937 resultados para TRANSITION-STATE


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In this paper I review the ways in which the glassy state is obtained both in nature and in materials science and highlight a "new twist"--the recent recognition of polymorphism within the glassy state. The formation of glass by continuous cooling (viscous slowdown) is then examined, the strong/fragile liquids classification is reviewed, and a new twist-the possibility that the slowdown is a result of an avoided critical point-is noted. The three canonical characteristics of relaxing liquids are correlated through the fragility. As a further new twist, the conversion of strong liquids to fragile liquids by pressure-induced coordination number increases is demonstrated. It is then shown that, for comparable systems, it is possible to have the same conversion accomplished via a first-order transition within the liquid state during quenching. This occurs in the systems in which "polyamorphism" (polymorphism in the glassy state) is observed, and the whole phenomenology is accounted for by Poole's bond-modified van der Waals model. The sudden loss of some liquid degrees of freedom through such weak first-order transitions is then related to the polyamorphic transition between native and denatured hydrated proteins, since the latter are also glass-forming systems--water-plasticized, hydrogen bond-cross-linked chain polymers (and single molecule glass formers). The circle is closed with a final new twist by noting that a short time scale phenomenon much studied by protein physicists-namely, the onset of a sharp change in d/dT ( is the Debye-Waller factor)--is general for glass-forming liquids, including computer-simulated strong and fragile ionic liquids, and is closely correlated with the experimental glass transition temperature. The latter thus originates in strong anharmonicity in certain components of the vibrational density of states, which permits the system to access the multiple minima of its configuration space. The connection between the anharmonicity in these modes, vibrational localization, the Kauzmann temperature, and the fragility of the liquid is proposed as the key problem in glass science.

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The levels in Sn-129 populated from the beta(-) decay of In-129 isomers were investigated at the ISOLDE facility of CERN using the newly commissioned ISOLDE Decay Station (IDS). The lowest 1/2(+) state and the 3/2(+) ground state in 129Sn are expected to have configurations dominated by the neutron s(1/2) (l = 0) and d(3/2) (l = 2) single-particle states, respectively. Consequently, these states should be connected by a somewhat slow l-forbidden M1 transition. Using fast-timing spectroscopy we havemeasured the half-life of the 1/2(+) 315.3-keV state, T-1/2 = 19(10) ps, which corresponds to a moderately fast M1 transition. Shell-model calculations using the CD-Bonn effective interaction, with standard effective charges and g factors, predict a 4-ns half-life for this level. We can reconcile the shell-model calculations to the measured T-1/2 value by the renormalization of the M1 effective operator for neutron holes.

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We perform numerical simulations, including parallel tempering, a four-state Potts glass model with binary random quenched couplings using the JANUS application-oriented computer. We find and characterize a glassy transition, estimating the critical temperature and the value of the critical exponents. Nevertheless, the extrapolation to infinite volume is hampered by strong scaling corrections. We show that there is no ferromagnetic transition in a large temperature range around the glassy critical temperature. We also compare our results with those obtained recently on the “random permutation” Potts glass.

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We investigate the critical properties of the four-state commutative random permutation glassy Potts model in three and four dimensions by means of Monte Carlo simulations and a finite-size scaling analysis. By using a field programmable gate array, we have been able to thermalize a large number of samples of systems with large volume. This has allowed us to observe a spin-glass ordered phase in d=4 and to study the critical properties of the transition. In d=3, our results are consistent with the presence of a Kosterlitz-Thouless transition, but also with different scenarios: transient effects due to a value of the lower critical dimension slightly below 3 could be very important.

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We present a detailed numerical study on the effects of adding quenched impurities to a three dimensional system which in the pure case undergoes a strong first order phase transition (specifically, the ferromagnetic/paramagnetic transition of the site-diluted four states Potts model). We can state that the transition remains first-order in the presence of quenched disorder (a small amount of it) but it turns out to be second order as more impurities are added. A tricritical point, which is studied by means of Finite-Size Scaling, separates the first-order and second-order parts of the critical line. The results were made possible by a new definition of the disorder average that avoids the diverging-variance probability distributions that arise using the standard methodology. We also made use of a recently proposed microcanonical Monte Carlo method in which entropy, instead of free energy, is the basic quantity.

