Accurate computations of the structures and binding energies of the imidazole ... benzene and pyrrole ... benzene complexes

Using explicitly-correlated coupled-cluster theory with single and double excitations, the intermolecular distances and interaction energies of the T-shaped imidazole⋯⋯benzene and pyrrole⋯⋯benzene complexes have been computed in a large augmented correlation-consistent quadruple-zeta basis set, adding also corrections for connected triple excitations and remaining basis-set-superposition errors. The results of these computations are used to assess other methods such as Møller–Plesset perturbation theory (MP2), spin-component-scaled MP2 theory, dispersion-weighted MP2 theory, interference-corrected explicitly-correlated MP2 theory, dispersion-corrected double-hybrid density-functional theory (DFT), DFT-based symmetry-adapted perturbation theory, the random-phase approximation, explicitly-correlated ring-coupled-cluster-doubles theory, and double-hybrid DFT with a correlation energy computed in the random-phase approximation.

Measurement of Higgs boson production in the diphoton decay channel in pp collisions at center-of-mass energies of 7 and 8 TeV with the ATLAS detector

A measurement of the production processes of the recently discovered Higgs boson is performed in the two-photon final state using 4.5  fb −1 of proton-proton collisions data at s √ =7  TeV and 20.3  fb −1 at s √ =8  TeV collected by the ATLAS detector at the Large Hadron Collider. The number of observed Higgs boson decays to diphotons divided by the corresponding Standard Model prediction, called the signal strength, is found to be μ=1.17±0.27 at the value of the Higgs boson mass measured by ATLAS, m H =125.4  GeV . The analysis is optimized to measure the signal strengths for individual Higgs boson production processes at this value of m H . They are found to be μ ggF =1.32±0.38 , μ VBF =0.8±0.7 , μ WH =1.0±1.6 , μ ZH =0.1 +3.7 −0.1 , and μ tt ¯ H =1.6 +2.7 −1.8 , for Higgs boson production through gluon fusion, vector-boson fusion, and in association with a W or Z boson or a top-quark pair, respectively. Compared with the previously published ATLAS analysis, the results reported here also benefit from a new energy calibration procedure for photons and the subsequent reduction of the systematic uncertainty on the diphoton mass resolution. No significant deviations from the predictions of the Standard Model are found.

Measurement of the Higgs boson mass from the H→γγ and H→ZZ ∗ →4ℓ collisions at center-of-mass energies of 7 and 8 TeV with the ATLAS detector

An improved measurement of the mass of the Higgs boson is derived from a combined fit to the reconstructed invariant mass spectra of the decay channels H→γγ and H→ZZ ∗ →4ℓ . The analysis uses the pp collision data sample recorded by the ATLAS experiment at the CERN Large Hadron Collider at center-of-mass energies of 7 TeV and 8 TeV, corresponding to an integrated luminosity of 25  fb −1 . The measured value of the Higgs boson mass is m H =125.36±0.37(stat)±0.18(syst)  GeV . This result is based on improved energy-scale calibrations for photons, electrons, and muons as well as other analysis improvements, and supersedes the previous result from ATLAS. Upper limits on the total width of the Higgs boson are derived from fits to the invariant mass spectra of the H→γγ and H→ZZ ∗ →4ℓ decay channels.

Signatures of the 2-day wave and sudden stratospheric warmings in Arctic water vapour observed by ground-based microwave radiometry

The ground-based microwave radiometer MIAWARA-C recorded the upper stratospheric and lower mesospheric water vapour distribution continuously from June 2011 to March 2013 above the Arctic station of Sodankylä, Finland (67.4° N, 26.6° E) without major interruptions and offers water vapour profiles with temporal resolution of 1 h for average conditions. The water vapour time series of MIAWARA-C shows strong periodic variations in both summer and winter related to the quasi-2-day wave. Above 0.1 hPa the amplitudes are strongest in summer. The stratospheric wintertime 2-day wave is pronounced for both winters on altitudes below 0.1 hPa and reaches a maximum amplitude of 0.8 ppmv in November 2011. Over the measurement period, the instrument monitored the changes in water vapour linked to two sudden stratospheric warmings in early 2012 and 2013. Based on the water vapour measurements, the descent rate in the vortex after the warmings is 364 m d−1 for 2012 and 315 m d−1 for 2013.

Cold Microwave-Enabled Protein Detection and Quantification.

Protein screening/detection is an essential tool in many laboratories. Owing to the relatively large time investments that are required by standard protocols, the development of methods with higher throughput while maintaining an at least comparable signal-to-noise ratio is highly beneficial in many research areas. This chapter describes how cold microwave technology can be used to enhance the rate of molecular interactions and provides protocols for dot blots, Western blots, and ELISA procedures permitting a completion of all incubation steps (blocking and antibody steps) within 24-45 min.

Atmospheric water parameters measured by a ground-based microwave radiometer and compared with the WRF model

The microwave radiometer TROWARA measures integrated water vapour (IWV) and integrated cloud liquid water (ILW) at Bern since 1994 with a time resolution of 7 s. In this study, we compare TROWARA measurements with a simulation of summer 2012 in Switzerland performed with the Weather Research and Forecasting (WRF) model. It is found that the WRF model agrees very well with TROWARA’s IWV variations with a mean bias of only 0.7 mm. The ILW distribution of the WRF model, although similar in shape to TROWARA’s distribution, overestimates the fraction of clear sky periods (83% compared to 60%).

