High-energy transitions of shallow magnetodonors in a GaAs/Al0.3Ga0.7As multiple quantum well

The high-energy states of a shallow donor in a GaAs/Ga0.7Al0.3As multiple-quantum-well structure subjected to a magnetic field in the growth direction are studied both theoretically and experimentally. Effects due to higher confinement subbands as well as due to the electron-phonon interaction are investigated. We show that most of the peaks in the infrared photoconductivity spectrum are due to direct transitions from the ground state to the m = +/-1 magnetodonor states associated with the first subband, but transitions to the m = +/-1 states of the third subband are also apparent. The remaining photoconductivity peaks are explained by phonon-assisted impurity transitions.

Benchmarking Energy Transitions: An Irish Case Study

The challenges of a low carbon energy transition have now been recognized by most nation states, each of whom have responded with differing visions, strategies and programmes, with variable veracity and effectiveness. Given the complexity of each country’s energy system (and sub-systems such as mobility, food etc), the differing sources and wealth of indigenous energy resources, the variable legacy of the fossil fuel regime and differing capacity to respond to global shifts in energy markets, it is clear that each country will respond to this challenge in very different ways.
This poses difficulties for understanding the extent to which a transition may be taking hold in any territory as simple indicators such as GHG emission data or increases in renewable energy ignore the complex contexts in which transitions take place. Drawing on the results of a study, funded by the Irish Environmental Protection Agency (Characterizing and Catalyzing Transitions) and using the wider theoretical framework of socio-technological transitions, this paper will explore the challenges, virtues and constraints of attempting to ‘benchmark’ the Republic of Ireland’s transition. This will lead to wider observations on the normative nature of benchmarking and a critical review of how we conceptualize the very idea of transition.

Catalysing the Irish Energy Transition: Capacities and Challenges

The transition to a “low carbon, climate resilient and environmentally sustainable economy by the end of the 
year 2050” has been conceptualised as the “national transition objective” in the Irish Climate Action and Low Carbon Development Bill, passed in late 2015. This has raised a myriad of questions over how this can be operationalised and resourced and whether it can maintain political momentum. This paper assesses the utility of framings informed by the transitions (MLP) and technological innovation systems perspectives in contributing to transformative societal processes, by examining their application in an Irish case study on policy and technology. Through a qualitative exploration of the broader societal and policy context of the energy sector and a more detailed examination of the innovation systems of selected niche technologies (bioenergy and electric vehicles), the Irish case study sought to identify potential catalysts for a sustainability transition in the energy sector in Ireland: where these exist, how these are being built or enabled, and barriers to change. Following a discussion on the theoretical approaches used, a description will be given of how these were applied in the conducting of the research on transition in Ireland case study and the key findings which emerged. A critical reflection will then be made on the utility of these perspectives (as applied) to contribute to broader processes of societal transformation in Ireland.

Perfil logístico de la cadena de hidrocarburos en Colombia Parte I

El presente estudio analiza las diferentes variables que inciden en el sector petrolero para la adecuada identificación de los alcances, desventajas y oportunidades para el establecimiento de un proyecto de representación exclusiva en el mismo. Dentro de las variables a saber se destacan el transporte y la distribución, el análisis sectorial, que pasa por la cadena de producción, actividad actual y proyecciones, para llegar a la descripción de los requisitos de una adecuada cadena de suministro. Por último, se concluyen con algunas estrategias y recomendaciones que permitan el posicionamiento y éxito del proyecto, resaltando los variables tiempo y producción como las primordiales para cualquier representación exclusiva en el sector, incluso sobre el precio.

Perfil Logístico del Sector Hidrocarburos en Colombia – Parte 2

El perfil logístico del sector hidrocarburos parte de una caracterización mundial y nacional del mismo en el que se resalta la posición del país respecto a la región en cuanto a la participación en consumo y producción de petróleo, además de contar con un análisis del comportamiento de los principales indicadores como lo son los históricos del precio del barril de petróleo, producción diaria, participación en el PIB, Inversión Extranjera Directa o IED y Balanza Comercial. Luego se presentan las principales problemáticas del sector en cuanto a medio ambiente, infraestructura, conflicto armado, disminución de reservas, alternativas energéticas, etc., que presentan un obstáculo para el desarrollo y competitividad del sector. A continuación se encuentra la información asociada con la cadena de suministro de los hidrocarburos, se caracteriza el producto y se trata eslabón por eslabón comenzando por los proveedores, pasando por producción, almacenamiento, distribución, transporte clientes, logística inversa y finalizando con un mapa de agregación de valor o VSM por sus siglas en inglés. A partir de esto se analiza el estado de productividad y competitividad del sector; se dan a conocer las principales asociaciones y agremiaciones del mismo, se realiza un análisis especial a la situación de fletes y transporte. Todo con el fin de dar a conocer una fotografía del estado actual de los hidrocarburos en Colombia.

