A new 3-D polymeric spin transition compound: [tris(1,4-bis-(tetrazol-1-yl) butane-N1,N1′)iron(II)] bis(perchlorate)

A series of novel polymeric compounds of formula [M(btzb)3][ClO4]2 (Mll = Fe, Ni or Cu) with btzb = 1,4-bis-(tetrazol-1-yl)butane have been prepared and their physical properties investigated. The btzb ligand has been prepared and its crystal structure determined, together with a tentative crystal structure of the 3-D compound [Fe(btzb)3][ClO4]2. The model of the latter shows two symmetry-related, interpenetrating Fe-btzb networks in which the iron(II) ions approach each other as close as 8.3 and 9.1 Å. This supramolecular catenane undergoes a sharp thermal spin transition around 160 K with hysteresis (20 K) along with a pronounced thermochromic effect. The spin crossover behaviour has been followed by magnetic, DSC, optical spectroscopy and 57Fe Mössbauer spectroscopy measurements. Irradiation with green light at low temperature leads to population of the metastable high-spin state for the thermally active iron(ll) ions. The nature of the spin crossover behaviour has been discussed in detail.

[Fe(μ-btzmp)2(btzmp)2](ClO4)2:a doubly-bridged 1D spin-transition bistetrazole-based polymer showing thermal hysteresis behaviour

The reaction of btzmp (1,2-bis(tetrazol-1-yl)-2-methylpropane) with Fe(ClO4)2 generates a 1D polymeric species, [Fe(μ-btzmp)2(btzmp)2](ClO4)2, showing a steep spin transition (T½↑ = 136 K and T ½↓ = 133 K) with a 3 K thermal hysteresis. The crystal structure at 100 and 200 K reveals that, in contrast to other bistetrazole based spin-transition systems such as [Fe(endi)3](BF4)2 and [Fe(btzp)3](ClO4)2, the present compound has only two ligands bridging the metallic centres, while the other two coordination positions are occupied by two mono-coordinated (non-bridging) btzmp ligands. This peculiarity confers an unprecedented crystal packing in the series of 1D bistetrazole based polymers. The change in spin state is accompanied by an order/disorder transition of the ClO4- counterion. A careful examination of the structural changes occurring upon the spin transition indicates that this order/disorder is most likely affected by the modification of the [tetrazole-centroid]-ND-Fe angle (which is typical of bistetrazole spin-transition materials). Apart from X-ray analysis, also magnetic susceptibility, Mössbauer and UV-vis spectroscopies have been used to characterise the HS and the LS states of [Fe(µ-btzmp)2(btzmp)2](ClO4)2. © The Royal Society of Chemistry.

Transition and foreign aid policies in the Visegrád countries:a path dependant approach

The paper argues that the current emerging international development policies of the Visegrád (V4) countries are heavily influenced by the certain aspects of the Communist past and the transition process. Due to these influences, the V4 countries have difficulties in adapting the foreign aid practices of Western donors and this leads to the emergence of a unique Central and Eastern European development cooperation model. As an analytical background, the paper builds on the path dependency theory of transition. A certain degree of path dependence is clearly visible in V4 foreign aid policies, and the paper analyses some aspects of this phenomenon: how these new emerging foreign aid donors select their partner countries, how much they spend on aid, how they formulate their aid delivery policies and institutions and what role the non-state actors play. The main conclusions of the paper are that the legacies of the Communist past have a clear influence and the V4 countries still have a long way to go in adapting their aid policies to international requirements.

On OBDD Transformations Representing Finite State Automata

We present OBDD transformation problem representing finite labeled transition systems corresponding to some congruence relation. Transformations are oriented toward obtaining the OBDD of a minimized transition system for this congruence relation.

Timed Transition Automata as Numerical Planning Domain

A general technique for transforming a timed finite state automaton into an equivalent automated planning domain based on a numerical parameter model is introduced. Timed transition automata have many applications in control systems and agents models; they are used to describe sequential processes, where actions are labelling by automaton transitions subject to temporal constraints. The language of timed words accepted by a timed automaton, the possible sequences of system or agent behaviour, can be described in term of an appropriate planning domain encapsulating the timed actions patterns and constraints. The time words recognition problem is then posed as a planning problem where the goal is to reach a final state by a sequence of actions, which corresponds to the timed symbols labeling the automaton transitions. The transformation is proved to be correct and complete and it is space/time linear on the automaton size. Experimental results shows that the performance of the planning domain obtained by transformation is scalable for real world applications. A major advantage of the planning based approach, beside of the solving the parsing problem, is to represent in a single automated reasoning framework problems of plan recognitions, plan synthesis and plan optimisation.

