Time-multiscale methods for the simulation of slow transport problems in atomistic systems

En esta tesis presentamos una teoría adaptada a la simulación de fenómenos lentos de transporte en sistemas atomísticos. En primer lugar, desarrollamos el marco teórico para modelizar colectividades estadísticas de equilibrio. A continuación, lo adaptamos para construir modelos de colectividades estadísticas fuera de equilibrio. Esta teoría reposa sobre los principios de la mecánica estadística, en particular el principio de máxima entropía de Jaynes, utilizado tanto para sistemas en equilibrio como fuera de equilibrio, y la teoría de las aproximaciones del campo medio. Expresamos matemáticamente el problema como un principio variacional en el que maximizamos una entropía libre, en lugar de una energía libre. La formulación propuesta permite definir equivalentes atomísticos de variables macroscópicas como la temperatura y la fracción molar. De esta forma podemos considerar campos macroscópicos no uniformes. Completamos el marco teórico con reglas de cuadratura de Monte Carlo, gracias a las cuales obtenemos modelos computables. A continuación, desarrollamos el conjunto completo de ecuaciones que gobiernan procesos de transporte. Deducimos la desigualdad de disipación entrópica a partir de fuerzas y flujos termodinámicos discretos. Esta desigualdad nos permite identificar la estructura que deben cumplir los potenciales cinéticos discretos. Dichos potenciales acoplan las tasas de variación en el tiempo de las variables microscópicas con las fuerzas correspondientes. Estos potenciales cinéticos deben ser completados con una relación fenomenológica, del tipo definido por la teoría de Onsanger. Por último, aportamos validaciones numéricas. Con ellas ilustramos la capacidad de la teoría presentada para simular propiedades de equilibrio y segregación superficial en aleaciones metálicas. Primero, simulamos propiedades termodinámicas de equilibrio en el sistema atomístico. A continuación evaluamos la habilidad del modelo para reproducir procesos de transporte en sistemas complejos que duran tiempos largos con respecto a los tiempos característicos a escala atómica. ABSTRACT In this work, we formulate a theory to address simulations of slow time transport effects in atomic systems. We first develop this theoretical framework in the context of equilibrium of atomic ensembles, based on statistical mechanics. We then adapt it to model ensembles away from equilibrium. The theory stands on Jaynes' maximum entropy principle, valid for the treatment of both, systems in equilibrium and away from equilibrium and on meanfield approximation theory. It is expressed in the entropy formulation as a variational principle. We interpret atomistic equivalents of macroscopic variables such as the temperature and the molar fractions, wich are not required to be uniform, but can vary from particle to particle. We complement this theory with Monte Carlo summation rules for further approximation. In addition, we provide a framework for studying transport processes with the full set of equations driving the evolution of the system. We first derive a dissipation inequality for the entropic production involving discrete thermodynamic forces and fluxes. This discrete dissipation inequality identifies the adequate structure for discrete kinetic potentials which couple the microscopic field rates to the corresponding driving forces. Those kinetic potentials must finally be expressed as a phenomenological rule of the Onsanger Type. We present several validation cases, illustrating equilibrium properties and surface segregation of metallic alloys. We first assess the ability of a simple meanfield model to reproduce thermodynamic equilibrium properties in systems with atomic resolution. Then, we evaluate the ability of the model to reproduce a long-term transport process in complex systems.

Identification of thermophilic species by the amino acid compositions deduced from their genomes

The global amino acid compositions as deduced from the complete genomic sequences of six thermophilic archaea, two thermophilic bacteria, 17 mesophilic bacteria and two eukaryotic species were analysed by hierarchical clustering and principal components analysis. Both methods showed an influence of several factors on amino acid composition. Although GC content has a dominant effect, thermophilic species can be identified by their global amino acid compositions alone. This study presents a careful statistical analysis of factors that affect amino acid composition and also yielded specific features of the average amino acid composition of thermophilic species. Moreover, we introduce the first example of a ‘compositional tree’ of species that takes into account not only homologous proteins, but also proteins unique to particular species. We expect this simple yet novel approach to be a useful additional tool for the study of phylogeny at the genome level.

