Sub-Doppler UV spectroscopy by resonance-enhanced two-photon ionization: the structure of the benzene20,22Ne cluster

In this work it is demonstrated that mass selected multiphoton ionization is a powerful technique for high resolution spectroscopy, isotope cluster separation and investigation of the structure of van der Waals clusters. The rotationally resolved UV spectra of the benzene-20Ne and benzene-22Ne clusters are selectively measured in a natural isotopic mixture of benzene and benzene-Ne clusters in a cooled supersonic jet. The analysis of these spectra yields accurate values for the rotational constants of both species. From this data it is found that the Ne atom is located on the C6 rotational axis of the benzene ring at an average distance of 3.46 Å with a slight difference for the two isotopes. This distance decreases by 40 mÅ when benzene is electronically excited. The influence of the large amplitude van der Waals vibrations on the average bond length is discussed

High-resolution UV spectrum of the benzene—N2 van der Waals complex

The rotationally resolved spectrum of the 610 band of the S1 ← S0 electronic transition of the benzene—N2 van der Waals complex has been recorded and 119 transitions assigned. The C6H6·N2 complex, produced in a pulsed molecular beam, was detected by mass-selected two-photon two-colour ionization employing a high-resolution (ΔνUV = 100 MHz, fwhm) pulsed-amplified cw laser for the resonant intermediate excitation. The observed rotational structure is that of a rigid symmetric top with weaker additional rotational transitions most likely arising from the free internal rotation of the N2 in the plane parallel to the benzene ring. The N2 is located parallel to the benzene ring at a distance of 3.50 Å; this decreases by 45 mÅ in the excited electronic state

Back to the roots of "channel three"

Rotationally resolved fluorescence excitation and resonance enhanced multiphoton ionization (MPI) spectra of the 610130 one-photon band of benzene at the onset of ``channel three'' are reported. The fluorescence decay is monitored after rotationally selected excitation and a large variation of the nonradiative decay time (<1 to 6.8 ns) is found for the different rotational states at the vibrational excess energy of 3287 cm−1 in S1. The rotational structure of the fluorescence excitation spectrum and the MPI spectrum measured with delayed laser pulses differ considerably. All observed lines of the MPI spectrum were assigned and the rotational line structure can only be understood with a model which incorporates interference between different decay channels. Due to this interference, particular rotational states decay fairly slowly and give rise to lines in the spectrum while states with neighboring rotational quantum numbers decay rapidly and are therefore not found in the spectrum. The previously reported drastic increase of the electronic, nonradiative decay of benzene in this region of excess energy, which led to the postulation of ``channel three,'' cannot be confirmed. Instead, the optically excited rovibronic states are thought to be coupled to background states within S1 which are themselves broadened due to strong coupling to the highly excited S0 electronic state rather than due to an unknown (``channel three'') or isomerization process. The Journal of Chemical Physics is copyrighted by The American Institute of Physics

Van der Waals bond lengths and electronic spectral shifts of the benzene---Kr and benzene---Xe complexes

Rotationally resolved UV-spectra are presented for the 610 bands of benzene---Kr and benzene---Xe complexes yielding precise rotational constants and van der Waals bond lengths for the ground and excited vibronic state, and electronic band shifts. These value complement the previously published data for the other rare gases and the various quantities have now been determined for all the benzene—rare gas complexes. Measured values of the bond length were used to calculate the band shifts from recent theoretical predictions. They are compared with the experimental values of this work

Changes in trabecular bone, hematopoiesis and bone marrow vessels in aplastic anemia, primary osteoporosis, and old age

Retrospective histologic analyses of bone biopsies and of post mortem samples from normal persons of different age groups, and of bone biopsies of age- and sex-matched groups of patients with primary osteoporosis and aplastic anemia show characteristic age dependent as well as pathologic changes including atrophy of osseous trabeculae and of hematopoiesis, and changes in the sinusoidal and arterial capillary compartments. These results indicate the possible role of a microvascular defect in the pathogenesis of osteoporosis and aplastic anemia

Evolution of the complex refractive index in the UV spectral region in ageing secondary organic aerosol

The chemical and physical properties of secondary organic aerosol (SOA) formed by the photochemical degradation of biogenic and anthropogenic volatile organic compounds (VOC) are as yet still poorly constrained. The evolution of the complex refractive index (RI) of SOA, formed from purely biogenic VOC and mixtures of biogenic and anthropogenic VOC, was studied over a diurnal cycle in the SAPHIR photochemical outdoor chamber in Jülich, Germany. The correlation of RI with SOA chemical and physical properties such as oxidation level and volatility was examined. The RI was retrieved by a newly developed broadband cavity-enhanced spectrometer for aerosol optical extinction measurements in the UV spectral region (360 to 420 nm). Chemical composition and volatility of the particles were monitored by a high-resolution time-of-flight aerosol mass spectrometer, and a volatility tandem differential mobility analyzer. SOA was formed by ozonolysis of either (i) a mixture of biogenic VOC (α-pinene and limonene), (ii) biogenic VOC mixture with subsequent addition of an anthropogenic VOC (<i>p</i>-xylene-d₁₀), or (iii) a mixture of biogenic and anthropogenic VOC. The SOA aged by ozone/OH reactions up to 29.5 h was found to be non-absorbing in all cases. The SOA with <i>p</i>-xylene-d₁₀ showed an increase of the scattering component of the RI correlated with an increase of the O / C ratio and with an increase in the SOA density. There was a greater increase in the scattering component of the RI when the SOA was produced from the mixture of biogenic VOCs and anthropogenic VOC than from the sequential addition of the VOCs after approximately the same ageing time. The increase of the scattering component was inversely correlated with the SOA volatility. Two RI retrievals determined for the pure biogenic SOA showed a constant RI for up to 5 h of ageing. Mass spectral characterization shows the three types of the SOA formed in this study have a significant amount of semivolatile components. The influence of anthropogenic VOCs on the oxygenated organic aerosol as well as the atmospheric implications are discussed

