Detecting ultrafast interatomic electronic processes in media by fluorescence

Interatomic coulombic decay (ICD), a radiationless transition in weakly bonded systems, such as solutes or van der Waals bound aggregates, is an effective source for electrons of low kinetic energy. So far, the ICD processes could only be probed in ultra-high vacuum by using electron and/or ion spectroscopy. Here we show that resonant ICD processes can also be detected by measuring the subsequently emitted characteristic fluorescence radiation, which makes their study in dense media possible.

Estimation of electronic coupling in π -stacked donor-bridge-acceptor systems: correction of the two-state model

Comparison of donor-acceptor electronic couplings calculated within two-state and three-state models suggests that the two-state treatment can provide unreliable estimates of Vda because of neglecting the multistate effects. We show that in most cases accurate values of the electronic coupling in a π stack, where donor and acceptor are separated by a bridging unit, can be obtained as Ṽ da = (E2 - E1) μ12 Rda + (2 E3 - E1 - E2) 2 μ13 μ23 Rda2, where E1, E2, and E3 are adiabatic energies of the ground, charge-transfer, and bridge states, respectively, μij is the transition dipole moments between the states i and j, and Rda is the distance between the planes of donor and acceptor. In this expression based on the generalized Mulliken-Hush approach, the first term corresponds to the coupling derived within a two-state model, whereas the second term is the superexchange correction accounting for the bridge effect. The formula is extended to bridges consisting of several subunits. The influence of the donor-acceptor energy mismatch on the excess charge distribution, adiabatic dipole and transition moments, and electronic couplings is examined. A diagnostic is developed to determine whether the two-state approach can be applied. Based on numerical results, we showed that the superexchange correction considerably improves estimates of the donor-acceptor coupling derived within a two-state approach. In most cases when the two-state scheme fails, the formula gives reliable results which are in good agreement (within 5%) with the data of the three-state generalized Mulliken-Hush model

Portugal and air transport in the early 21st century

The Nature of air transport 1. Air transport is important • It is a big industry • It is vital to many industries and regions 2. It is multi-facited • Airlines • Airports • Air traffic control • Domestic and international 3. It is a network Industry • Portugal is part of Europe (legal fact) • Portugal is part of the world (globalization) 4. It is not wanted for its own sake • It “facilitates” and does not create 5. It has environmental implications • Noise • Greenhouse gas emissions

Stratosphere-troposphere transport in a numerical simulation of midlatitude convection

The transport of stratospheric air deep into the troposphere via convection is investigated numerically using the UK Met Office Unified Model. A convective system that formed on 27 June 2004 near southeast England, in the vicinity an upper level potential vorticity anomaly and a lowered tropopause, provides the basis for analysis. Transport is diagnosed using a stratospheric tracer that can either be passed through or withheld from the model’s convective parameterization scheme. Three simulations are performed at increasingly finer resolutions, with horizontal grid lengths of 12, 4, and 1 km. In the 12 and 4 km simulations, tracer is transported deeply into the troposphere by the parameterized convection. In the 1 km simulation, for which the convective parameterization is disengaged, deep transport is still accomplished but with a much smaller magnitude. However, the 1 km simulation resolves stirring along the tropopause that does not exist in the coarser simulations. In all three simulations, the concentration of the deeply transported tracer is small, three orders of magnitude less than that of the shallow transport near the tropopause, most likely because of the efficient dilution of parcels in the lower troposphere.

Nitrate transport in Chalk catchments: monitoring, modelling and policy implications

Rising nitrate levels have been observed in UK Chalk catchments in recent decades, with concentrations now approaching or exceeding legislated maximum values in many areas. In response, strategies seeking to contain concentrations through appropriate land management are now in place. However, there is an increasing consensus that Chalk systems, a predominant landscape type over England and indeed northwest Europe, can retard decades of prior nitrate loading within their deep unsaturated zones. Current levels may not fully reflect the long-term impact of present-day practices, and stringent land management controls may not be enough to avert further medium-term rises. This paper discusses these issues in the context of the EU Water Framework Directive, drawing on data from recent experimental work and a new model (INCA-Chalk) that allows the impacts of different land use management practices to be explored. Results strongly imply that timelines for water quality improvement demanded by the Water Framework directive are not realistic for the Chalk, and give an indication of time-scales over which improvements might be achieved. However, important unresolved scientific issues remain, and further monitoring and targeted data collection is recommended to reduce prediction uncertainties and allow cost effective strategies for mitigation to be designed and implemented. (C) 2007 Elsevier Ltd. All rights reserved.