Interleaflet clear space is reduced in the membrane of COP I and COP II-coated buds/vesicles.

Intracellular transfers between membrane-bound compartments occur through vesicles that bud from a donor compartment to fuse subsequently with an acceptor membrane. We report that the membrane that delimits COP I or COP II-coated buds/vesicles from the endoplasmic reticulum and the Golgi complex has a thinner interleaflet clear space as compared with the surrounding, noncoated parental membrane. This change is compatible with a compositional change of the membrane bilayer during the budding process.

Conversion of low density polyethylene into fuel through co-processing with vacuum gas oil in a fluid catalytic cracking riser reactor

In this work, mixtures of vacuum gas oil and low density polyethylene, a major component of common industrial and consumer household plastics, were pyrolytically co-processed in a fluid catalytic cracking (FCC) riser reactor as a viable alternative for the energy and petrochemical revalorisation of plastic wastes into valuable petrochemical feedstocks and fuel within an existing industrial technology. Using equilibrium FCC catalyst, the oil–polymer blends were catalytically cracked at different processing conditions of temperatures between 773 K and 973 K and catalyst feed ratios of 5:1, 7:1 and 10:1. The influence of each of these processing parameters on the cracking gas and liquid yield patterns were studied and presented. Further analysed and presented are the different compositional distributions of the obtained liquids and gaseous products. The analysis of the results obtained revealed that with very little modifications to existing process superstructure, yields and compositional distributions of products from the fluid catalytic cracking of the oil–polymer blend in many cases were very similar to those of the processed oil feedstock, bringing to manifest the viability of the feedstock co-processing without significant detriments to FCC product yields and quality.

CONSTITUTIONAL JUSTICE IN AFRICA: An Examination of Constitutional Positivism, Fundamental Law and Rights in Ghana and Nigeria

This work explores the idea of constitutional justice in Africa with a focus on constitutional interpretation in Ghana and Nigeria. The objective is to develop a theory of constitutional interpretation based upon a conception of law that allows the existing constitutions of Ghana and Nigeria to be construed by the courts as law in a manner that best serves the collective wellbeing of the people. The project involves an examination of both legal theory and substantive constitutional law. The theoretical argument will be applied to show how a proper understanding of the ideals of the rule of law and constitutionalism in Ghana and Nigeria necessitate the conclusion that socio-economic rights in those countries are constitutionally protected and judicially enforceable. The thesis argues that this conclusion follows from a general claim that constitutions should represent a ‘fundamental law’ and must be construed as an aspirational moral ideal for the common good of the people. The argument is essentially about the inherent character of ‘legality’ or the ‘rule of law.’ It weaves together ideas developed by Lon Fuller, Ronald Dworkin, T.R.S. Allan and David Dyzenhaus, as well as the strand of common law constitutionalism associated with Sir Edward Coke, to develop a moral sense of ‘law’ that transcends the confines of positive or explicit law while remaining inherently ‘legal’ as opposed to purely moral or political. What emerges is an unwritten fundamental law of reason located between pure morality or natural law on the one hand and strict, explicit, or positive law on the other. It is argued that this fundamental law is, or should be, the basis of constitutional interpretation, especially in transitional democracies like Ghana and Nigeria, and that it grounds constitutional protection for socio-economic rights. Equipped with this theory of law, courts in developing African countries like Ghana and Nigeria will be in a better position to contribute towards developing a real sense of constitutional justice for Africa.