The new institutionalism in the context of Kosovo's transition:regulatory institutions in contested states

This article explores the new institutionalist literature in political economy in the context of Kosovo's contested statehood, focusing on institutional arbitrage and legitimacy. This article considers both the consequences of institutions for actors' behaviour and the norms that shape this, as well as the factors determining the legitimacy of institutions. In doing so, it combines the new institutionalist theory with documentary and interview material collected during research on energy regulation in one contested state, Kosovo. Rather than singling out one particular variety of "new institutionalism", the article attempts to blend insights from historical (or "political"), rational choice, and sociological institutionalism. © 2014 © 2014 Taylor & Francis.

Laminar-turbulent transition in Raman fiber lasers:a first passage statistics based analysis

Loss of coherence with increasing excitation amplitudes and spatial size modulation is a fundamental problem in designing Raman fiber lasers. While it is known that ramping up laser pump power increases the amplitude of stochastic excitations, such higher energy inputs can also lead to a transition from a linearly stable coherent laminar regime to a non-desirable disordered turbulent state. This report presents a new statistical methodology, based on first passage statistics, that classifies lasing regimes in Raman fiber lasers, thereby leading to a fast and highly accurate identification of a strong instability leading to a laminar-turbulent phase transition through a self-consistently defined order parameter. The results have been consistent across a wide range of pump power values, heralding a breakthrough in the non-invasive analysis of fiber laser dynamics.

A hydrothermally stable transition alumina by condensation-enhanced self-assembly and pyrolysis crystallization:application in the steam reforming of methane

The preparation of a steam-based hydrothermally stable transition alumina is reported. The gel was derived from a synthetic sol-gel route where Al-tri-sec-butoxide is hydrolysed in the presence of a non-ionic surfactant (EO20PO70EO20), HCl as the catalyst and water (H2O/Al = 6); the condensation was enhanced by treating the hydrolysed gel with tetrabutylammonium hydroxide (TBAOH), after which it was dried at 60 °C by solvent evaporation. The so-obtained mesophase was crystallized under argon at 1200 °C (1 h) producing a transition alumina containing δ/α, and possibly θ, alumina phases. Due to its surface acidity, the pyrolysis conditions transform the block copolymer into a cross-linked char structure that embeds the alumina crystallites. Calcination at 650 °C generates a fully porous material by burning the char; a residual carbon of 0.2 wt.% was found, attributed to the formation of surface (oxy)carbides. As a result, this route produces a transition alumina formed by nanoparticles of about 30 nm in size on average, having surface areas in the range of 59-76 m2 g-1 with well-defined mesopores centered at 14 nm. The material withstands steam at 900 °C with a relative surface area rate loss lower than those reported for δ-aluminas, the state-of-the-art MSU-X γ-alumina and other pure γ-aluminas. The hydrothermal stability was confirmed under relevant CH4 steam reforming conditions after adding Ni; a much lower surface area decay and higher CH4 conversion compared to a state-of-the-art MSU-X based Ni catalyst were observed. Two effects are important in explaining the properties of such an alumina: the char protects the particles against sintering, however, the dominant effect is provided by the TBAOH treatment that makes the mesophase more resistant to coarsening and sintering. This journal is © the Partner Organisations 2014.

Transition and Foreign Aid Policies in the Visegrád Countries: A Path Dependant Approach

The paper argues that the current emerging international development policies of the Visegrád (V4) countries are heavily influenced by the certain aspects of the communist past and the transition process. Due to these influences, the V4 countries have difficulties in adapting the foreign aid practices of Western donors and this leads to the emergence of a unique Central and Eastern European development cooperation model. As an analytical background, the paper builds on the path dependency theory of transition. A certain degree of path dependence is clearly visible in V4 foreign aid policies, and the paper analyzes some aspects of this phenomenon: how these new emerging foreign aid donors select their partner countries, how much they spend on aid, how they formulate their aid delivery policies and institutions and what role the non state actors play. The main conclusions of the paper are that the legacies of the communist past have a clear influence and the V4 countries still have a long way to go in adapting their aid policies to international requirements.

