Static dipole polarizability of C70 fullerene

The electronic and vibrational contributions to the static dipole polarizability of C70 fullerene are determined using the finite-field method within the density functional formalism. Large polarized Gaussian basis sets augmented with diffuse functions are used and the exchange-correlation effects are described within the Perdew-Burke-Ernzerhof generalized gradient approximation (PBE-GGA). The calculated polarizability of C70 is 103 Angstrom^3, in excellent agreement with the experimental value of 102 Angstrom^3, and is completely determined by the electronic part, vibrational contribution being negligible. The ratio of polarizabilities of C70 and C60 is 1.26. The comparison of polarizability calculated with only local terms (LDA) in the PBE functional to that obtained with PBE-GGA shows that LDA is sufficient to determine the static dipole polarizability of C70.Comment: IOP style, 1 figur

Ligand electronic fine-tuning and its repercussion on the photocatalytic activity and mechanistic pathways of the copper-photocatalysed aza-Henry reaction

A family of six structurally related heteroleptic copper(i) complexes of the form of [Cu(N^N)(P^P)]+ bearing a 2,9-dimethyl-1,10-phenanthroline diimine (N^N) ligand and a series of electronically tunable xantphos (P^P) ligands have been synthesized and their optoelectronic properties characterized. The reactivity of these complexes in the copper-photocatalyzed aza-Henry reaction of N-phenyltetrahydroisoquinoline was evaluated, while the related excited state kinetics were comprehensively studied. By subtlety changing the electron-donating properties of the P^P ligands with negligible structural differences, we could tailor the photoredox properties and relate them to the reactivity. Moreover, depending on the exited-state redox potential of the catalysts, the preferred mechanism can shift between reductive quenching, energy transfer and oxidative quenching pathways. A combined study of the structural modulation of copper(i) photocatalysts, optoelectronic properties and photocatalytic reactivity resulted in a clearer understanding of both the rational design of the photocatalyst and the complexity of competing photoinduced electron and energy transfer mechanisms. © The Royal Society of Chemistry

Opening a new window to other worlds with spectropolarimetry

A high level of diversity has already been observed among the planets of our own Solar System. As such, one expects extrasolar planets to present a wide range of distinctive features, therefore the characterisation of Earth- and super Earth-like planets is becoming of key importance in scientific research. The SEARCH (Spectropolarimetric Exoplanet AtmospheRe CHaracerisation) mission proposal of this paper represents one possible approach to realising these objectives. The mission goals of SEARCH include the detailed characterisation of a wide variety of exoplanets, ranging from terrestrial planets to gas giants. More specifically, SEARCH will determine atmospheric properties such as cloud coverage, surface pressure and atmospheric composition, and may also be capable of identifying basic surface features. To resolve a planet with a semi major axis of down to 1.4AU and 30pc distant SEARCH will have a mirror system consisting of two segments, with elliptical rim, cut out of a parabolic mirror. This will yield an effective diameter of 9 meters along one axis. A phase mask coronagraph along with an integral spectrograph will be used to overcome the contrast ratio of star to planet light. Such a mission would provide invaluable data on the diversity present in extrasolar planetary systems and much more could be learned from the similarities and differences compared to our own Solar System. This would allow our theories of planetary formation, atmospheric accretion and evolution to be tested, and our understanding of regions such as the outer limit of the Habitable Zone to be further improved.Comment: 23 pages, accepted for publication in Experimental Astronom

The DACAPO-PESO campaign: Dynamics, Aerosol, Cloud and Precipitation Observations in the Pristine Environment of the Southern Ocean: An overview

This article gives an overview of the DACAPO-PESO field experiment, which has taken place in Punta Arenas, Chile, from November 2018 to November 2021, and showcases first exciting research results that have already emerged from it.In diesem Artikel wird ein Überblick über das DACAPO-PESO Experiment gegeben, welches von November 2018 bis November 2021 in Punta Arenas, Chile, stattgefunden hat. Außerdem werden erste spannende Forschungsergebnisse vorgestellt, die bereits daraus gewonnen wurden