The Theory of Interhybridity: Socio-political Dimensions and Migration Experiences of Post-communist Western Balkan States

The Western Balkans integration within the EU has started a legal process which is the rejection of former communist legal/political approaches and the transformation of former communist institutions. Indeed, the EU agenda has brought vertical/horizontal integration and Europeanization of national institutions (i.e. shifting power to the EU institutions and international authorities). At this point, it is very crucial to emphasize the fact that the Western Balkans as a whole region has currently an image that includes characteristics of both the Soviet socialism and the European democracy. The EU foreign policies and enlargement strategy for Western Balkans have significant effects on four core factors (i.e. Schengen visa regulations, remittances, asylum and migration as an aggregate process). The convergence/divergence of EU member states’ priorities for migration policies regulate and even shape directly the migration dynamics in migrant sender countries. From this standpoint, the research explores how main migration factors are influenced by political and judicial factors such as; rule of law and democracy score, the economic liberation score, political and human rights, civil society score and citizenship rights in Western Balkan countries. The proposal of interhybridity explores how the hybridization of state and non-state actors within home and host countries can solve labor migration-related problems. The economical and sociopolitical labor-migration model of Basu (2009) is overlapping with the multidimensional empirical framework of interhybridity. Indisputably, hybrid model (i.e. collaboration state and non-state actors) has a catalyst role in terms of balancing social problems and civil society needs. Paradigmatically, it is better to perceive the hybrid model as a combination of communicative and strategic action that means the reciprocal recognition within the model is precondition for significant functionality. This will shape social and industrial relations with moral meanings of communication.

Mass Surveillance of Personal Data by EU Member States and its Compatibility with EU Law. CEPS Liberty and Security in Europe No. 61, 6 November 2013

In the wake of the disclosures surrounding PRISM and other US surveillance programmes, this paper assesses the large-scale surveillance practices by a selection of EU member states: the UK, Sweden, France, Germany and the Netherlands. Given the large-scale nature of these practices, which represent a reconfiguration of traditional intelligence gathering, the paper contends that an analysis of European surveillance programmes cannot be reduced to a question of the balance between data protection versus national security, but has to be framed in terms of collective freedoms and democracy. It finds that four of the five EU member states selected for in-depth examination are engaging in some form of large-scale interception and surveillance of communication data, and identifies parallels and discrepancies between these programmes and the NSA-run operations. The paper argues that these programmes do not stand outside the realm of EU intervention but can be analysed from an EU law perspective via i) an understanding of national security in a democratic rule of law framework where fundamental human rights and judicial oversight constitute key norms; ii) the risks posed to the internal security of the Union as a whole as well as the privacy of EU citizens as data owners and iii) the potential spillover into the activities and responsibilities of EU agencies. The paper then presents a set of policy recommendations to the European Parliament.

A New Start for the EU’s Area of Freedom, Security and Justice? Setting of Priorities for the New European Commission. CEPS Commentary, 23 September 2014

The nomination of a First Vice-President (Frans Timmermans) in charge of rule of law and the EU Charter of Fundamental is one of the more far-reaching innovations contained in the new institutional shape of the Juncker Commission. This CEPS Commentary by Sergio Carrera and Elspeth Guild welcomes the fact that a new fundamental rights and rule of law First Vice-President will exercise a coordination and advisory role over the other two JHA Commissioners – Věra Jourová, responsible for Justice, Consumers and Gender Equality (DG Justice); and Dimitris Avramopoulos, responsible for Migration and Home Affairs (DG Home Affairs), but expresses a note caution whether this new role and triangular relationship can be made to work effectively in practice.

In a state of necessity. How has Orban changed Hungary. OSW Point of View Number 41, April 2014

Viktor Orban’s sweeping victory in the 2010 election ensured his party, Fidesz, a constitutional two-thirds majority in parliament. The party took over the rule of the country from the discredited political left when Hungary was plunged in political and economic crisis. Claiming that the circumstances were unusual and that it had a strong electoral mandate, Fidesz introduced radical changes in the country and thus challenged the previous economic and political order. These changes have led to an unprecedented concentration of power and provoked a discussion on the limits of democracy and the rule of law in the European Union. The state’s economic role has strengthened. The Orban government has been unable to overcome economic stagnation but it has managed to stabilise Hungary’s budget situation, which needs to deal with the high debt. Hungary’s relations with most partners in the EU and NATO have cooled due to controversial moves made by its government. As regards foreign policy and economic co-operation, Orban has granted high priority to the ‘Eastern opening’, where Russia has assumed the leading role.

