122 research outputs found

    Optical and electron-energy-loss studies of the monomeric and dimeric phases of decamethylferrocenium tetracyanoquinodimethanide, (DMeFc)(TCNQ)

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    Journal ArticleThe optical properties of the two crystallographic phases of 1:l decaniethylferrocenium tetracyanoauinodimethanide, (DMeFc)(TCNQ), have been measured from 0.1 to 10 eV. One phase consists of isolated paramagnetic TCNQ anion monomers while the other contains isolated diamagnetic dimers. The spectrum of the monomeric phase exhibits a strong localized monomer exciton which is not normally observed in solid TCNQ salts, while the dimeric phase shows a charge-transfer excitation as well as a shifted local exciton. From the frequency- dependent conductivity of the dimeric phase the effective on-site Coulomb interaction and the transfer matrix element are measured to be 1.0 and 0.27 eV, respectively. The infrared absorption spectrum of the dimeric phase shows an unusual activity of the symmetric phonon modes due to the interaction of these modes with the radical electron, whereas in the monomeric phase only normally infrared active phonons are observed. In electron-energy-loss measurements an anomalous momentum dependence of the line shape of the monomeric exciton was observed. This result is attributed to a dielectric effect caused by the decrease in strength of local excitons with increasing momentum

    Calibrating Convective properties of Solar-like Stars in the Kepler Field of View

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    Stellar models generally use simple parametrizations to treat convection. The most widely used parametrization is the so-called "Mixing Length Theory" where the convective eddy sizes are described using a single number, \alpha, the mixing-length parameter. This is a free parameter, and the general practice is to calibrate \alpha using the known properties of the Sun and apply that to all stars. Using data from NASA's Kepler mission we show that using the solar-calibrated \alpha is not always appropriate, and that in many cases it would lead to estimates of initial helium abundances that are lower than the primordial helium abundance. Kepler data allow us to calibrate \alpha for many other stars and we show that for the sample of stars we have studied, the mixing-length parameter is generally lower than the solar value. We studied the correlation between \alpha and stellar properties, and we find that \alpha increases with metallicity. We therefore conclude that results obtained by fitting stellar models or by using population-synthesis models constructed with solar values of \alpha are likely to have large systematic errors. Our results also confirm theoretical expectations that the mixing-length parameter should vary with stellar properties.Comment: 16 pages, 4 figures, accepted for publication in ApJ

    Utilisation of an operative difficulty grading scale for laparoscopic cholecystectomy

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    Background A reliable system for grading operative difficulty of laparoscopic cholecystectomy would standardise description of findings and reporting of outcomes. The aim of this study was to validate a difficulty grading system (Nassar scale), testing its applicability and consistency in two large prospective datasets. Methods Patient and disease-related variables and 30-day outcomes were identified in two prospective cholecystectomy databases: the multi-centre prospective cohort of 8820 patients from the recent CholeS Study and the single-surgeon series containing 4089 patients. Operative data and patient outcomes were correlated with Nassar operative difficultly scale, using Kendall’s tau for dichotomous variables, or Jonckheere–Terpstra tests for continuous variables. A ROC curve analysis was performed, to quantify the predictive accuracy of the scale for each outcome, with continuous outcomes dichotomised, prior to analysis. Results A higher operative difficulty grade was consistently associated with worse outcomes for the patients in both the reference and CholeS cohorts. The median length of stay increased from 0 to 4 days, and the 30-day complication rate from 7.6 to 24.4% as the difficulty grade increased from 1 to 4/5 (both p < 0.001). In the CholeS cohort, a higher difficulty grade was found to be most strongly associated with conversion to open and 30-day mortality (AUROC = 0.903, 0.822, respectively). On multivariable analysis, the Nassar operative difficultly scale was found to be a significant independent predictor of operative duration, conversion to open surgery, 30-day complications and 30-day reintervention (all p < 0.001). Conclusion We have shown that an operative difficulty scale can standardise the description of operative findings by multiple grades of surgeons to facilitate audit, training assessment and research. It provides a tool for reporting operative findings, disease severity and technical difficulty and can be utilised in future research to reliably compare outcomes according to case mix and intra-operative difficulty
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