Catchment-scale modelling of flow and nutrient transport in the Chalk unsaturated zone

The unsaturated zone exerts a major control on the delivery of nutrients to Chalk streams, yet flow and transport processes in this complex, dual-porosity medium have remained controversial. A major challenge arises in characterising these processes, both at the detailed mechanistic level and at an appropriate level for inclusion within catchment-scale models for nutrient management. The lowland catchment research (LOCAR) programme in the UK has provided a unique set of comprehensively instrumented groundwater-dominated catchments. Of these, the Pang and Lambourn, tributaries of the Thames near Reading, have been a particular focus for research into subsurface processes and surface water-groundwater interactions. Data from LOCAR and other sources, along with a new dual permeability numerical model of the Chalk, have been used to explore the relative roles of matrix and fracture flow within the unsaturated zone and resolve conflicting hypotheses of response. From the improved understanding gained through these explorations, a parsimonious conceptualisation of the general response of flow and transport within the Chalk unsaturated zone was formulated. This paper summarises the modelling and data findings of these explorations, and describes the integration of the new simplified unsaturated zone representation with a catchment-scale model of nutrients (INCA), resulting in a new model for catchment-scale flow and transport within Chalk systems: INCA-Chalk. This model is applied to the Lambourn, and results, including hindcast and forecast simulations, are presented. These clearly illustrate the decadal time-scales that need to be considered in the context of nutrient management and the EU Water Framework Directive. (C) 2007 Elsevier B.V. All rights reserved.

Identification of stimulatory and inhibitory inputs to the hypothalamic-pituitary-adrenal axis during hypoglycaemia or transport in ewes

This study used the novel approach of statistical modelling to investigate the control of hypothalamic-pituitary-adrenal (HPA) axis and quantify temporal relationships between hormones. Two experimental paradigms were chosen, insulin-induced hypoglycaemia and 2 h transport, to assess differences in control between noncognitive and cognitive stimuli. Vasopressin and corticotropin-releasing hormone (CRH) were measured in hypophysial portal plasma, and adrenocorticotropin hormone (ACTH) and cortisol in jugular plasma of conscious sheep, and deconvolution analysis was used to calculate secretory rates, before modelling. During hypoglycaemia, the relationship between plasma glucose and vasopressin or CRH was best described by log(10) transforming variables (i.e. a positive power-curve relationship). A negative-feedback relationship with log(10) cortisol concentration 2 h previously was detected. Analysis of the 'transport' stimulus suggested that the strength of the perceived stimulus decreased over time after accounting for cortisol facilitation and negative-feedback. The time course of vasopressin and CRH responses to each stimulus were different However, at the pituitary level, the data suggested that log(10) ACTH secretion rate was related to log(10) vasopressin and CRH concentrations with very similar regression coefficients and an identical ratio of actions (2.3 : 1) for both stimuli. Similar magnitude negative-feedback effects of log(10) cortisol at -110 min (hypoglycaemia) or -40 min (transport) were detected, and both models contained a stimulatory relationship with cortisol at 0 min (facilitation). At adrenal gland level, cortisol secretory rates were related to simultaneously measured untransformed ACTH concentration but the regression coefficient for the hypoglycaemia model was 2.5-fold greater than for transport. No individual sustained maximum cortisol secretion for longer than 20 min during hypoglycaemia and 40 min during transport. These unique models demonstrate that corticosteroid negative-feedback is a significant control mechanism at both the pituitary and hypothalamus. The amplitude of HPA response may be related to stimulus intensity and corticosteroid negative-feedback, while duration depended on feedback alone.

Condensation and moisture transport in cold roofs: effect of roof underlay

Cold pitched roofs, with their form of construction situating insulation on a horizontal ceiling, are intrinsically vulnerable to condensation. This study reports the results derived from using a simulation package (Heat, Air and Moisture modelling tool, or HAM-Tools) to investigate the risk of condensation in cold pitched roofs in housing fitted with a vapour-permeable underlay (VPU) of known characteristics. In order to visualize the effect of the VPUs on moisture transfer, several scenarios were modelled, and compared with the results from a conventional bituminous felt with high resistance (200 MNs/g, Sd = 40 m). The results indicate that ventilation is essential in the roof to reduce condensation. However, a sensitivity analysis proved that reducing the overall tightness of the ceiling and using lower-resistance VPUs would help in controlling condensation formation in the roof. To a large extent, the proposed characteristic performance of the VPU as predicted by manufacturers and some researchers may only be realistic if gaps in the ceiling are sealed completely during construction, which may be practically difficult given current construction practice.