Consequences of N,C,N '- and C,N,N '-coordination modes on electronic and photophysical properties of cyclometalated aryl ruthenium(II) complexes

The effects of isoelectronic replacement of a neutral nitrogen donor atom by an anionic carbon atom in terpyridine ruthenium(II) complexes on the electronic and photophysical properties of the resulting N,C,N'- and C,N,N'-cyclometalated aryl ruthenium(II) complexes were investigated. To this end, a series of complexes was prepared either with ligands containing exclusively nitrogen donor atoms, that is, [Ru(R-1-tpy)(R-2-tpy)](2+) (R-1, R-2 = H, CO2Et), or bearing either one N,C,N'- or C,N,N'-cyclometalated ligand and one tpy ligand, that is, [Ru(R-1-(NCN)-C-Lambda-N-Lambda)(R-2-tpy)](+) and [Ru(R-1-(CNN)-N-Lambda-N-Lambda)(R-2-tpy)](+), respectively. Single-crystal X-ray structure determinations showed that cyclometalation does not significantly alter the overall geometry of the complexes but does change the bond lengths around the ruthenium(II) center, especially the nitrogen-to-ruthenium bond length trans to the carbanion. Substitution of either of the ligands with electron-withdrawing ester functionalities fine-tuned the electronic properties and resulted in the presence of an IR probe. Using trends obtained from redox potentials, emission energies, IR spectroelectrochemical responses, and the character of the lowest unoccupied molecular orbitals from DFT studies, it is shown that the first reduction process and luminescence are associated with the ester-substituted C,N,N'-cyclometalated ligand in [Ru(EtO2C-(CNN)-N-Lambda-N-Lambda)(tpy)](+). Cyclometalation in an N,C,N'-bonding motif changed the energetic order of the ruthenium d(zx), d(yz), and d(xy) orbitals. The red-shifted absorption in the N,C,N'-cyclometalated complexes is assigned to MLCT transitions to the tpy ligand. The red shift observed upon introduction of the ester moiety is associated with an increase in intensity of low-energy transitions, rather than a red shift of the main transition. Cyclometalation in the C,N,N'-binding motif also red-shifts the absorption, but the corresponding transition is associated with both ligand types. Luminescence of the cyclometalated complexes is relatively independent of the mode of cyclometalation, obeying the energy gap law within each individual series.

The role of conventional generation in managing variability

As electricity systems incorporate increasing levels of variable renewable generation, conventional plant will be required to operate more flexibly, with potential impacts for economic viability and reliability. Northern Ireland is pursuing an ambitious target of 40% of electricity to be supplied from renewable sources by 2020. The dominant source of this energy is anticipated to come from inherently variable wind power, one of the most mature renewable technologies. Conventional thermal generators will have a significant role to play in maintaining security of supply. However, running conventional generation more flexibly in order to cater for a wind led regime can reduce its efficiency, as well as shortening its lifespan and increasing O&M costs. This paper examines the impacts of variable operation on existing fossil fuel based generators, with a particular focus on Northern Ireland. Access to plant operators and industry experts has provided insight not currently evident in the energy literature. Characteristics of plant operation and the market framework are identified that present significant challenges in moving to the proposed levels of wind penetration. Opportunities for increasing flexible operation are proposed and future research needs identified.

Europium doped zinc sulfide: a correlation between experimental and theoretical calculations

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The Role of Molecular Conformation and Polarizable Embedding for One- and Two-Photon Absorption of Disperse Orange 3 in Solution

Solvent effects on the one- and two-photon absorption (IPA and 2PA) of disperse orange 3 (DO3) in dimethyl sulfoxide (DMSO) are studied using a discrete polarizable embedding (PE) response theory. The scheme comprises a quantum region containing the chromophore and an atomically granulated classical region for the solvent accounting for full interactions within and between the two regions. Either classical molecular dynamics (MD) or hybrid Car-Parrinello (CP) quantum/classical (QM/MM) molecular dynamics simulations are employed to describe the solvation of DO3 in DMSO, allowing for an analysis of the effect of the intermolecular short-range repulsion, long-range attraction, and electrostatic interactions on the conformational changes of the chromophore and also the effect of the solute-solvent polarization. PE linear response calculations are performed to verify the character, solvatochromic shift, and overlap of the two lowest energy transitions responsible for the linear absorption spectrum of DO3 in DMSO in the visible spectral region. Results of the PE linear and quadratic response calculations, performed using uncorrelated solute-solvent configurations sampled from either the classical or hybrid CP QM/MM MD simulations, are used to estimate the width of the line shape function of the two electronic lowest energy excited states, which allow a prediction of the 2PA cross-sections without the use of empirical parameters. Appropriate exchange-correlation functionals have been employed in order to describe the charge-transfer process following the electronic transitions of the chromophore in solution.