Negotiating identities, striving for state recognition: Blacks in Córdoba, Argentina 1776–1853

Race in Argentina played a significant role as a highly durable construct by identifying and advancing subjects (1776–1810) and citizens (1811–1853). My dissertation explores the intricacies of power relations by focusing on the ways in which race informed the legal process during the transition from a colonial to national State. It argues that the State’s development in both the colonial and national periods depended upon defining and classifying African descendants. In response, people of African descendent used the State’s assigned definitions and classifications to advance their legal identities. It employs race and culture as operative concepts, and law as a representation of the sometimes, tense relationship between social practices and the State’s concern for social peace. This dissertation examines the dynamic nature of the court. It utilizes the theoretical concepts multicentric legal orders that are analyzed through weak and strong legal pluralisms, and jurisdictional politics, from the late eighteenth to early nineteenth centuries. This dissertation juxtaposes various levels of jurisdiction (canon/state law and colonial/national law) to illuminate how people of color used the legal system to ameliorate their social condition. In each chapter the primary source materials are state generated documents which include criminal, ecclesiastical, civil, and marriage dissent court cases along with notarial and census records. Though it would appear that these documents would provide a superficial understanding of people of color, my analysis provides both a top-down and bottom-up approach that reflects a continuous negotiation for African descendants’ goal for State recognition. These approaches allow for implicit or explicit negotiation of a legal identity that transformed slaves and free African descendants into active agents of their own destinies.

Exploring thermal and mechanical properties of selected transition elements under extreme conditions: Experiments at high pressures and high temperatures

Transition metals (Ti, Zr, Hf, Mo, W, V, Nb, Ta, Pd, Pt, Cu, Ag, and Au) are essential building units of many materials and have important industrial applications. Therefore, it is important to understand their thermal and physical behavior when they are subjected to extreme conditions of pressure and temperature. This dissertation presents: • An improved experimental technique to use lasers for the measurement of thermal conductivity of materials under conditions of very high pressure (P, up to 50 GPa) and temperature (T up to 2500 K). • An experimental study of the phase relationship and physical properties of selected transition metals, which revealed new and unexpected physical effects of thermal conductivity in Zr, and Hf under high P-T. • New phase diagrams created for Hf, Ti and Zr from experimental data. • P-T dependence of the lattice parameters in α-hafnium. Contrary to prior reports, the α-ω phase transition in hafnium has a negative dT/dP slope. • New data on thermodynamic and physical properties of several transition metals and their respective high P-T phase diagrams. • First complete thermodynamic database for solid phases of 13 common transition metals was created. This database has: All the thermochemical data on these elements in their standard state (mostly available and compiled); All the equations of state (EoS) formulated from pressure-volume-temperature data (measured as a part of this study and from literature); Complete thermodynamic data for selected elements from standard to extreme conditions. The thermodynamic database provided by this study can be used with available thermodynamic software to calculate all thermophysical properties and phase diagrams at high P-T conditions. For readers who do not have access to this software, tabulated values of all thermodynamic and volume data for the 13 metals at high P-T are included in the APPENDIX. In the APPENDIX, a description of several other high-pressure studies of selected oxide systems is also included. Thermophysical properties (Cp, H, S, G) of the high P-T ω-phase of Ti, Zr and Hf were determined during the optimization of the EoS parameters and are presented in this study for the first time. These results should have important implications in understanding hexagonal-close-packed to simple-hexagonal phase transitions in transition metals and other materials.

A 2,500-year record of environmental change in Highlands Hammock State Park (Central Florida, U.S.A.) inferred from siliceous microfossils

Analysis of siliceous microfossils of a 79 cm long peat sediment core from Highlands Hammock State Park, Florida, revealed distinct changes in the local hydrology during the past 2,500 years. The coring site is a seasonally inundated forest where water availability is directly influenced by precipitation. Diatoms, chrysophyte statospores, sponge remains and phytoliths were counted in 25 samples throughout the core. Based on the relative abundance of diatom species, the record was subdivided into four diatom assemblage zones, which mainly reflect the hydrological state of the study site. An age-depth relationship based on radiocarbon measurements of eight samples reveals a basal age of the core of approximately 2,500 cal. yrs. BP. Two significant changes of diatom assemblage composition were found that could be linked to both, natural and anthropogenic influences. At 700 cal. yrs. BP, the diatom record documents a shift from tychoplanktonicAulacoseira species to epiphytic Eunotia species, indicating a shortening of the hydroperiod, i.e. the time period during which a wetland is covered by water. This transition was interpreted as being triggered by natural climate change. In the middle of the twentieth century a second major turnover took place, at that time however, as a result of human impact on the park hydrology through the construction of dams and canals close to the study site.

