Molecular-orbital Studies Via Satellite-free X-ray Fluorescence: Cl-K Absorption and K–Valence-level Emission Spectra of Chlorofluoromethanes

X-ray absorption and emission measurements in the vicinity of the chlorine K edge of the three chlorofluoromethanes have been made using monochromatic synchrotron radiation as the source of excitation. By selectively tuning the incident radiation to just above the Cl 1s single-electron ionization threshold for each molecule, less complex x-ray-emission spectra are obtained. This reduction in complexity is attributed to the elimination of multielectron transitions in the Cl K shell, which commonly produce satellite features in x-ray emission. The resulting satellite-free x-ray-emission spectra exhibit peaks due only to electrons in valence molecular orbitals filling a single Cl 1s vacancy. These simplified emission spectra and the associated x-ray absorption spectra are modeled using straightforward procedures and compared with semiempirical ground-state molecular-orbital calculations. Good agreement is observed between the present experimental and theoretical results for valence-orbital energies and those obtained from ultraviolet photoemission, and between relative radiative yields determined both experimentally and theoretically in this work

Polarized X-ray-emission Studies of Methyl Chloride and the Chlorofluoromethanes

A new technique sensitive to molecular orientation and geometry, and based on measuring the polarization of x-ray emission, has been applied to the Cl-containing molecules methyl chloride (CH3Cl) and the chlorofluoromethanes (CF3Cl, CF2Cl2, and CFCl3) in the gas phase. Upon selective excitation using monochromatic synchrotron radiation in the Cl K-edge (Cl 1s) near-threshold region, polarization-selective x-ray emission studies reveal highly polarized molecular valence x-ray fluorescence for all four molecules. The degree and the orientation of the polarized emission are observed to be sensitive to the incident excitation energy near the Cl Kedge. In some cases, the polarization direction for x-ray emission reverses for small changes in incident excitation energy (a few eV). It is shown that the polarized x-ray emission technique can be used to infer, directly from experiment, symmetries of occupied and unoccupied valence molecular orbitals, an- isotropies in absorption and emission, and orientational and geometrical information. It is suggested that the x-ray polarized-fluorescence phenomenon, reported here for simple molecules, can be used as a new approach to study more complicated systems in a variety of environments

Application of the anatomical fiducials framework to a clinical dataset of patients with Parkinson’s disease

Establishing spatial correspondence between subject and template images is necessary in neuroimaging research and clinical applications such as brain mapping and stereotactic neurosurgery. Our anatomical fiducial (AFID) framework has recently been validated to serve as a quantitative measure of image registration based on salient anatomical features. In this study, we sought to apply the AFIDs protocol to the clinic, focusing on structural magnetic resonance images obtained from patients with Parkinson’s disease (PD). We confirmed AFIDs could be placed to millimetric accuracy in the PD dataset with results comparable to those in normal control subjects. We evaluated subject-to-template registration using this framework by aligning the clinical scans to standard template space using a robust open preprocessing workflow. We found that registration errors measured using AFIDs were higher than previously reported, suggesting the need for optimization of image processing pipelines for clinical grade datasets. Finally, we examined the utility of using point-to-point distances between AFIDs as a morphometric biomarker of PD, finding evidence of reduced distances between AFIDs that circumscribe regions known to be affected in PD including the substantia nigra. Overall, we provide evidence that AFIDs can be successfully applied in a clinical setting and utilized to provide localized and quantitative measures of registration error. AFIDs provide clinicians and researchers with a common, open framework for quality control and validation of spatial correspondence and the location of anatomical structures, facilitating aggregation of imaging datasets and comparisons between various neurological conditions