Cloud condensation nuclei activity, droplet growth kinetics, and hygroscopicity of biogenic and anthropogenic secondary organic aerosol (SOA)

© 2016 Author(s).Interaction of biogenic volatile organic compounds (VOCs) with Anthropogenic VOC (AVOC) affects the physicochemical properties of secondary organic aerosol (SOA). We investigated cloud droplet activation (CCN activity), droplet growth kinetics, and hygroscopicity of mixed anthropogenic and biogenic SOA (ABSOA) compared to pure biogenic SOA (BSOA) and pure anthropogenic SOA (ASOA). Selected monoterpenes and aromatics were used as representative precursors of BSOA and ASOA, respectively. We found that BSOA, ASOA, and ABSOA had similar CCN activity despite the higher oxygen to carbon ratio (O/C) of ASOA compared to BSOA and ABSOA. For individual reaction systems, CCN activity increased with the degree of oxidation. Yet, when considering all different types of SOA together, the hygroscopicity parameter, κ$_CCN$, did not correlate with O/C. Droplet growth kinetics of BSOA, ASOA, and ABSOA were comparable to that of (NH$_4$)$_2$SO$_4$, which indicates that there was no delay in the water uptake for these SOA in supersaturated conditions. In contrast to CCN activity, the hygroscopicity parameter from a hygroscopic tandem differential mobility analyzer (HTDMA) measurement, κ$_HTDMA$, of ASOA was distinctively higher (0.09-0.10) than that of BSOA (0.03-0.06), which was attributed to the higher degree of oxidation of ASOA. The ASOA components in mixed ABSOA enhanced aerosol hygroscopicity. Changing the ASOA fraction by adding biogenic VOC (BVOC) to ASOA or vice versa (AVOC to BSOA) changed the hygroscopicity of aerosol, in line with the change in the degree of oxidation of aerosol. However, the hygroscopicity of ABSOA cannot be described by a simple linear combination of pure BSOA and ASOA systems. This indicates that additional processes, possibly oligomerization, affected the hygroscopicity. Closure analysis of CCN and HTDMA data showed κ$_HTDMA$ was lower than κ$_CCN$ by 30-70 %. Better closure was achieved for ASOA compared to BSOA. This discrepancy can be attributed to several reasons. ASOA seemed to have higher solubility in subsaturated conditions and/or higher surface tension at the activation point than that of BSOA.EUROCHAMP2 European Commission 7th framework, NordForsk, VILLUM Foundatio

Measurement of the tt¯tt¯ production cross section in pp collisions at √s=13 TeV with the ATLAS detector

A measurement of four-top-quark production using proton-proton collision data at a centre-of-mass energy of 13 TeV collected by the ATLAS detector at the Large Hadron Collider corresponding to an integrated luminosity of 139 fb−1 is presented. Events are selected if they contain a single lepton (electron or muon) or an opposite-sign lepton pair, in association with multiple jets. The events are categorised according to the number of jets and how likely these are to contain b-hadrons. A multivariate technique is then used to discriminate between signal and background events. The measured four-top-quark production cross section is found to be 26+17−15 fb, with a corresponding observed (expected) significance of 1.9 (1.0) standard deviations over the background-only hypothesis. The result is combined with the previous measurement performed by the ATLAS Collaboration in the multilepton final state. The combined four-top-quark production cross section is measured to be 24+7−6 fb, with a corresponding observed (expected) signal significance of 4.7 (2.6) standard deviations over the background-only predictions. It is consistent within 2.0 standard deviations with the Standard Model expectation of 12.0 ± 2.4 fb

Measurement and interpretation of same-sign W boson pair production in association with two jets in pp collisions at s = 13 TeV with the ATLAS detector

This paper presents the measurement of fducial and diferential cross sections for both the inclusive and electroweak production of a same-sign W-boson pair in association with two jets (W±W±jj) using 139 fb−1 of proton-proton collision data recorded at a centre-of-mass energy of √s = 13 TeV by the ATLAS detector at the Large Hadron Collider. The analysis is performed by selecting two same-charge leptons, electron or muon, and at least two jets with large invariant mass and a large rapidity diference. The measured fducial cross sections for electroweak and inclusive W±W±jj production are 2.92 ± 0.22 (stat.) ± 0.19 (syst.)fb and 3.38±0.22 (stat.)±0.19 (syst.)fb, respectively, in agreement with Standard Model predictions. The measurements are used to constrain anomalous quartic gauge couplings by extracting 95% confdence level intervals on dimension-8 operators. A search for doubly charged Higgs bosons H±± that are produced in vector-boson fusion processes and decay into a same-sign W boson pair is performed. The largest deviation from the Standard Model occurs for an H±± mass near 450 GeV, with a global signifcance of 2.5 standard deviations