Layered graphitic carbon host formation during liquid-free solid state growth of metal pyrophosphates

We report a successful ligand- and liquid-free solid state route to form metal pyrophosphates within a layered graphitic carbon matrix through a single step approach involving pyrolysis of previously synthesized organometallic derivatives of a cyclotriphosphazene. In this case, we show how single crystal Mn2P2O7 can be formed on either the micro- or the nanoscale in the complete absence of solvents or solutions by an efficient combustion process using rationally designed macromolecular trimer precursors, and present evidence and a mechanism for layered graphite host formation. Using in situ Raman spectroscopy, infrared spectroscopy, X-ray diffraction, high resolution electron microscopy, thermogravimetric and differential scanning calorimetric analysis, and near-edge X-ray absorption fine structure examination, we monitor the formation process of a layered, graphitic carbon in the matrix. The identification of thermally and electrically conductive graphitic carbon host formation is important for the further development of this general ligand-free synthetic approach for inorganic nanocrystal growth in the solid state, and can be extended to form a range of transition metals pyrophosphates. For important energy storage applications, the method gives the ability to form oxide and (pyro)phosphates within a conductive, intercalation possible, graphitic carbon as host–guest composites directly on substrates for high rate Li-ion battery and emerging alternative positive electrode materials

Single-crystal micro/nanostructures and thin films of lamellar molybdenum oxide by solid-state pyrolysis of organometallic derivatives of a cyclotriphosphazene

The solid-state pyrolysis of organometallic derivatives of a cyclotriphosphazene is demonstrated to be a new, simple and versatile solid-state templating method for obtaining single-crystal micro- and nanocrystals of transition and valve metal oxides. The technique, when applied to Mo-containing organometallics N3P3[OC6H4CH2CN·Mo(CO)5]6 and N3P3[OC6H4CH2CN·Mo(CO)4 py]6, results in stand-alone and surface-deposited lamellar MoO3 single crystals, as determined by electron and atomic force microscopies and X-ray diffraction. The size and morphology of the resulting crystals can be tuned by the composition of the precursor. X-ray photoelectron and infrared spectroscopies indicate that the deposition of highly lamellar MoO3 directly on an oxidized (400 nm SiO2) surface or (100) single-crystal silicon surfaces yields a layered uniphasic single-crystal film formed by cluster diffusion on the surface during pyrolysis of the metal-carbonyl derivatives. For MoO3 in its layered form, this provides a new route to an important intercalation material for high energy density battery materials.

Lead oxide-modified TiO2 photocatalyst: tuning light absorption and charge carrier separation by lead oxidation state

Modification of TiO2 with metal oxide nanoclusters such as FeOx, NiOx has been shown to be a promising approach to the design of new photocatalysts with visible light absorption and improved electron–hole separation. To study further the factors that determine the photocatalytic properties of structures of this type, we present in this paper a first principles density functional theory (DFT) investigation of TiO2 rutile(110) and anatase(001) modified with PbO and PbO2 nanoclusters, with Pb2+ and Pb4+ oxidation states. This allows us to unravel the effect of the Pb oxidation state on the photocatalytic properties of PbOx-modified TiO2. The nanoclusters adsorb strongly at all TiO2 surfaces, creating new Pb–O and Ti–O interfacial bonds. Modification with PbO and PbO2 nanoclusters introduces new states in the original band gap of rutile and anatase. However the oxidation state of Pb has a dramatic impact on the nature of the modifications of the band edges of TiO2 and on the electron–hole separation mechanism. PbO nanocluster modification leads to an upwards shift of the valence band which reduces the band gap and upon photoexcitation results in hole localisation on the PbO nanocluster and electron localisation on the surface. By contrast, for PbO2 nanocluster modification the hole will be localised on the TiO2 surface and the electron on the nanocluster, thus giving rise to two different band gap reduction and electron–hole separation mechanisms. We find no crystal structure sensitivity, with both rutile and anatase surfaces showing similar properties upon modification with PbOx. In summary the photocatalytic properties of heterostructures of TiO2 with oxide nanoclusters can be tuned by oxidation state of the modifying metal oxide, with the possibility of a reduced band gap causing visible light activation and a reduction in charge carrier recombination.