Modeling of carrier transport in nanowires

We consider a physical model of ultrafast evolution of an initial electron distribution in a quantum wire. The electron evolution is described by a quantum-kinetic equation accounting for the interaction with phonons. A Monte Carlo approach has been developed for solving the equation. The corresponding Monte Carlo algorithm is NP-hard problem concerning the evolution time. To obtain solutions for long evolution times with small stochastic error we combine both variance reduction techniques and distributed computations. Grid technologies are implemented due to the large computational efforts imposed by the quantum character of the model.

Modelling sediment supply and transport in the River Lugg: strategies for controlling sediment loads

The River Lugg has particular problems with high sediment loads that have resulted in detrimental impacts on ecology and fisheries. A new dynamic, process-based model of hydrology and sediments (INCA- SED) has been developed and applied to the River Lugg system using an extensive data set from 1995–2008. The model simulates sediment sources and sinks throughout the catchment and gives a good representation of the sediment response at 22 reaches along the River Lugg. A key question considered in using the model is the management of sediment sources so that concentrations and bed loads can be reduced in the river system. Altogether, five sediment management scenarios were selected for testing on the River Lugg, including land use change, contour tillage, hedging and buffer strips. Running the model with parameters altered to simulate these five scenarios produced some interesting results. All scenarios achieved some reduction in sediment levels, with the 40% land use change achieving the best result with a 19% reduction. The other scenarios also achieved significant reductions of between 7% and 9%. Buffer strips produce the best result at close to 9%. The results suggest that if hedge introduction, contour tillage and buffer strips were all applied, sediment reductions would total 24%, considerably improving the current sediment situation. We present a novel cost-effectiveness analysis of our results where we use percentage of land removed from production as our cost function. Given the minimal loss of land associated with contour tillage, hedges and buffer strips, we suggest that these management practices are the most cost-effective combination to reduce sediment loads.

Transport in the low-latitude tropopause zone diagnosed using particle trajectories

Recent literature has described a “transition zone” between the average top of deep convection in the Tropics and the stratosphere. Here transport across this zone is investigated using an offline trajectory model. Particles were advected by the resolved winds from the European Centre for Medium-Range Weather Forecasts reanalyses. For each boreal winter clusters of particles were released in the upper troposphere over the four main regions of tropical deep convection (Indonesia, central Pacific, South America, and Africa). Most particles remain in the troposphere, descending on average for every cluster. The horizontal components of 5-day trajectories are strongly influenced by the El Niño–Southern Oscillation (ENSO), but the Lagrangian average descent does not have a clear ENSO signature. Tropopause crossing locations are first identified by recording events when trajectories from the same release regions cross the World Meteorological Organization lapse rate tropopause. Most crossing events occur 5–15 days after release, and 30-day trajectories are sufficiently long to estimate crossing number densities. In a further two experiments slight excursions across the lapse rate tropopause are differentiated from the drift deeper into the stratosphere by defining the “tropopause zone” as a layer bounded by the average potential temperature of the lapse rate tropopause and the profile temperature minimum. Transport upward across this zone is studied using forward trajectories released from the lower bound and back trajectories arriving at the upper bound. Histograms of particle potential temperature (θ) show marked differences between the transition zone, where there is a slow spread in θ values about a peak that shifts slowly upward, and the troposphere below 350 K. There forward trajectories experience slow radiative cooling interspersed with bursts of convective heating resulting in a well-mixed distribution. In contrast θ histograms for back trajectories arriving in the stratosphere have two distinct peaks just above 300 and 350 K, indicating the sharp change from rapid convective heating in the well-mixed troposphere to slow ascent in the transition zone. Although trajectories slowly cross the tropopause zone throughout the Tropics, all three experiments show that most trajectories reaching the stratosphere from the lower troposphere within 30 days do so over the west Pacific warm pool. This preferred location moves about 30°–50° farther east in an El Niño year (1982/83) and about 30° farther west in a La Niña year (1988/89). These results could have important implications for upper-troposphere–lower-stratosphere pollution and chemistry studies.