Zeeman effect in atmospheric O₂ measured by ground-based microwave radiometry

In this work we study the Zeeman effect on stratospheric O₂ using ground-based microwave radiometer measurements. The interaction of the Earth magnetic field with the oxygen dipole leads to a splitting of O₂ energy states, which polarizes the emission spectra. A special campaign was carried out in order to measure this effect in the oxygen emission line centered at 53.07 GHz. Both a fixed and a rotating mirror were incorporated into the TEMPERA (TEMPERature RAdiometer) in order to be able to measure under different observational angles. This new configuration allowed us to change the angle between the observational path and the Earth magnetic field direction. Moreover, a high-resolution spectrometer (1 kHz) was used in order to measure for the first time the polarization state of the radiation due to the Zeeman effect in the main isotopologue of oxygen from ground-based microwave measurements. The measured spectra showed a clear polarized signature when the observational angles were changed, evidencing the Zeeman effect in the oxygen molecule. In addition, simulations carried out with the Atmospheric Radiative Transfer Simulator (ARTS) allowed us to verify the microwave measurements showing a very good agreement between model and measurements. The results suggest some interesting new aspects for research of the upper atmosphere.

GROMOS-C, a novel ground-based microwave radiometer for ozone measurement campaigns

Stratospheric ozone is of major interest as it absorbs most harmful UV radiation from the sun, allowing life on Earth. Ground-based microwave remote sensing is the only method that allows for the measurement of ozone profiles up to the mesopause, over 24 hours and under different weather conditions with high time resolution. In this paper a novel ground-based microwave radiometer is presented. It is called GROMOS-C (GRound based Ozone MOnitoring System for Campaigns), and it has been designed to measure the vertical profile of ozone distribution in the middle atmosphere by observing ozone emission spectra at a frequency of 110.836 GHz. The instrument is designed in a compact way which makes it transportable and suitable for outdoor use in campaigns, an advantageous feature that is lacking in present day ozone radiometers. It is operated through remote control. GROMOS-C is a total power radiometer which uses a pre-amplified heterodyne receiver, and a digital fast Fourier transform spectrometer for the spectral analysis. Among its main new features, the incorporation of different calibration loads stands out; this includes a noise diode and a new type of blackbody target specifically designed for this instrument, based on Peltier elements. The calibration scheme does not depend on the use of liquid nitrogen; therefore GROMOS-C can be operated at remote places with no maintenance requirements. In addition, the instrument can be switched in frequency to observe the CO line at 115 GHz. A description of the main characteristics of GROMOS-C is included in this paper, as well as the results of a first campaign at the High Altitude Research Station at Jungfraujoch (HFSJ), Switzerland. The validation is performed by comparison of the retrieved profiles against equivalent profiles from MLS (Microwave Limb Sounding) satellite data, ECMWF (European Centre for Medium-Range Weather Forecast) model data, as well as our nearby NDACC (Network for the Detection of Atmospheric Composition Change) ozone radiometer measuring at Bern.

MEMLS3&a: Microwave Emission Model of Layered Snowpacks adapted to include backscattering

The Microwave Emission Model of Layered Snowpacks (MEMLS) was originally developed for microwave emissions of snowpacks in the frequency range 5–100 GHz. It is based on six-flux theory to describe radiative transfer in snow including absorption, multiple volume scattering, radiation trapping due to internal reflection and a combination of coherent and incoherent superposition of reflections between horizontal layer interfaces. Here we introduce MEMLS3&a, an extension of MEMLS, which includes a backscatter model for active microwave remote sensing of snow. The reflectivity is decomposed into diffuse and specular components. Slight undulations of the snow surface are taken into account. The treatment of like- and cross-polarization is accomplished by an empirical splitting parameter q. MEMLS3&a (as well as MEMLS) is set up in a way that snow input parameters can be derived by objective measurement methods which avoid fitting procedures of the scattering efficiency of snow, required by several other models. For the validation of the model we have used a combination of active and passive measurements from the NoSREx (Nordic Snow Radar Experiment) campaign in Sodankylä, Finland. We find a reasonable agreement between the measurements and simulations, subject to uncertainties in hitherto unmeasured input parameters of the backscatter model. The model is written in Matlab and the code is publicly available for download through the following website: http://www.iapmw.unibe.ch/research/projects/snowtools/memls.html.

Microwave Spectroscopy and Structures of Several Substituted Acetylenes and Fluorocarbons

The structures of two substituted acetylene compounds have been characterized from their microwave rotational spectra. In the first study, two structures of 6-methyl-3-heptyne have been determined. This compound can be thought of as an ethyl group separated from an isobutyl group by a C≡C spacer. Both structures have the ethyl and isobutyl groups eclipsed, consistent with the dominant interaction determining the orientation about the acetylene axis being the weak dispersion attraction between the end groups. One structure is with the isobutyl group in a symmetric conformation and the other with the isobutyl group asymmetric. In addition, the microwave spectrum of the butane analogue 3,5-octadiyne has been observed. This compound consists of two ethyl groups separated by two C≡C spacers. The study is still in progress, but it appears that the ethyl end groups are freely rotating. Therefore, it seems that the dispersion attractions between the end groups are too weak at this longer distance of about 7 Å. The structures of several fluorocarbons have also been studied by microwave spectroscopy. The structures of perfluoropentane and perfluorohexane have been shown to be helical, like the polymer polytetrafluoroethylene (Teflon©). The structure of perfluoropropane and two conformers of 1H-heptafluoropropane have been determined to be non-helical. It is apparent that the steric and dipole repulsions between fluorine atoms that have been attributed to the helical structure of longer fluorocarbon chains are not sufficient in a three carbon chain to cause a twist in the structures.

Advanced Physical Chemistry Problems (VI), Free Energies

This is a set of P. Chem. problems posed at a slightly higher level than the normal textbook level, for students who are continuing in the study of this subject.