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Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/43582/1/11159_2005_Article_BF01450280.pd

Long-term validation of Aeolus L2B wind products at Punta Arenas, Chile, and Leipzig, Germany

Ground-based observations of horizontal winds have been performed at Leipzig (51.35∘ N, 12.43∘ E), Germany, and at Punta Arenas (53.15∘ S, 70.91∘ W), Chile, in the framework of the German initiative EVAA (Experimental Validation and Assimilation of Aeolus observations) with respect to the validation of the Mie and Rayleigh wind products of Aeolus (L2B data). In Leipzig, at the Leibniz Institute for Tropospheric Research (TROPOS), radiosondes have been launched for the Aeolus overpasses on each Friday (ascending orbit) since the middle of May 2019. In Punta Arenas, scanning Doppler cloud radar observations have been performed in the framework of the DACAPO-PESO campaign (dacapo.tropos.de) for more than 3 years from the end of 2018 until the end of 2021 and could be used to validate Aeolus measurements on its ascending and descending orbits. We present two case studies and long‐term statistics of the horizontal winds derived with the ground-based reference instruments compared to Aeolus horizontal line-of-sight (HLOS) winds. The wind products of Aeolus considered are the Mie cloudy and Rayleigh clear products. It was found that the deviation of the Aeolus HLOS winds from the ground reference is usually of Gaussian shape, which allowed the use of the median bias and the scaled median absolute deviation (MAD) for the determination of the systematic and random errors of Aeolus wind products, respectively. The case study from August 2020 with impressive atmospheric conditions at Punta Arenas shows that Aeolus is able to capture strong wind speeds of up to more than 100 m s−1. The long-term validation was performed in Punta Arenas covering the period from December 2018 to November 2021 and in Leipzig from May 2019 until September 2022. This analysis showed that the systematic error of the Aeolus wind products could be significantly lowered during the mission lifetime with the changes introduced into the processing chain (different versions are called baselines). While in the early mission phase, systematic errors of more than 2 m s−1 (absolute values) were observed for both wind types (Mie and Rayleigh), these biases could be reduced with the algorithm improvements, such as the introduction of the correction for temperature fluctuations at the main telescope of Aeolus (M1 temperature correction) with Baseline 09. Hence, since Baseline 10, a significant improvement in the Aeolus data was found, leading to a low systematic error (close to 0 m s−1) and similar values for the midlatitudinal sites in both hemispheres. The random errors for both wind products were first decreasing with an increasing baseline but later increasing again due to performance losses of the Aeolus lidar instrument. Nevertheless, no significant increase in the systematic error in the Aeolus wind products was found. Thus, one can conclude that the uncertainty introduced by the reduced atmospheric return signal received by Aeolus mostly affects the random error. Even when considering all the challenges during the mission, we can confirm the general validity of Aeolus observations during its lifetime. Therefore, this space explorer mission could demonstrate that it is possible to perform active wind observations from space with the applied technique.</p

Global hybrids from the semiclassical atom theory satisfying the local density linear response

We propose global hybrid approximations of the exchange-correlation (XC) energy functional which reproduce well the modified fourth-order gradient expansion of the exchange energy in the semiclassical limit of many-electron neutral atoms and recover the full local density approximation (LDA) linear response. These XC functionals represent the hybrid versions of the APBE functional [Phys. Rev. Lett. 106, 186406, (2011)] yet employing an additional correlation functional which uses the localization concept of the correlation energy density to improve the compatibility with the Hartree-Fock exchange as well as the coupling-constant-resolved XC potential energy. Broad energetical and structural testings, including thermochemistry and geometry, transition metal complexes, non-covalent interactions, gold clusters and small gold-molecule interfaces, as well as an analysis of the hybrid parameters, show that our construction is quite robust. In particular, our testing shows that the resulting hybrid, including 20\% of Hartree-Fock exchange and named hAPBE, performs remarkably well for a broad palette of systems and properties, being generally better than popular hybrids (PBE0 and B3LYP). Semi-empirical dispersion corrections are also provided.Comment: 12 pages, 4 figure

Chlamydiae in febrile children with respiratory tract symptoms and age-matched controls, Ghana.

