Optical properties and exciton transfer between N-heterocyclic carbene iridium (III) complexes for blue light-emitting diode applications from first principles

N-heterocyclic carbene (NHC) iridium (III) complexes are considered as promising candidates for blue emitters in organic light-emitting diodes. They can play the roles of the emitter as well as of electron and hole transporters in the same emission layer. We investigate optical transitions in such complexes with account of geometry and electronic structure changes upon excitation or charging and exciton transfer between the complexes from first principles. It is shown that excitation of NHC iridium complexes is accompanied by a large reorganization energy $\sim$0.7 eV and a significant loss in the oscillator strength, which should lead to low exciton diffusion. Calculations with account of spin-orbit coupling reveal a small singlet-triplet splitting $\sim$0.1 eV, whereas the oscillator strength for triplet excitations is found to be an order of magnitude smaller than for the singlet ones. The contributions of the F\"orster and Dexter mechanisms are analyzed via the explicit integration of transition densities. It is shown that for typical distances between emitter complexes in the emission layer, the contribution of the Dexter mechanism should be negligible compared to the F\"orster mechanism. On the other hand, the ideal dipole approximation, although gives the correct order of the exciton coupling, fails to reproduce the result taking into account spatial distribution of the transition density. For charged NHC complexes, we find a number of optical transitions close to the emission peak of the blue emitter with high exciton transfer rates that can be responsible for exciton-polaron quenching. The nature of these transitions is analyzed.Comment: 20 pages, 7 figure

Crossover from diffusive to strongly localized regime in two-dimensional systems

We have studied the conductance distribution function of two-dimensional disordered noninteracting systems in the crossover regime between the diffusive and the localized phases. The distribution is entirely determined by the mean conductance, g, in agreement with the strong version of the single-parameter scaling hypothesis. The distribution seems to change drastically at a critical value very close to one. For conductances larger than this critical value, the distribution is roughly Gaussian while for smaller values it resembles a log-normal distribution. The two distributions match at the critical point with an often appreciable change in behavior. This matching implies a jump in the first derivative of the distribution which does not seem to disappear as system size increases. We have also studied 1/g corrections to the skewness to quantify the deviation of the distribution from a Gaussian function in the diffusive regime.Comment: 4 pages, 4 figure

Re-entrance and entanglement in the one-dimensional Bose-Hubbard model

Re-entrance is a novel feature where the phase boundaries of a system exhibit a succession of transitions between two phases A and B, like A-B-A-B, when just one parameter is varied monotonically. This type of re-entrance is displayed by the 1D Bose Hubbard model between its Mott insulator (MI) and superfluid phase as the hopping amplitude is increased from zero. Here we analyse this counter-intuitive phenomenon directly in the thermodynamic limit by utilizing the infinite time-evolving block decimation algorithm to variationally minimize an infinite matrix product state (MPS) parameterized by a matrix size chi. Exploiting the direct restriction on the half-chain entanglement imposed by fixing chi, we determined that re-entrance in the MI lobes only emerges in this approximate when chi >= 8. This entanglement threshold is found to be coincident with the ability an infinite MPS to be simultaneously particle-number symmetric and capture the kinetic energy carried by particle-hole excitations above the MI. Focussing on the tip of the MI lobe we then applied, for the first time, a general finite-entanglement scaling analysis of the infinite order Kosterlitz-Thouless critical point located there. By analysing chi's up to a very moderate chi = 70 we obtained an estimate of the KT transition as t_KT = 0.30 +/- 0.01, demonstrating the how a finite-entanglement approach can provide not only qualitative insight but also quantitatively accurate predictions.Comment: 12 pages, 8 figure

Manifestation of ageing in the low temperature conductance of disordered insulators

We are interested in the out of equilibrium phenomena observed in the electrical conductance of disordered insulators at low temperature, which may be signatures of the electron coulomb glass state. The present work is devoted to the occurrence of ageing, a benchmark phenomenon for the glassy state. It is the fact that the dynamical properties of a glass depend on its age, i.e. on the time elapsed since it was quench-cooled. We first critically analyse previous studies on disordered insulators and question their interpretation in terms of ageing. We then present new measurements on insulating granular aluminium thin films which demonstrate that the dynamics is indeed age dependent. We also show that the results of different relaxation protocols are related by a superposition principle. The implications of our findings for the mechanism of the conductance slow relaxations are then discussed

