On the Electronic Spectroscopy of Closed Shell Cations Derived From Resonance Stabilized Radicals: Insights From Theory and Franck-Condon Analysis

Context. Recent attention has been directed on closed-shell aromatic cations as potential carriers of the diffuse interstellar bands. The spectra of mass-selected, matrix-isolated benzylium, and tropylium cations were recently reported. The visible spectrum of benzylium exhibits a large Franck-Condon (FC) envelope, inconsistent with diffuse interstellar band carriers. Aims. We perform a computational analysis of the experimentally studied benzylium spectrum before extending the methods to a range of larger, closed-shell aromatic cations to determine the potential for this class of systems as diffuse interstellar band carriers. Methods. Density functional theory (DFT), time-dependant ((TD)DFT), and multi-configurational self-consistent field second-order perturbation theory (MRPT2) methods in concert with multidimensional FC analysis is used to model the benzylium spectrum. These methods are extended to larger closed-shell aromatic hydrocarbon cations derived from resonance-stabilized radicals, which are predicted to show strong S0 → Sn transitions in the visible region. The ionization energies of a range of these systems are also calculated by DFT. Results. The simulated benzylium spectrum was found to yield excellent agreement with the experimental spectrum showing an extended progression in a low frequency (510 cm-1) ring distortion mode. The FC progression was found to be significantly quenched in the larger species: 1-indanylium, 1-naphthylmethylium, and fluorenium. Excitation and ionization energies of the closed-shell cations were found to be consistent with diffuse interstellar band carriers, with the former lying in the visible range and the latter straddling the Lyman limit in the 13−14 eV range. Conclusions. Large closed-shell polycyclic aromatic hydrocarbon cations remain viable candidate carriers of the diffuse interstellar bands

Remote sensing of intertidal morphological change in Morecambe Bay, U.K., between 1991 and 2007

Tidal Flats are important examples of extensive areas of natural environment that remain relatively unaffected by man. Monitoring of tidal flats is required for a variety of purposes. Remote sensing has become an established technique for the measurement of topography over tidal flats. A further requirement is to measure topographic changes in order to measure sediment budgets. To date there have been few attempts to make quantitative estimates of morphological change over tidal flat areas. This paper illustrates the use of remote sensing to measure quantitative and qualitative changes in the tidal flats of Morecambe Bay during the relatively long period 1991–2007. An understanding of the patterns of sediment transport within the Bay is of considerable interest for coastal management and defence purposes. Tidal asymmetry is considered to be the dominant cause of morphological change in the Bay, with the higher currents associated with the flood tide being the main agency moulding the channel system. Quantitative changes were measured by comparing a Digital Elevation Model (DEM) of the intertidal zone formed using the waterline technique applied to satellite Synthetic Aperture Radar (SAR) images from 1991–1994, to a second DEM constructed from airborne laser altimetry data acquired in 2005. Qualitative changes were studied using additional SAR images acquired since 2003. A significant movement of sediment from below Mean Sea Level (MSL) to above MSL was detected by comparing the two Digital Elevation Models, though the proportion of this change that could be ascribed to seasonal effects was not clear. Between 1991 and 2004 there was a migration of the Ulverston channel of the river Leven north-east by about 5 km, followed by the development of a straighter channel to the west, leaving the previous channel decoupled from the river. This is thought to be due to independent tidal and fluvial forcing mechanisms acting on the channel. The results demonstrate the effectiveness of remote sensing for measurement of long-term morphological change in tidal flat areas. An alternative use of waterlines as partial bathymetry for assimilation into a morphodynamic model of the coastal zone is also discussed

Gestational diabetes mellitus- right person, right treatment, right time?

Background: Personalised treatment that is uniquely tailored to an individual’s phenotype has become a key goal of clinical and pharmaceutical development across many, particularly chronic, diseases. For type 2 diabetes, the importance of the underlying clinical heterogeneity of the condition is emphasised and a range of treatments are now available, with personalised approaches being developed. While a close connection between risk factors for type 2 diabetes and gestational diabetes has long been acknowledged, stratification of screening, treatment and obstetric intervention remains in its infancy. Conclusions: Although there have been major advances in our understanding of glucose tolerance in pregnancy and of the benefits of treatment of gestational diabetes, we argue that far more vigorous approaches are needed to enable development of companion diagnostics, and to ensure the efficacious and safe use of novel therapeutic agents and strategies to improve outcomes in this common condition

Scaling Law for the Cosmological Constant from Quantum Cosmology with Seven Extra Dimensions

According to a model of quantum cosmology the maximum number of degrees of freedom allowed in our three dimensions was determined by the size of seven extra dimensions in an initial excited state before inflation. The size of the extra dimensions can be inferred from a simple scheme for unifying the strong force and gravity. Coupled with the Bekenstein-Hawking entropy bound, these considerations lead to a scaling law for the cosmological constant that has been proposed independently by several authors.Comment: matches published version in IJT

Moduli Stabilization with the String Higgs Effect

We review the notion of the Higgs effect in the context of string theory. We find that by including this effect in time dependent backgrounds, one is led to a natural mechanism for stabilizing moduli at points of enhanced gauge symmetry. We consider this mechanism for the case of the radion (size of the extra dimensions) and find that as decompactification of the large spatial dimensions takes place the radion will remain stabilized at the self dual radius. We discuss how this mechanism can be incorporated into models of string cosmology and brane inflation to resolve some outstanding problems. We also address some issues regarding which string states should be included when constructing low energy actions in string cosmology.Comment: 20 pages, references added, typos correcte

Calculating the transfer function of noise removal by principal component analysis and application to AzTEC observations

Instruments using arrays of many bolometers have become increasingly common in the past decade. The maps produced by such instruments typically include the filtering effects of the instrument as well as those from subsequent steps performed in the reduction of the data. Therefore interpretation of the maps is dependent upon accurately calculating the transfer function of the chosen reduction technique on the signal of interest. Many of these instruments use non-linear and iterative techniques to reduce their data because such methods can offer improved signal-to-noise over those that are purely linear, particularly for signals at scales comparable to that subtended by the array. We discuss a general approach for measuring the transfer function of principal component analysis (PCA) on point sources that are small compared to the spatial extent seen by any single bolometer within the array. The results are applied to previously released AzTEC catalogues of the COSMOS, Lockman Hole, Subaru XMM-Newton Deep Field, GOODS-North and GOODS-South fields. Source flux density and noise estimates increase by roughly +10 per cent for fields observed while AzTEC was installed at the Atacama Submillimeter Telescope Experiment and +15-25 per cent while AzTEC was installed at the James Clerk Maxwell Telescope. Detection significance is, on average, unaffected by the revised technique. The revised photometry technique will be used in subsequent AzTEC releases.Comment: 14 pages, 4 figure