Synthesis and Redox and Photophysical Properties of Benzodifuran-Spiropyran Ensembles

Two benzodifuran (BDF)-coupled spiropyran (SP) systems and their BDF reference compounds were obtained in good yields through HuisgenMeldalSharpless click chemistry and then subjected to investigation of their electrochemical and photophysical properties. In both SP and merocyanine (MC) forms of the coupled molecules, the BDF-based emission is quenched to around 1 of the quantum yield of emission from the BDF reference compounds. Based on electrochemical data, this quenching is attributed to oxidative electron-transfer quenching. Irradiation at 366nm results in ring opening to the MC forms of the BDF-coupled SP compounds and the SP reference compound with a quantum efficiency of about 50. The rate constants for the thermal ring closing are approximately 3.4x103s1. However, in the photostationary states the MC fractions of the coupled molecules are substantially lower than that of the reference SP compound, attributed to the observed acceleration of the ring-closing reaction upon irradiation. As irradiation at 366nm invariably also excites higher-energy transitions of the BDF units in the coupled compounds, the ring-opening reaction is accelerated relative to the SP reference, which results in lower MC fractions in the photostationary state. Reversible photochromism of these BDF-coupled SP compounds renders them promising in the field of molecular switches.

Socio-technical transitions and policy change - Advocacy coalitions in Swiss energy policy

Policies and politics are an integral part of socio-technical transitions but have not received much attention in the transitions literature so far. Drawing on the advocacy coalition framework, our paper addresses this gap with a study on actors and coalitions in Swiss energy policy. Our results show that advocacy coalitions in Switzerland have largely remained stable despite the Fukushima shock. However, heterogeneity of beliefs has increased and in 2013, even a majority of actors expressed their support for the energy transition – an indication that major policy change might be ahead. It seems that in socio-technical transitions, changes in the policy issue and in the actor base also work toward policy change, next to changes in core beliefs. We make suggestions how the advocacy coalition framework can inform analysis and theory building in transition studies. We also present first ideas about the interplay of socio-technical systems and policy systems.

Energy levels and radiative rates for transitions in Cr-like Co IV and Ni V

We report calculations of energy levels and radiative rates (A-values) for transitions in Cr-like Co IV and Ni V. The quasi-relativistic Hartree-Fock (QRHF) code is adopted for calculating the data although grasp (general-purpose relativistic atomic structure package) and flexible atomic code (fac) have also been employed for comparison purposes. No radiative rates are available in the literature to compare with our results, but our calculated energies are in close agreement with those compiled by NIST for a majority of the levels. However, there are discrepancies for a few levels of up to 3%. The A-values are listed for all significantly contributing E1, E2 and M1 transitions, and the corresponding lifetimes reported, although unfortunately no previous theoretical or experimental results exist to compare with our data.

Effect of disorder on quantum phase transitions in anisotropic XY spin chains in a transverse field

We present some exact results for the effect of disorder on the critical properties of an anisotropic XY spin chain in a transverse held. The continuum limit of the corresponding fermion model is taken and in various cases results in a Dirac equation with a random mass. Exact analytic techniques can then be used to evaluate the density of states and the localization length. In the presence of disorder the ferromagnetic-paramagnetic or Ising transition of the model is in the same universality class as the random transverse field Ising model solved by Fisher using a real-space renormalization-group decimation technique (RSRGDT). If there is only randomness in the anisotropy of the magnetic exchange then the anisotropy transition (from a ferromagnet in the x direction to a ferromagnet in the y direction) is also in this universality class. However, if there is randomness in the isotropic part of the exchange or in the transverse held then in a nonzero transverse field the anisotropy transition is destroyed by the disorder. We show that in the Griffiths' phase near the Ising transition that the ground-state energy has an essential singularity. The results obtained for the dynamical critical exponent, typical correlation length, and for the temperature dependence of the specific heat near the Ising transition agree with the results of the RSRODT and numerical work. [S0163-1829(99)07125-8].

Reversible luminescence thermochromism in dipotassiumsodium tris[dicyanoargentate(I)] and the role of structural phase transitions

As a function of temperature, the layered compound K2Na[Ag(CN)213 displays dramatic variations in luminescence thermochromism with major trend changes occurring around 80 K. In order to understand these interesting optical properties, high-resolution neutron diffraction investigations were performed on a polycrystalline sample of this material in the temperature range from 1.5 to 300 K, and previous synchrotron X-ray data of Larochelle et al. (Solid State Commun. 114, 155 (2000)) were reinterpreted. The corresponding significant structural changes were found to be continuous with an anomalous increase of the monoclinic c-lattice parameter with decreasing temperature, associated with slight reorientations of two inequivalent, approximately linear N-C-Ag-C-N units. In the whole temperature range, the crystal structure is monoclinic with the space group C2/m. Based on the structural results, the major luminescence thermochromism changes around 80 K are attributed to the dominance of a back energy transfer process from low- to high-energy excitons at high temperatures. (E) 2002 Elsevier Science (USA).