Od demokracji "wirtualnej" ku europejskiej: Geneze i konsekwencje przelomu politycznego w Moldawii. Prace OSW 32/2009. = From "virtual" to European democracy - the origins and consequences of the political breakthrough in Moldova. OSW Study 32/2009

2009 may become a turning point in the history of post-Soviet Moldova. The country’s political class and society are faced with a fundamental choice. On the one hand, if the Party of Communists of the Republic of Moldova, which has governed the country since 2001, remains in power, this would mean a consolidation of the authoritarian rule of the party leader Vladimir Voronin, perpetuation of the superficial nature of democratic institutions and a continuation of the manoeuvring between the European Union and Russia (with the increasing risk of falling into the latter’s exclusive zone of influence). On the other hand, the take over of political power by the opposition parties creates an opportunity for Moldova to resume building a democratic, pluralistic political system based on the rule of law and to develop closer links with the European Union within the framework of the European Neighbourhood Policy, including the Eastern Partnership.

The EU-Ukraine Action Plan on Visa Liberalisation: an assessment of Ukraine's readiness. OSW Commentary No. 45, 2011-01-17

The Action Plan on visas adopted during the recent EU-Ukraine summit is a success for Ukraine. It is the first time that Kyiv has succeeded in obtaining a definition of the conditions and criteria whose fulfilment will enable Ukraine to apply for the lifting of EU visas for its citizens. Ukraine's strong point has been its political will; the lifting of this visa regime has been a priority for all Ukrainian governments since 2005. Since Viktor Yanukovych became president, Ukraine has adopted or prepared key legal acts that brought it nearer to European standards in the area of border and migration management. One of Kyiv's strengths is also its relatively well reformed and efficiently managed border service. Moreover, illegal transit migration via Ukraine is decreasing, and fewer Ukrainians are trying to enter or stay in the EU illegally. Also, Kyiv has efficiently implemented the EU-Ukraine readmission agreement. The hardest task for Ukraine will be to meet the EU’s expectations concerning values, the condition of Ukrainian democracy, and the rule of law. Corruption remains the main barrier to Ukraine's development and modernisation; the courts are weak and the judicial system inefficient. The main undertaking of the new migration service that is being formed at the moment will be to create a civil system of registration, monitoring and regulating the stays of foreign nationals. This may prove difficult, as the supervisory authority (the Ministry of the Interior) remains an unreformed, police-type bureaucratic institution. Ukraine is lagging behind countries such as Russia, Belarus and Moldova when it comes to the introduction of biometric documents. Another problem is the lack of an electronic information system on foreign nationals, visas and border crossings which would be accessible to all the relevant services and institutions. For these reasons, the complete abolition of visas seems to be a longterm perspective, especially considering that many EU countries, which themselves are faced with the problem of migrants’ integration, are rather sceptical about the further liberalisation of movement of people with their eastern neighbours. In the immediate future, if Ukraine meets some of the requirements set by the EU, it will be able to seek the extension of the visa facilitations that have been in operation since 2008.

