First-principles study of the inversion thermodynamics and electronic structure of FeM2X4 (thio)spinels (M = Cr, Mn, Co, Ni; X = O, S)

FeM2X4 spinels, where M is a transition metal and X is oxygen or sulfur, are candidate materials for spin filters, one of the key devices in spintronics. We present here a computational study of the inversion thermodynamics and the electronic structure of these (thio)spinels for M = Cr, Mn, Co, Ni, using calculations based on the density functional theory with on-site Hubbard corrections (DFT+U). The analysis of the configurational free energies shows that different behaviour is expected for the equilibrium cation distributions in these structures: FeCr2X4 and FeMn2S4 are fully normal, FeNi2X4 and FeCo2S4 are intermediate, and FeCo2O4 and FeMn2O4 are fully inverted. We have analyzed the role played by the size of the ions and by the crystal field stabilization effects in determining the equilibrium inversion degree. We also discuss how the electronic and magnetic structure of these spinels is modified by the degree of inversion, assuming that this could be varied from the equilibrium value. We have obtained electronic densities of states for the completely normal and completely inverse cation distribution of each compound. FeCr2X4, FeMn2X4, FeCo2O4 and FeNi2O4 are half-metals in the ferrimagnetic state when Fe is in tetrahedral positions. When M is filling the tetrahedral positions, the Cr-containing compounds and FeMn2O4 are half-metallic systems, while the Co and Ni spinels are insulators. The Co and Ni sulfide counterparts are metallic for any inversion degree together with the inverse FeMn2S4. Our calculations suggest that the spin filtering properties of the FeM2X4 (thio)spinels could be modified via the control of the cation distribution through variations in the synthesis conditions.

Improving climate change detection through optimal seasonal averaging: the case of the North Atlantic jet and European precipitation

The detection of anthropogenic climate change can be improved by recognising the seasonality in the climate change response. This is demonstrated for the North Atlantic jet (zonal wind at 850 hPa, U850) and European precipitation responses projected by the CMIP5 climate models. The U850 future response is characterised by a marked seasonality: an eastward extension of the North Atlantic jet into Europe in November-April, and a poleward shift in May-October. Under the RCP8.5 scenario, the multi-model mean response in U850 in these two extended seasonal means emerges by 2035-2040 for the lower--latitude features and by 2050-2070 for the higher--latitude features, relative to the 1960-1990 climate. This is 5-15 years earlier than when evaluated in the traditional meteorological seasons (December--February, June--August), and it results from an increase in the signal to noise ratio associated with the spatial coherence of the response within the extended seasons. The annual mean response lacks important information on the seasonality of the response without improving the signal to noise ratio. The same two extended seasons are demonstrated to capture the seasonality of the European precipitation response to climate change and to anticipate its emergence by 10-20 years. Furthermore, some of the regional responses, such as the Mediterranean precipitation decline and the U850 response in North Africa in the extended winter, are projected to emerge by 2020-2025, according to the models with a strong response. Therefore, observations might soon be useful to test aspects of the atmospheric circulation response predicted by some of the CMIP5 models.

Response of the North Atlantic wave climate to atmospheric modes of variability

This study investigates the relationship between the wind wave climate and the main climate modes of atmospheric variability in the North Atlantic Ocean. The modes considered are the North Atlantic Oscillation (NAO), the East Atlantic (EA) pattern, the East Atlantic Western Russian (EA/WR) pattern and the Scandinavian (SCAN) pattern. The wave dataset consists of buoys records, remote sensing altimetry observations and a numerical hindcast providing significant wave height (SWH), mean wave period (MWP) and mean wave direction (MWD) for the period 1989–2009. After evaluating the reliability of the hindcast, we focus on the impact of each mode on seasonal wave parameters and on the relative importance of wind-sea and swell components. Results demonstrate that the NAO and EA patterns are the most relevant, whereas EA/WR and SCAN patterns have a weaker impact on the North Atlantic wave climate variability. During their positive phases, both NAO and EA patterns are related to winter SWH at a rate that reaches 1 m per unit index along the Scottish coast (NAO) and Iberian coast (EA) patterns. In terms of winter MWD, the two modes induce a counterclockwise shift of up to 65° per negative NAO (positive EA) unit over west European coasts. They also increase the winter MWP in the North Sea and in the Bay of Biscay (up to 1 s per unit NAO) and along the western coasts of Europe and North Africa (1 s per unit EA). The impact of winter EA pattern on all wave parameters is mostly caused through the swell wave component.