Tricyanidoferrates(−IV) and ruthenates(−IV) with non‐innocent cyanido ligands

Exceptionally electron-rich, nearly trigonal-planar tricyanidometalate anions [Fe(CN)(3)](7-) and [Ru(CN)(3)](7-) were stabilized in LiSr3[Fe(CN)(3)] and AE(3.5)[M(CN)(3)] (AE=Sr, Ba; M=Fe, Ru). They are the first examples of group 8 elements with the oxidation state of -IV. Microcrystalline powders were obtained by a solid-state route, single crystals from alkali metal flux. While LiSr3[Fe(CN)(3)] crystallizes in P6(3)/m, the polar space group P6(3) with three-fold cell volume for AE(3.5)[M(CN)(3)] is confirmed by second harmonic generation. X-ray diffraction, IR and Raman spectroscopy reveal longer C-N distances (124-128 pm) and much lower stretching frequencies (1484-1634 cm(-1)) than in classical cyanidometalates. Weak C-N bonds in combination with strong M-C pi-bonding is a scheme also known for carbonylmetalates. Instead of the formal notation [Fe-IV(CN-)(3)](7-), quantum chemical calculations reveal non-innocent intermediate-valent CN1.67- ligands and a closed-shell d(10) configuration for Fe, that is, Fe2-

Afforestation impact on soil temperature in regional climate model simulations over Europe

In the context of the first phase of the Coordinated Regional Climate Downscaling Experiment in the European domain (EURO-CORDEX) flagship plot study on Land Use and Climate Across Scales (LUCAS), we investigate the biophysical impact of afforestation on the seasonal cycle of soil temperature over the European continent with an ensemble of 10 regional climate models. For this purpose, each ensemble member performed two idealized land cover experiments in which Europe is covered either by forests or grasslands. The multi-model mean exhibits a reduction of the annual amplitude of soil temperature (AAST) due to afforestation over all European regions, although this is not a robust feature among the models. In the Mediterranean, the spread of simulated AAST response to afforestation is between −4 and +2 ∘C at 1 m below the ground, while in Scandinavia the inter-model spread ranges from −7 to +1 ∘C. We show that the large range in the simulated AAST response is due to the representation of the summertime climate processes and is largely explained by inter-model differences in leaf area index (LAI), surface albedo, cloud fraction and soil moisture, when all combined into a multiple linear regression. The changes in these drivers essentially determine the ratio between the increased radiative energy at surface (due to lower albedo in forests) and the increased sum of turbulent heat fluxes (due to mixing-facilitating characteristics of forests), and consequently decide the changes in soil heating with afforestation in each model. Finally, we pair FLUXNET sites to compare the simulated results with observation-based evidence of the impact of forest on soil temperature. In line with models, observations indicate a summer ground cooling in forested areas compared to open lands. The vast majority of models agree with the sign of the observed reduction in AAST, although with a large variation in the magnitude of changes. Overall, we aspire to emphasize the biophysical effects of afforestation on soil temperature profile with this study, given that changes in the seasonal cycle of soil temperature potentially perturb crucial biochemical processes. Robust knowledge on biophysical impacts of afforestation on soil conditions and its feedbacks on local and regional climate is needed in support of effective land-based climate mitigation and adaption policies

European consensus statement on essential colposcopy

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European Consensus Statement on Expert Colposcopy

Peer reviewedPublisher PD

Nonlinear Integer Programming

Research efforts of the past fifty years have led to a development of linear integer programming as a mature discipline of mathematical optimization. Such a level of maturity has not been reached when one considers nonlinear systems subject to integrality requirements for the variables. This chapter is dedicated to this topic. The primary goal is a study of a simple version of general nonlinear integer problems, where all constraints are still linear. Our focus is on the computational complexity of the problem, which varies significantly with the type of nonlinear objective function in combination with the underlying combinatorial structure. Numerous boundary cases of complexity emerge, which sometimes surprisingly lead even to polynomial time algorithms. We also cover recent successful approaches for more general classes of problems. Though no positive theoretical efficiency results are available, nor are they likely to ever be available, these seem to be the currently most successful and interesting approaches for solving practical problems. It is our belief that the study of algorithms motivated by theoretical considerations and those motivated by our desire to solve practical instances should and do inform one another. So it is with this viewpoint that we present the subject, and it is in this direction that we hope to spark further research.Comment: 57 pages. To appear in: M. J\"unger, T. Liebling, D. Naddef, G. Nemhauser, W. Pulleyblank, G. Reinelt, G. Rinaldi, and L. Wolsey (eds.), 50 Years of Integer Programming 1958--2008: The Early Years and State-of-the-Art Surveys, Springer-Verlag, 2009, ISBN 354068274