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Perylene bisimides (PBIs) are n-type semiconducting and photogenerating materials widely used in a variety of optoelectronic devices. Particularly interesting are PBIs that are simultaneously water-soluble and liquid-crystalline (PBI-W+LC) and, thus, attractive for the development of high-performing easily processable applications in biology and “green” organic electronics. In this work, singular temperatures connected to charge transport mechanism transitions in a PBI-W+LC derivative are determined with high accuracy by means of temperature-dependent photocurrent studies. These singular temperatures include not only the ones observed at 60 and 110 °C, corresponding to phase transition temperatures from crystalline to liquid-crystalline (LC) and from LC to the isotropic phase, respectively, as confirmed by differential scanning calorimetry (DSC), but also a transition at 45 °C, not observed by DSC. By analyzing the photocurrent dependence simultaneously on temperature and on light intensity, this transition is interpreted as a change from monomolecular to bimolecular recombination. These results might be useful for other semiconducting photogenerating materials, not necessarily PBIs or even organic semiconductors, which also show transport behavior changes at singular temperatures not connected with structural or phase transitions.

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[Introduction.] This paper discusses the uncertain future of Member State BITs with third countries in the light of the developing EU investment policy. The question will be examined on the basis of the proposed Regulation establishing transitional arrangements for bilateral investment agreements between Member States and third countries presented by the Commission on 7 July 20101 and the European Parliament’s Position adopted at first reading on 10 May 2011.2 The proposed Regulation and the Commission Communication of the same day are meant to be the “first steps in the development of an EU international investment policy”.3 The first chapters present the legal framework relevant for this question and its evolution to better understand the particular challenges of this transition process. The second chapter examines the relationship of EU law and investment law, with a brief introduction of the notion of investment law and the scope of the EU’s new investment competence. The third chapter outlines the legal framework for the continuation and termination of treaties under international and EU law. The fourth chapter concerns BITs, first covering the particular nature of BITs and then the CJEU’s judgments in the BIT Cases of 2009. The fifth chapter consists of a step by step analysis of the different provisions of the proposed Regulation.

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This CEPS Policy Brief examines the provisions for bail-in in the European Union – that is, the principle whereby any public measure to recapitalise a bank with insufficient prudential capital must be preceded by a write-down or conversion into equity of creditors’ claims – in state aid policies and in the new resolution framework for failing banks, with two aims: i) to assess whether and how they are coordinated and ii) more importantly, whether they address satisfactorily the question of systemic stability that may arise when investors fear that creditors’ claims are likely to be bailed-in in a bank crisis. The issue is especially relevant in the present context, as the comprehensive assessment exercise underway for EU banks falling under the direct supervision of the European Central Bank may lead supervisors to require substantial capital injections simultaneously for many of the banks involved, possibly shaking investors’ confidence across EU banking markets. The authors conclude that the two sets of rules are, broadly speaking, mutually consistent and that they already contain sufficient safeguards to address systemic stability concerns. However, the balance of the elements underpinning the European Commission’s decisions in individual cases may not be clear to bank creditors and potential investors in financial markets. The impression of unneeded rigidity on this very sensitive issue has been heightened by official statements over-emphasising that each case will be assessed individually under competition rules, thus feeding the concern that the systemic dimension of the issue may have been underestimated. Therefore, further clarification by the Commission may be needed on how the various criteria will be applied during the ongoing transition to banking union – perhaps through a new communication completing the state aid framework for banks in view of the adoption of the new resolution rules.

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The European Council Summit of 23-24 October 2014 may have been relatively low key, but many important decisions were made which could encourage historical changes. In this post-summit analysis, Janis A. Emmanouilidis examines the agreement reached on a new climate and energy policy framework for 2020-2030 which despite falling short of the European Commission’s original proposals, it nevertheless delivers a positive message to international community ahead of the global climate negotiations next year. He also highlights the significance of the request from euro-zone leaders for a new report on ‘better economic governance’ by December. More broadly, he uses this moment of transition in the EU’s leadership to analyse the current state and future direction of the Union, and underlines the need to provide a coherent and holistic response to the damage caused by the crisis and the challenges facing the Union, on the basis of an ambitious but pragmatic ‘package deal’ – a new pact between EU governments, and between the Union and its citizens – to heal the divisions of recent years and restore public faith in the benefits of EU membership.