Impact of the North Atlantic Oscillation on transatlantic flight routes and clear-air turbulence

The variation of wind-optimal transatlantic flight routes and their turbulence potential is investigated to understand how upper-level winds and large-scale flow patterns can affect the efficiency and safety of long-haul flights. In this study, the wind-optimal routes (WORs) that minimize the total flight time by considering wind variations are modeled for flights between John F. Kennedy International Airport (JFK) in New York, New York, and Heathrow Airport (LHR) in London, United Kingdom, during two distinct winter periods of abnormally high and low phases of North Atlantic Oscillation (NAO) teleconnection patterns. Eastbound WORs approximate the JFK–LHR great circle (GC) route following northerly shifted jets in the +NAO period. Those WORs deviate southward following southerly shifted jets during the −NAO period, because eastbound WORs fly closely to the prevailing westerly jets to maximize tailwinds. Westbound WORs, however, spread meridionally to avoid the jets near the GC in the +NAO period to minimize headwinds. In the −NAO period, westbound WORs are north of the GC because of the southerly shifted jets. Consequently, eastbound WORs are faster but have higher probabilities of encountering clear-air turbulence than westbound ones, because eastbound WORs are close to the jet streams, especially near the cyclonic shear side of the jets in the northern (southern) part of the GC in the +NAO (−NAO) period. This study suggests how predicted teleconnection weather patterns can be used for long-haul strategic flight planning, ultimately contributing to minimizing aviation’s impact on the environment

Abrupt transitions in the NAO control of explosive North Atlantic cyclone development

Explosive cyclones are intense extra-tropical low pressure systems featuring large deepening rates. In the Euro-Atlantic sector, they are a major source of life-threatening weather impacts due to their associated strong wind gusts, heavy precipitation and storm surges. The wintertime variability of the North Atlantic cyclonic activity is primarily modulated by the North Atlantic Oscillation (NAO). In this study, we investigate the interannual and multi-decadal variability of explosive North Atlantic cyclones using track density data from two reanalysis datasets (NCEP and ERA-40) and a control simulation of an atmosphere/ocean coupled General Circulation Model (GCM—ECHAM5/MPIOM1). The leading interannual and multi-decadal modes of variability of explosive cyclone track density are characterized by a strengthening/weakening pattern between Newfoundland and Iceland, which is mainly modulated by the NAO at both timescales. However, the NAO control of interannual cyclone variability is not stationary in time and abruptly fluctuates during periods of 20–25 years long both in NCEP and ECHAM5/MPIOM1. These transitions are accompanied by structural changes in the leading mode of explosive cyclone variability, and by decreased/enhanced baroclinicity over the sub-polar/sub-tropical North Atlantic. The influence of the ocean is apparently important for both the occurrence and persistence of such anomalous periods. In the GCM, the Atlantic Meridional Overturning Circulation appears to influence the large-scale baroclinicity and explosive cyclone development over the North Atlantic. These results permit a better understanding of explosive cyclogenesis variability at different climatic timescales and might help to improve predictions of these hazardous events.

Future change of climate in South America in the late twenty-first century: intercomparison of scenarios from three regional climate models

Regional climate change projections for the last half of the twenty-first century have been produced for South America, as part of the CREAS (Cenarios REgionalizados de Clima Futuro da America do Sul) regional project. Three regional climate models RCMs (Eta CCS, RegCM3 and HadRM3P) were nested within the HadAM3P global model. The simulations cover a 30-year period representing present climate (1961-1990) and projections for the IPCC A2 high emission scenario for 2071-2100. The focus was on the changes in the mean circulation and surface variables, in particular, surface air temperature and precipitation. There is a consistent pattern of changes in circulation, rainfall and temperatures as depicted by the three models. The HadRM3P shows intensification and a more southward position of the subtropical Pacific high, while a pattern of intensification/weakening during summer/winter is projected by the Eta CCS/RegCM3. There is a tendency for a weakening of the subtropical westerly jet from the Eta CCS and HadRM3P, consistent with other studies. There are indications that regions such of Northeast Brazil and central-eastern and southern Amazonia may experience rainfall deficiency in the future, while the Northwest coast of Peru-Ecuador and northern Argentina may experience rainfall excesses in a warmer future, and these changes may vary with the seasons. The three models show warming in the A2 scenario stronger in the tropical region, especially in the 5A degrees N-15A degrees S band, both in summer and especially in winter, reaching up to 6-8A degrees C warmer than in the present. In southern South America, the warming in summer varies between 2 and 4A degrees C and in winter between 3 and 5A degrees C in the same region from the 3 models. These changes are consistent with changes in low level circulation from the models, and they are comparable with changes in rainfall and temperature extremes reported elsewhere. In summary, some aspects of projected future climate change are quite robust across this set of model runs for some regions, as the Northwest coast of Peru-Ecuador, northern Argentina, Eastern Amazonia and Northeast Brazil, whereas for other regions they are less robust as in Pantanal region of West Central and southeastern Brazil.

On the first terrestrial ostracod of the Superfamily Cytheroidea (Crustacea, Ostracoda): description of Intrepidocythere ibipora n. gen. n. sp from forest leaf litter in Sao Paulo State, Brazil

Of the three superfamilies of Ostracoda present in fresh water, only the Cytheroidea had thus far no records in terrestrial environments. Here, we report on a new genus and species, Intrepidocythere ibipora n. gen. n. sp., of the ostracod superfamily Cytheroidea, from forest leaf litter in Sao Paulo State, Brazil. Judging from morphological similarities, this new genus is believed to be closely related to the genus Elpidium. Possible pathways that led to the colonisation of terrestrial habitats are discussed, and an overview is given on the distribution of the known terrestrial ostracod lineages. The present findings strengthen the idea that terrestrial ostracods are more common than previously thought, at least in tropical areas.