The Cadiz Contourite Channel: Sandy contourites, bedforms and dynamic current interaction

The Cadiz Contourite Channel is the largest and most prominent contourite channel in the middle slope of the Gulf of Cadiz, and is known to channelise the southern branch of the Lower Core of Mediterranean Outflow Water (MOW) as it flows westwards from the Gibraltar Gateway. The channel lies in water depth between 650 and 1500 m, is 150 km long, 2–12 km wide, up to 120 m deep, and broadly s-shaped in plan view. It has several associated subparallel marginal channels and shorter spillover channel segments. Its geometry is controlled by the interaction of a strong bottom current with the seafloor morphology, affected by neotectonic deformation and diapiric intrusion. Bottom photographs and dredge hauls reveal a channel floor shaped by high-energy flow, in places with bare rock, boulders and gravel, and elsewhere covered with sandy contourites. The rocky substrate and derived clasts are formed of authigenic iron-rich carbonates, testifying the high degree of fluid escape from adjacent diapiric ridges and mud volcanoes. The sandy substrate shows a wide range of current-induced bedforms including small, straight-crested ripples, large sinuous sand waves and dunes (wavelength 3.5–5 m, height 0.3–0.9 m), weak surface lineation on sands, and aligned gravel stringers and deep erosive scours around large boulders. Bedform orientation indicates flows directed to the south/south-west (main channel) and west (spillover channel), which can be related to MOW bottom currents, and current velocities that vary between about 0.2 and 0.8 m s− 1, even in the same channel location. However, current vane orientation was clearly responding, at least in part, to tidal effects and periodicity in the Gulf of Cadiz at the time the photographs were taken. Maximum current velocities are achieved by a combination of barotropic and internal tides (probably generated at the continental slope) that reinforce the normal MOW flow. In addition, meteorologically-induced internal waves with periods shorter than tidal ones may exert an even greater influence on current intensity, especially when they occur at times of sudden changes of meteorological forcing. This effect further influences MOW variability. In all cases, the funnelling effect of the Cadiz Channel amplifies tidal or meteorologically-induced bottom currents

Interplay of deep-marine sedimentary processes with seafloor morphology offshore Madeira Island (Central NE-Atlantic)

The deep-water sedimentary processes and morphological features offshore Madeira Island, located in the Central-NE Atlantic have been scantly studied. The analysis of new multibeam bathymetry, echo-sounder profiles and few multichannel seismic reflection profiles allowed us to identify the main geomorphologies, geomorphic processes and their interplay. Several types of features were identified below 3800 m water depth, shaped mainly by i) the interplay between northward-flowing Antarctic Bottom Water (AABW) and turbidity currents and ii) interaction of the AABW with oceanic reliefs and the Madeira lower slope. Subordinate and localized geomorphic processes consist of tectono-magmatic, slope instability, turbidity currents and fluid migration. The distribution of the morphological features defines three regional geomorphological sectors. Sector 1 represents a deep seafloor with its abyssal hills, basement highs and seamounts inherited from Early Cretaceous seafloor spreading. Sector 2 is exclusively shaped by turbidity current flows that formed channels and associated levees. Sector 3 presents a more complex morphology dominated by widespread depositional and erosional features formed by AABW circulation, and localized mixed contourite system developed by the interplay between the AABW circulation and WNW-ESE-flowing turbidite currents. The interaction of the AABW with abyssal hills, seamounts and basement ridges leads to the formation of several types of contourites: patch drifts, double-crest mounded bodies, and elongated, mounded and separated drifts. The patch drifts formed downstream of abyssal hills defining an previously unknown field of relatively small contourites. We suggest they may be a result of localized vortexes that formed when the AABW’s flow impinges these oceanic reliefs producingthe erosional scours that bound these features. The bottom currents in the area are known to be too weak (1–2 cm s− 1) to produce the patch drifts and scours. Therefore, we suggest that these features could be relics at present, having developed when the AABW was stronger than today, as during glacial/end of glacial stages

Palaeoenvironments, relative sea-level changes and tectonic influence on the Quaternary seismic units of the Huelva continental shelf (Gulf of Cadiz, southwestern Iberian Peninsula)