Counter-reforms in times of prosperity. OSW Point of View, September 2006

In 2000, Vladimir Putin came to power after nearly a decade of the rule of the first Russian president, Boris Yeltsin. As prime minister, and later as a candidate for president, Putin announced that he would reform the state. The main assumptions of this reform were presented during a congress of the pro-Kremlin Unity movement, in Putin's address entitled 'Russia at the turn of the millennium' which was delivered on 29 December 1999, and later in a open letter to voters published on 25 February 2000. Both declarations were rather general, but they gave a clear picture of the principal directions of and priority areas for the future president's efforts: they outlined Russia's development path as pro-market and democratic. Nearly seven years have passed since Vladimir Putin came to power, a time for a summary of his achievements. In a way, Vladimir Putin has partially delivered on his initial declarations; indeed, Russia has undergone a deep transformation. However, when seen in the light of the president’s initial promises, the changes appear to be no more than 'counter-reforms', because instead of putting into practice the policy he outlined seven years ago, they have largely followed a different, if not entirely opposite direction.

The Great Game around Turkmenistan. OSW Point of View, August 2008

The rise of a new leader of the state of Turkmenistan – President Gurbanguly Berdymukhammedov, who became ruler of the central Asian state after the 21-year rule of Saparmurad Niyazov, the self-proclaimed Turkmenbashi, who died on December 21, 2006 – has initiated changes in Turkmenistan’s political life. The new president has broken with the previous policy of self-isolation, and has directed the country towards openness to the outside world. Opportunities have thereby arisen for competitors in the ‘Great Game’, to gain political influence in Turkmenistan and access to hitherto unexploited Turkmen deposits of gas and oil. A new stage in the Great Game, which has been played for influence in Central Asia and control of access to its energy resources for many years, can thus be said to have been launched, and Turkmenistan has become the main setting for it. The major actors involved are Russia, the United States, China and the European Union.

Morocco at the Crossroads: Seizing the window of opportunity for sustainable development. MEDPRO Technical Report No. 2/April 2011

The question of state sustainability is highly relevant in the case of Morocco. Despite the image of a modernising and liberalising country, Morocco is undergoing a delicate phase in its development. The recent upheavals in the Maghreb and the Middle East alongside the growing problems of poor education and high unemployment are likely to bring to the surface the unsustainable elements of Morocco’s status quo. The central issues concern the quality of institutions, reforms aimed at promoting the rule of law, curbing corruption and overhauling the judiciary. This paper will argue that while institutional quality is a pre-requisite for successful and sustainable socioeconomic performance, this cannot be achieved unless major reforms in the political system are carried out. There exists a window of opportunity to accelerate reforms and to address the acute centralisation of Moroccan politics and decision-making, the lack of accountability of the monarchic institutions, as well as the fragility of representative bodies, such as parties and trade unions. Seizing this window of opportunity could spare Morocco a period of instability, while also assuring continuity in the framework of the transition that started in 1999 when the new king came to power.

The European Council’s Guidelines for the Area of Freedom, Security and Justice 2020: Subverting the ‘Lisbonisation’ of Justice and Home Affairs? CEPS Essay No. 13, 14 July 2014

In its Conclusions of 26-27 June 2014, the European Council has adopted the new “Strategic Guidelines for Legislative and Operational Planning for the coming years within the EU’s Area of Freedom, Security and Justice (AFSJ)”. These Guidelines reveal a pre-Lisbon Treaty mindset among the EU member states and the Justice and Home Affairs Council. This essay argues that the Guidelines are mainly driven by the interests and agendas of national Ministries of Interior and Justice and are only “strategic” to the extent that they aim at first, re-injecting ‘intergovernmentalism’ or bringing back the old EU Third Pillar ways of working to the new EU institutional setting of the AFSJ and second, at sidelining the EU Charter of Fundamental Rights and rule of law in the AFSJ. The paper argues that the European Council Guidelines seek to prevent the advances in Justice and Home Affairs cooperation as envisaged in the Treaty of Lisbon, particularly its emphasis on supranational democratic, legal and judicial accountability. As a consequence of this move to ‘de-Lisbonise’ JHA cooperation, fundamental rights and rule of law-related initiatives will be neglected and the interest of the individual will be displaced from the centre of gravity in the coming AFSJ 2020 policy agenda.