First-principles calculation of the AlAs/GaAs interface band structure using a self-energy-corrected local density approximation

We apply a self-energy-corrected local density approximation (LDA) to obtain corrected bulk band gaps and to study the band offsets of AlAs grown on GaAs (AlAs/GaAs). We also investigate the Al(x)Ga(1-x)As/GaAs alloy interface, commonly employed in band gap engineering. The calculations are fully ab initio, with no adjustable parameters or experimental input, and at a computational cost comparable to traditional LDA. Our results are in good agreement with experimental values and other theoretical studies. Copyright (C) EPLA, 2011

Orbital-polarization terms: From a phenomenological to a first-principles description of orbital magnetism in density-functional theory

Phenomenological orbital-polarizition (OP) terms have been repeatedly introduced in the single-particle equations of spin-density-functional theory, in order to improve the description of orbital magnetic moments in systems containing transition metal ions. Here we show that these ad hoc corrections can be interpreted as approximations to the exchange-correlation vector potential A(xc) of current-density functional theory (CDFT). This connection provides additional information on both approaches: phenomenological OP terms are connected to first-principles theory, leading to a rationale for their empirical success and a reassessment of their limitations and the approximations made in their derivation. Conversely, the connection of OP terms with CDFT leads to a set of simple approximations to the CDFT potential A(xc), with a number of desirable features that are absent from electron-gas-based functionals. (C) 2008 Wiley Periodicals, Inc.

First stereocontrolled acetylation of a hydroxypropargylpiperidone by lipase CALB

Hydroxypropargylpiperidones rac-1-3 were efficiently obtained by a one-pot three-component coupling reaction; enantioenriched propargylpiperidones were then obtained by a kinetic resolution process using the lipase from Candida antarctica. Lipase CALB has been shown to efficiently catalyse the stereocontrolled acetylation of hydroxypropargylpiperidones rac-3 by promoting stereodiscrimination at the carbinolic centre. The enzymatic catalytic processes allow the separation of the (S,R)- and (S,S)-3 diastereoisomers into the corresponding acetates produced as a (R,S)- and (R,R)-6 diastereoisomeric pair. The CALB was able to discriminate the stereogenic centre of the secondary (R)-enantiomer of rac-3 according to the Kaslauzkas rule. The remote stereogenic centre was not discriminated by the lipase. The functionalised enantioenriched diastereoisomers obtained are important building blocks in organic synthesis. (C) 2010 Elsevier Ltd. All rights reserved.

First chemoenzymatic synthesis of organoselenium amines and amides

A series of organoselenium amines have been synthesized and submitted to the enzymatic kinetic resolution by acetylation mediated by CAL-B (Novozym 435) to give the corresponding chiral amides in an enantiomerically pure form. After evaluating the appropriate lipase, solvent, temperature,and lipase/substrate ratio in the kinetic resolution, the chiral organoselenium amides were obtained with enantiomeric excess of up to 99%. (C) 2008 Elsevier Ltd. All rights reserved.

Sine ira et studio : En kvalitativ analys av institutionaliseringsprocessens konsekvenser inom den nypaganistiska rörelsen Church of All Worlds

Uppsatsen har för avsikt att undersöka hur den nypaganistiska, och i första hand nordamerikanska, rörelsen Church of All Worlds reagerar mot förändring och institutionalisering. För att förstå institutionaliseringsprocessens bakomliggande krafter och identifiera dess konsekvenser, är det övergripande syftet med uppsatsen att utifrån en fallstudie av Church of All Worlds undersöka hur organisationen under sina verksamhetsår förändrats i fråga om (1) förhållande till samhället, (2) ideologi, (3) organisatorisk struktur och (4) ledarskap. Utgångspunkten är att betrakta rörelsen som dels religiös och spirituell, dels organisatorisk och ekonomisk, varför uppsatsen lutar sin teoribildning mot både religions- och samhällsvetenskapen och mot organisationsteorin. Som samhälleliga samt organisatoriska faktorer till Church of All Worlds institutionalisering finner vi den postmoderna motreaktionen mot industrisamhällets missförhållanden samt kritiken mot existensen av den objektiva sanningen. Institutionaliseringens följder är emellertid att rörelsen slutligen upptas som en del av det sen-moderna samhällssystemet. Förändringen märks i första hand då rörelsen under 80-talet förvandlas till en ekonomiskt intresserad organisation med tjänstehierarkier och reglerat ansvar som påföljder. Den byråkratiska arbetsordningen urlakar inte bara rörelsens ideologi, utan tvingar också den nu demokratiskt tillsatte ledaren till radikala åtgärder för att återfå sin makt, något som når sin kulmen i en konflikt med ledarens sorti som yttersta konsekvens.