Members of the javax.xml.bind.JAXBElement@d71ef36 order are obligate intracellular pathogens causing acute and chronic infectious diseases. javax.xml.bind.JAXBElement@1d3522b1 are established agents of community- and zoonotically acquired respiratory tract infections, and emerging pathogens among the javax.xml.bind.JAXBElement@378e5899 -related bacteria have been implicated in airway infections. The role of both in airway infections in Africa is underexplored. We performed a case -control study on the prevalence of javax.xml.bind.JAXBElement@12f1b6f0 and javax.xml.bind.JAXBElement@10fbf3c7 -related emerging pathogens in children with febrile respiratory tract infections in West Africa, Ghana. Using a pan- javax.xml.bind.JAXBElement@246f6bc3 broad-range real-time PCR, we detected chlamydial DNA in 11 (1.9%) of 572 hospitalized febrile children with respiratory tract symptoms and in 24 (4.3%) of 560 asymptomatic age-matched controls (p 0.03). javax.xml.bind.JAXBElement@6160b547 were found to be common among both symptomatic and healthy Ghanaian children, with javax.xml.bind.JAXBElement@7e39c9ad being the most prevalent species. javax.xml.bind.JAXBElement@31136866 were detected in two children without symptoms but not in the symptomatic group. We identified neither javax.xml.bind.JAXBElement@6e7d2cf4 nor javax.xml.bind.JAXBElement@ad366f1 but a member of a new chlamydial family that shared 90.2% sequence identity with the 16S rRNA gene of the zoonotic pathogen javax.xml.bind.JAXBElement@3a17b2a7 . In addition, we found a new javax.xml.bind.JAXBElement@10edaddb -related species that belonged to a novel family sharing 91.3% 16S rRNA sequence identity with javax.xml.bind.JAXBElement@177039be Syngnamydia venezia. The prevalence and spectrum of chlamydial species differed from previous results obtained from children of other geographic regions and our study indicates that both, javax.xml.bind.JAXBElement@605214f and javax.xml.bind.JAXBElement@18029a2 -related bacteria, are not clearly linked to clinical symptoms in Ghanaian children

Reproducibility and day time bias correction of optoelectronic leg volumetry: a prospective cohort study

Background Leg edema is a common manifestation of various underlying pathologies. Reliable measurement tools are required to quantify edema and monitor therapeutic interventions. Aim of the present work was to investigate the reproducibility of optoelectronic leg volumetry over 3 weeks' time period and to eliminate daytime related within-individual variability. Methods Optoelectronic leg volumetry was performed in 63 hairdressers (mean age 45 ± 16 years, 85.7% female) in standing position twice within a minute for each leg and repeated after 3 weeks. Both lower leg (legBD) and whole limb (limbBF) volumetry were analysed. Reproducibility was expressed as analytical and within-individual coefficients of variance (CVA, CVW), and as intra-class correlation coefficients (ICC). Results A total of 492 leg volume measurements were analysed. Both legBD and limbBF volumetry were highly reproducible with CVA of 0.5% and 0.7%, respectively. Within-individual reproducibility of legBD and limbBF volumetry over a three weeks' period was high (CVW 1.3% for both; ICC 0.99 for both). At both visits, the second measurement revealed a significantly higher volume compared to the first measurement with a mean increase of 7.3 ml ± 14.1 (0.33% ± 0.58%) for legBD and 30.1 ml ± 48.5 ml (0.52% ± 0.79%) for limbBF volume. A significant linear correlation between absolute and relative leg volume differences and the difference of exact day time of measurement between the two study visits was found (P < .001). A therefore determined time-correction formula permitted further improvement of CVW. Conclusions Leg volume changes can be reliably assessed by optoelectronic leg volumetry at a single time point and over a 3 weeks' time period. However, volumetry results are biased by orthostatic and daytime-related volume changes. The bias for day-time related volume changes can be minimized by a time-correction formula