A seismic stratigraphical study was conducted on the Huelva continental shelf (southwestern Iberian Peninsula) between the mouths of the Guadalquivir and Guadiana Rivers. Applying the basic concepts of seismic stratigraphy, 13 seismic units bound by erosive discontinuities have been identified. Two main kinds of seismic units can be distinguished: a) Units that internally show a wide variability of seismic configurations and sheet to lensoidal external shape, located in inner-to-middle shelf settings. These units are considered high-energy units (HEU), deposited during intervals of rising and highstand sea levels. They represent coastal deposits comprising two main depositional systems: coastal barriers in the form of shoreface deposits and landward lagoonal and tidal deposits. b) Units displaying low-angle oblique seismic configurations, with reflectors exhibiting good lateral continuity and amplitude. Their thickness increases seaward, with the largest depocentres located near the shelf-break, displaying therefore a typical wedge external shape. These units are located very frequently from middle shelf emplacements to outer shelf and upper slope settings, and are considered low-energy units (LEU). They are believed to have been formed during periods of falling sea level, representing the distal portions of coastal and deltaic bodies that have been preserved from erosion. The stacking pattern of the units shows three different tectonic settings: a central subsiding sector, bounded laterally by two tectonic highs, one of them structurally controlled (the western one) and the other conditioned by diapiric uplifting (the eastern one).Un análisis de estratigrafía sísmica se ha realizado en la plataforma continental de Huelva (suroeste de la península Ibérica) entre las desembocaduras de los ríos Guadiana y Guadalquivir. Aplicando los concep tos básicos de la estratigrafía sísmica, han sido identificadas 13 unidades sísmicas limitadas por discontinuidades erosivas. Dos tipos principales de unidades sísmicas han sido identificadas: a) Unidades que internamente muestran una gran variabilidad de facies sísmicas y forma externa de lámina o lenticular, localizadas en la plataforma interna-media. Estas unidades son consideradas de alta energía (high- energy units, HEU), depositadas durante intervalos de ascenso y alto nivel del mar. Se relacionan con depósitos costeros compuestos de dos sistemas deposicionales principales: barreras costeras formadas por depósitos de frente de playa y, hacia tierra, depósitos mareales y de laguna. b) Unidades caracterizadas por clinoformas progradacionales de bajo ángulo, con reflectores de alta amplitud y continuidad. Su espesor aumenta hacia el borde de plataforma, adquiriendo una forma típica de cuña. Estas unidades están localizadas frecuentemente desde la plataforma media hasta el talud superior y son consideradas como unidades de baja energía (low-energy units, LEU). Se interpreta que representan las porciones distales de cuerpos costeros y deltaicos que se han formado durante periodos de descenso relativo del nivel del mar, y que han sido preservadas de la erosión que sufrieron las capas más someras. El patrón de apilamiento de las unidades muestra tres emplazamientos tectónicos diferentes: un sector central subsidente limitado lateralmente por dos altos tectónicos, uno controlado estructuralmente (sector oeste) y otro condicionado por un levantamiento de origen diapírico (sector este).Instituto Español de Oceanografí

Sustainable bioethanol production combining biorefinery principles using combined raw materials from wheat undersown with clover-grass

To obtain the best possible net energy balance of the bioethanol production the biomass raw materials used need to be produced with limited use of non-renewable fossil fuels. Intercropping strategies are known to maximize growth and productivity by including more than one species in the crop stand, very often with legumes as one of the components. In the present study clover-grass is undersown in a traditional wheat crop. Thereby, it is possible to increase input of symbiotic fixation of atmospheric nitrogen into the cropping systems and reduce the need for fertilizer applications. Furthermore, when using such wheat and clover-grass mixtures as raw material, addition of urea and other fermentation nutrients produced from fossil fuels can be reduced in the whole ethanol manufacturing chain. Using second generation ethanol technology mixtures of relative proportions of wheat straw and clover-grass (15:85, 50:50, and 85:15) were pretreated by wet oxidation. The results showed that supplementing wheat straw with clover-grass had a positive effect on the ethanol yield in simultaneous saccharification and fermentation experiments, and the effect was more pronounced in inhibitory substrates. The highest ethanol yield (80% of theoretical) was obtained in the experiment with high fraction (85%) of clover-grass. In order to improve the sugar recovery of clover-grass, it should be separated into a green juice (containing free sugars, fructan, amino acids, vitamins and soluble minerals) for direct fermentation and a fibre pulp for pretreatment together with wheat straw. Based on the obtained results a decentralized biorefinery concept for production of biofuel is suggested emphasizing sustainability, localness, and recycling principle