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Any analysis of the prospects for stability and sustainability in the states of Syria and Lebanon reveals the strong ties that exist between these two countries and the impact of external influences on their overall development. Their trajectories, while starkly divergent in terms of the challenges confronting them at present, converge on a path of long-term unsustainability. Lebanon is in the midst of yet another transition phase, triggered by the collapse of Hariri’s government in January 2011. The current situation might be described as one of deteriorating status quo; the state is performing poorly in terms of its delivery of fundamental public services and its institutional legitimacy is tenuous in the face of emerging para-state structures and latent (occasionally active) violence. In Syria, challenges to the sustainability of the state have evolved dramatically since the beginning of 2011, and are now nearing a tipping point. In view of the mounting unrest and violence in the country, the future prospects for its economic and political development are dim. More ominously, the risk of widespread conflict, with sectarian overtones, cannot be discounted.

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From the Introduction. Arab revolutions have sparked real hopes for democracy, but the situation varies from one state to another and change has taken various directions, with unpredictable outcomes in the future. In light of current events, most of these countries seem to have failed in their democratic transition and also face the dissolution of their state apparatus in bloody civil wars. This leaves the door open to interpretations associating democracy with chaos. In this view, preserving post-colonial states – authoritarian in most cases – is better than having no state at all. This partially justified the coup that took place in Egypt, where the ‘Deep State’ has recovered its capabilities in a dictatorial manner. The Arab world thus faced an impasse: the state is either stable but authoritarian or democratic yet threatened with dissolution. The dilemma results in an impossible choice between stable dictatorship or freedom ending in chaos.

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Addressing high and volatile natural resource prices, uncertain supply prospects, reindustrialization attempts and environmental damages related to resource use, resource efficiency has evolved into a highly debated proposal among academia, policy makers, firms and international financial institutions (IFIs). In 2011, the European Union (EU) declared resource efficiency as one of its seven flagship initiatives in its Europe 2020 strategy. This paper contributes to the discussions by assessing its key initiative, the Roadmap to a Resource Efficient Europe (EC 2011 571), following two streams of evaluation. In a first step, resource efficiency is linked to two theoretical frameworks regarding sustainability, (i) the sustainability triangle (consisting of economic, social and ecological dimensions) and (ii) balanced sustainability (combining weak and strong sustainability). Subsequently, both sustainability frameworks are used to assess to which degree the Roadmap follows the concept of sustainability. It can be concluded that it partially respects the sustainability triangle as well as balanced sustainability, primarily lacking a social dimension. In a second step, following Steger and Bleischwitz (2009), the impact of resource efficiency on competitiveness as advocated in the Roadmap is empirically evaluated. Using an Arellano–Bond dynamic panel data model reveals no robust impact of resource efficiency on competiveness in the EU between 2004 and 2009 – a puzzling result. Further empirical research and enhanced data availability are needed to better understand the impacts of resource efficiency on competitiveness on the macroeconomic, microeconomic and industry level. In that regard, strengthening the methodologies of resource indicators seem essential. Last but certainly not least, political will is required to achieve the transition of the EU-economy into a resource efficient future.

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We compare a new mid-Pleistocene sea surface temperature (SST) record from the eastern tropical Atlantic to changes in continental ice volume, orbital insolation, Atlantic deepwater ventilation, and Southern Ocean front positions to resolve forcing mechanisms of tropical Atlantic SST during the mid-Pleistocene transition (MPT). At the onset of the MPT, a strong tropical cooling occurred. The change from a obliquity- to a eccentricity-dominated cyclicity in the tropical SST took place at about 650 kyr BP. In orbital cycles, tropical SST changes significantly preceded continental ice-volume changes but were in phase with movements of Southern Ocean fronts. After the onset of large-amplitude 100-kyr variations, additional late glacial warming in the eastern tropical Atlantic was caused by enhanced return flow of warm waters from the western Atlantic driven by strong trade winds. Pronounced 80-kyr variations in tropical SST occurred during the MPT, in phase with and likely directly forced by transitional continental ice-volume variations. During the MPT, a prominent anomalous long-term tropical warming occurred, likely generated by extremely northward displaced Southern Ocean fronts. While the overall pattern of global climate variability during the MPT was determined by changes in mean state and frequency of continental ice volume variations, tropical Atlantic SST variations were primarily driven by early changes in Subantarctic sea-ice extent and coupled Southern Ocean frontal positions.

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Federal Highway Administration, Office of Research, Development, and Technology, Washington, D.C.

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"Robert Leininger, Interim State Superintendent of Education."