering the sequential Monte Carlo (MC) /Quantum Mechanical approach. The MC simulations were performed considering the full retinal isomer molecules and 900 water molecules, 900 methanol, or 400 benzene ones. The OPLS/AA parametrization was chosen for retinal, methanol, and benzene molecules and the SPC model was used for water one. From the MC calculations 100 independent configurations were selected, with 100 solvent molecules in thermodynamical equilibrium at T = 298.15 K. Average point-charges were obtained from those independent configurations for water, methanol, and benzene solvent. TDDFT and CASSCF//CASPT2 methodologies were used to compute the vertical excitation energy of the retinal isomers in different environment. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110: 2076-2087, 2010

Excited Electronic States, Transition Probabilities, and Radiative Lifetimes of CAs: A Theoretical Contribution and Challenge to Experimentalists

High-level CASSCF/MRCI calculations with a quintuple-zeta quality basis set are reported by characterizing for the first time a manifold of electronic states of the CAs radical yet to be investigated experimentally. Along with the potential energy curves and the associated spectroscopic constants, the dipole moment functions for selected electronic states as well as the transition dipole moment functions for the most relevant electronic transitions are also presented. Estimates of radiative transition probabilities and lifetimes complement this investigation, which also assesses the effect of spin-orbit interaction on the A (2)Pi state. Whenever pertinent, comparisons of similarities and differences with the isovalent CN and CP radicals are made.

Exploring new molecular species on the (1)[H, Se, F] singlet potential energy surface: Energetics, structures, IR spectra, and heats of formation

Structural, energetic, and vibrational properties of new molecular species, HSeF and HFSe, the associated transition state, and dissociation fragments are investigated using a state-of-the-art theoretical approach, CCSD(T)/CBS. HSeF is a normal covalently bonded molecule 38.98 kcal mol (1) more stable than the complex HF-Se, which shows an unusual structure with a central fluorine atom and a bond angle of 101.8 degrees.A barrier (Delta G(#)) of 49.01 kcal mol (1) separates the two species. Vibrational frequencies are also quite distinct. Heats of formation are evaluated for the diatomic fragments and HSeF. Final Delta(f)H values depend on the experimental accuracy of those of Se(g) and H(2)Se. (c) 2009 Elsevier B.V. All rights reserved.

Can mass dissociation patterns of transition-metal complexes be predicted from electrochemical data?

The Cooks kinetic method has been very convenient to correlate the relative dissociation rates obtained by collision-induced fragmentation experiments with the energies of two related bonds in molecules and complexes in the gas phase. Reliable bond energy data are, however, not always available, particularly for polynuclear transition-metal complexes, such as the triruthenium acetate clusters of the general formula [Ru(3) (mu(3)-O)(mu-CH(3)COO)(6)(py)(2)(L)](+), where L = ring substituted N-heterocyclic ligands. Accordingly, their gas-phase collision-induced tandem mass spectrometry (CID MS/MS) dissociation patterns have been analyzed pursuing a relationship with the more easily accessible redox potentials (E(1/2)) and Lever`s E(L) parameters. In fact, excellent linear correlations of In(1/2A(L)/A(py)), where A(py) and A(L) are the abundance of the fragments retaining the pyridine (py) and L ligand, respectively, with E(1/2) and E(L) were found. This result shows that those electrochemical parameters are correlated with bond energies and can be used in the analysis of the dissociation data. Such modified Cooks method can be used, for example, to determine the electronic effects of substituents on the metal-ligand bonds for a series of transition-metal complexes. Copyright (C) 2008 John Wiley & Sons, Ltd.

Climate change and energy use : The role for anthropological research

The expression 'global climate change' no longer designates merely a discourse on possible future risks; today it us used as a shorthand for specific ongoing events that are having a serious impact on the lives of people around the world. In the light of this change and consequent efforts to limit carbon dioxide emissions, contributions from social scientists are increasingly in demand within the study of energy use. My concern here is not whether intervention is a proper role for anthropologists, but rather how we may position ourselves within energy- and climate-related research.